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CA2220439A1 - Medium modulus molded material comprising substantially linear polyethylene and fabrication method - Google Patents

Medium modulus molded material comprising substantially linear polyethylene and fabrication method

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Publication number
CA2220439A1
CA2220439A1 CA 2220439 CA2220439A CA2220439A1 CA 2220439 A1 CA2220439 A1 CA 2220439A1 CA 2220439 CA2220439 CA 2220439 CA 2220439 A CA2220439 A CA 2220439A CA 2220439 A1 CA2220439 A1 CA 2220439A1
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CA
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Patent type
Prior art keywords
ethylene
linear
polymer
weight
density
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2220439
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French (fr)
Inventor
Jeffrey J. Wooster
Dun Jozef J. I. Van
Theo L. V. Geussens
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Dow Global Technologies LLC
Original Assignee
Dow Belgium N.V.
Jeffrey J. Wooster
Dun Jozef J. I. Van
The Dow Chemical Company
Theo L. V. Geussens
Dow Global Technologies Inc.
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins

Abstract

Medium modulus molded polyethylene materials with improved impact strength are made. The polyethylene material is molded to pipes, bars and sheets. The molded material comprises high molecular weight linear polyethylene and a substantially linear ethylene/.alpha.-olefin interpolymer. The material is more than about 0.23 mm thick, has a density in the range of 0.923 to 0.95 grams/cubic centimeter (g/cc) and has an excellent impact resistance.

Description

W 096/35750 PCTrUS95/07643 MEDIUM MODLILUS MOLDED l\/IATERIAL COMPRISING SU85TANTIALLY LINEAR
POLYETHYLErlE AND FABRICATION METHOD

This application is related tothe pending application entitled "Medium Modulus 5 Film and Fabrication Method" filed herewith on May 9,1994, in the names of Brad A. Cobler, Larry D. Cady, Lisa E. Dodson and Osborne K. McKinney, to pending application serial number 081054,379 filed 4/28/93 in the names of Pak-Wing S. Chum, Ronald P. Markovich, George W.
Knight and Shih-Yaw Lai, and a continuation-in-part of co-pending application, serial number 08/239,496 filed on May 9,1994, in the names of Jeffrey J. Wooster, Bard A. Cobler, Larry D.
10 Cady, David G. Bertelsmcln, Lisa E. Dodson and Osborne K. McKinney.
This inventlon pertainsto ,a medium modulus molded polyethylene material and a method for preparing such material. 1 he novel molded material can be prepared by extrusion, compression molding or casting processes. The polyethylene material can be molded to articles, such as pipes, tubes, bars, wi re coatings, sheets or molded parts, such as automotive parts and hollow articles, such as containers. The molded material has surprisingly high impact properties.
Molded polyethyiene materials find wide usage, for example in gas pipe or water pipe applications. Such n1aterials must have a sufficient stiffness to provide long-term dimensional stability. Ful thermore, they must have a high impact strength to minimize failures 20 during usage. Advantageously, the materials should also be resistantto crack propagation, that means that an acciclental crack or failure should stop and not run over extended length of the material.
It is known to blend polyethylene with various polymers to improve its impact properties. E. Ceaucescu et al. (Revue Roumaine de Chimie,34,3, 711-724 (1989)) disclose that 25 the shock resistance of a high density polyethylene (HDPE) can be improved by incorporatmg a butad iene-styrene block copolymer therein. J. Rhee and B. Crist (Journal of Polymer Science:
PartB: PolymerPhysics,'~ol 32,159-169(1994))discusstheplainstrainfracturetoughnessof blends of HDPE and hydrogenated polybutadiene. W.S. Smith (Soc. Plast. Eng., Tech. Pap.
(1975),21, pages 394-396 describe the us,e of ethylene-propylene rubberfor improving the 30 impact ~L- e?nyLh and/or environmental stress crack resistance of polypropylene. Alternatively, the ethylene-propylene rulbber may be blended with low density polyethylene or high density polyethylene.
Matsuura et al., U.S. Patent 4,330,639 disclose a polymer composition to form polyethylene films which are said to have a high impact strength and a high tear strength. The 35 polymer composition corn prises an ethylene/C3-C8 a-olefin copolymer having an intrinsic viscosity of 1.3 to 8.3 dl/g and a density of 0.850 to 0.930 and an ethylene polymer having a melt index of 0.01 to 0.2, a flow parameter of 1.9 to 2.8 and a density not lower than 0.940.

W 096135750 PCTnUS95/07643 Bai ley et al . (U .S. Patent 4,461,873) disclose ethylene polymer mixtures havi ng a density in the range of 0.940 to 0.965 g/cc and comprising (a) 40 to 70 weight parts of a high molecular weight, low density ethylene polymer having a high load melt index in the range of 0.1to1.5g/10min.,adensityofO.930toO.945g/cc,aheterogeneityindexoflessthan 10and 5 having essentially no other brancning than short chain branching, and (b) 60 to 30 weight parts of a low molecularweight, high density ethylene polymer having a melt index in the range of 45 to 300 9/10 min., a density above 0.950, a heterogeneity index of less than 6 and being essentially linear. The polymer composition is said to be useful for the production of polyolefin films, pipe production and wire coating. The films are said to have good environmental stress crack behavior.
Shirodkar (U .S. Patent 5,041,501) discloses polymer blends of linear low density polyethylene (LLDPE) with a minor amount of an isotactic, partially crystalline butene-1 polymer for producing blown films having improved impact properties. Shirodkar (U.S. Patent 5,242,922) discloses polymer blends of HDPE with a minor amount of an isotactic, partially crystalline butene-1 polymer for producing containers with lower swell compared to those of the unblended HDPE.
Thiersault et al. (U.S. Patent 4,786,688) discloses polyethylene compositions containi ng from 50 to 98 weight percent of HDPE and from 2 to 50 weight percent of LLDPE
with a density below 0.930. The composition is said to be particularly adapted for the 20 manufacture of films and hollow bodies by blow-molding.
Calabro et al. (U.S. Patent 5,102,955) disclose a low density polymer having a broad molecular weight distribution, such that its melt flow ratio is 50 to 250, and a substantially constant melt index-corrected density. The polymer is produced by blending a first polymer component of high molecular weight with a second polymer component of low 25 molecular weight, with both polymer components having substantially the same melt index-corrected density. The polymer is said to produce films having improved strength properties, as compared to films made from individual polymer components.
European patent application EP-A-0,517,222 discloses a polyethylene moulding material which consists of from 50 to 80 weight percent of a HDPE, having a density of from 30 0.940to 0.960 g/cm3 and a MFI 190/2.16 of from 0.01 to 0.5 9/10 min. and a broad bimodal molar mass distribution, and of from 20 to 50 weight percent of a polyethylene of a density of fromO.910toO.925g/cm3andaMFI190/2.160ffromO.5to2.0g/10min. Thepolyethylene moulding material has a density of from 0.930 to 0.940 g/cm3 and a MFI 190/2.16 of from 0.05 to 1.0 9/10 min. The polyethylene of low density may be a li near polyethylene (LLDPE) with a 35 narrow unimodal molar mass distribution. The European patent application discloses that pipes, sheets and films of good long term and low temperature properties can be produced.
Particularly, the material is said to have extraordinary resistance to slow crack propagation (ESCR) .

W 096~750 PCTrUS9S/07643 Additionally, ternary pol~mer blends are known. For example, in U.S. Patent 4,824,912, Su et al. disclose LLDPE blended with minor amounts of a low molecular weight HDPE (LMW-HDPE) anci a high molecular weight HDPE (HMW-HDPE) for processability and film property improvemen1s over LLDPE used alone.
Applicants have found a novel medium modulus, molded polyethylene material having excellent impact ~lrer~yll, and good dimensional stability, and a method to prepare such molded material.
The novel molded material has a thickness of greaterthan about 0.23 mm and comprises:
10 (A) from 60 to 99 weight percent, basecl on the combined weights of components (A) and (B), of at least one high molecular weight linear ethylene polymer having a density in the range of 0.92 to 0.96 g/cc and an 15 melt index in the range of 0.1 to 3 9/10 minutes, and (B) from 1 to 40 weight percent, based on the combined weights of components (A) and (B), of at least one substantially linear ethylene/a-olefin interpolymer characterized as having:
i. ameltflowratio,l10/12, 2 5.63, ii amolecularweightdistribution,Mw/Mn,definedbytheequation:
MW/l\fin S (i10/12)-4.63,and iii. a critical shear rate at onset of surface melt fracture at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer 20 having essentially the sa me 12 and MW/l\An wherein the substantially linear ethylene/rl-olefin interpolymer is further characterized as containing at least one a-olefin monomer and having a density in the range of 0.85 to 0.92 9/cc and an i2 melt index in the range of 0.3 to 3 g/10 minutes.
One method for producing such medium modulus molded polyethylene material 25 is an extrusion process which comprises the steps of:
(1) providing an extrudable thermoplastic composition containing (A) from 60 to 99 weight percent, based on the combined weigh1:s of components (A) and (B), of at least one high weight molecular linear ethylene polymer having a density in the range of 0.92 to 0.96 g/cc and an i5 melt index in the range of 0.1 to 3 9/10 minutes, and (B) from l to 40 weight percent, 30 based on the combined weights of components (A) and (B), of at least one substantially linear ethylene/a-olefi n i nterpolymer characterized as havi ng:
i. ameltflowratio,l1o/12, 2 5.63, ii. a molecular weight distribution, MW/Mn, defined by the equation:
MW/Mn 5 (110/12)-4.63,and 35 iii. a critical shear rate at onset of surface melt fracture at least 50 percent greater than the critical shear r.a1:e at the onset of surface melt fracture of a linear olefin polymer having essentially the s,3llle 12 and MW/Mn W 096/35750 PCTrUS95107643 wherein the substantially linear ethylene/cl-olefin interpolymer is further characterized as containing at least one a-oiefin monomer and having a density in the range of 0.85 to 0.92 g/cc and an lz melt index in the range of 0.3 to 3 9/10 minutes, optionally pelletizing the composition, 5 (2) introducing said optionally pelletized composition of step (1) into an extrusion apparatus, and (3) extruding said composition of step (1) to form a material with a thickness greaterthan about 0.23 mm, and (4) conveying said material formed in step (3) for subsequent use down-line of the extrusion 10 apparatusofstep(2)orcollectingsaidmaterialformedinstep(3)forsubsequentuseoff-line.
The molded material of the present invention has improved impact performance that is not ordinarily expected for medium modulus polyethyiene. The novel molded material has an improved impact strength relative to prior art molded materials having about the same density, stiffness (measured as yield strength), melt index and thickness which are produced from blends of a) high molecular weight high density polyethyiene (HDPE) and b) linear low density poiyethylene (LLDPE), very low density polyethylene (VLDPE), butyl rubber, ethylene-propylene copolymer (EPM) or ethylene-propylene-diene terpolymer (EPDM). At ambient temperature, the novel molded materials often have at least 30 percent, and preferably at least S0 percent, improvement in impact properties relative to the mentioned polyethylene material.
20 The i mproved i mpact resistance reduces fai I ures of the molded materials due to crack propagation.
Figure 1 plotsdata describing the relationship between MW/Mn and l~o/12 for three distinct polymertypes: substantially linear polyethylene, heterogeneous linear polyethylene and homogeneous linear polyethylene.
25 Glossarv and Test Methods The term "interpolymer as used herein refers to polymers prepared by the polymerization of at least two different monomers. The generic term interpolymer thus embraces copolymers, usually employed to referto polymers prepared from two different monomers, and polymers prepared from more than two different monomers.
Low density polyethylene (" LDPE") herein designates an ethylene polymer which is generally prepared at high pressure using free radical initiators and typically has a density in the range of 0.915 to 0.940 g/cm3. LDPE is also known as "branched" polyethylene because of the relatively large number of long chain branches extending from the main polymer backbone.
High density polyethylene ("HDPE") herein des.gnates an ethylene polymer which has a density in the range of greater than 0.940 to 0.960 g/cm3. HDPE is prepared using a coordination catalyst, for example, Ziegler-Natta type catalysts, at low or moderate pressures, W 096~5750 PCTrUS95/07643 but sometimes at high pressure. HDPE is linear without any substantial side chain branching.
HDPE is a substantially crystalli ne polyn1er.
Linear, la,~ density polyethylene ("LLDPE") is generally prepared in the same manner as HDPE, but incorporates a relatively minor amount of an a-olefin comonomer such as 5 butene, hexene or octerle to i ntrod uce enough short chai n branches i nto the otherwise I i near polymertoreducethedensityoftheresultantpolymerintotherangeofthatofLDPE. The coordination catalysts u!;ed to interpolymerize ethylene and the a-olefin generally produce an LLDPE with a relatively broad weight molecular weight distribution, that is, MW/Mn greater than 3. Such LLDPE's alsc) have relatively broad composition distri bution i n that the proportion 10 of a-olefin comonomer molecules incorporated into the polymer molecules varies. Generally, the lower molecular weight polymer moiecules contain a relatively higher proportion of the Q-olefin comonomer than the higher molecular weight polymer molecules.
The term s " ultra low dens,ity polyethylene " (U LDPE), " very low density polyethylene" (VLDPE) and "linear ver),How density polyethylene" (LVLDPE) have been used i nterchangeably i n the polyethyl ene art to desi gnate the polymer subset of I i near low density polyethylenes having al density lessthan orequal to about 0.915 g/cc. The term "linear low density polyethylene" (L.LDPE) is then applied to those li near polyethylenes having a density above about 0.915 g/cc.
The terms "heterogeneous" and "heterogeneously branched" are used herein in 20 theconventionalsenseinreferencetoalinearethylene/a-olefinpolymerhavinga comparatively low short chain branching distribution index. The short chain branching distributionindex(SCBDl)isdefinedastheweightpercentofthepolymermoleculeshavinga comonomer content within 50 percent of the median total molar comonomer content. The short chain branching distribution index of polyolefins can be determined by well-known 25 temperature rising elu~ion fractionation techniques, such as those described by Wild et al., Journal of Polymer Science, Polv. Phvs. ~d., Vol. 20, p. 441 (1982), L. D. Cady, "The Role of Comonomer Type and Distribution in Ll DPE Product Performance," SPE Regional Technical Con~erence, Quaker Square Hilton, Akron, Ohio, October 1-2, pp.107 to 119 (1985), or U.S.
Patent 4,798,081. Heterogeneous l i near ethylene/a-olefin polymers typical Iy have a SCB Dl less 30 than about 30 percent.
The terms " homogeneous" and " homogeneously branched " are used i n the conventional sense in reference to an ethylene/a-olefin polymer in which the comonomer is randomly distributed v,/ithin a given polymer molecule and wherein substantially all of the polymer molecules have the same ethylene to comonomer molar ratio. Homogeneously35 branched polymers are characterized by a short chain branching distribution index (SCBDI) greater than or equal to 30 percent, preferably greater than or equal to 50 percent, more preferably greater than or equal to 90 percent.

W 096/3S750 PCTnUS95/07643 The term " homogeneous I i near ethylene/a-olefi n polymers" means that the olefin polymer has a homogeneous short branching distribution but does not have long chain branching. That is, the linear ethylene/a-olefin polymer has an absence of long chain branching Such polymers include linear low density polyethylene polymers and linear high 5 density polyethylene polymers and can be made using polymerization processes (for example, as described by Elston in U.S. Patent 3,645,992) which provide uniform branching (that is, homogeneously branched) distribution. Uniform branching distributions are those in which the comonomer is randomly distributed within a given interpolymer molecule and wherein substantially all of the interpolymer molecules have the same ethylene/comonomer ratio 10 within that interpolymer. In his polymerization process, Elston uses soluble vanadium catalyst systems to make such polymers, however, others such as Mitsui Chemical Corporation and Exxon Chemical Company have used so-called single site catalyst systems to make polymers having a similar homogeneous structure.
The term "homogeneous I i near ethylene/a-olefi n polymers" does not refer to high pressure branched polyethylene which is known to those ski l led i n the art to have numerous long chain branches. Typically, the homogeneous linearethylene/a-olefin polymer is an ethylene/a-olefin interpolymer, wherein the a-olefin is at least one Cs-C20 a-olefin (for example,1-pentene,4-methyl-1-pentene,1 -hexene or 1 -octene), preferably wherein at least one of the a-olefins is 1-octene. Most preferably, the ethylene/a-olefin interpolymer is a 20 copolymer of ethylene and a C5-C20 a-olefin, especial Iy an ethylene/C~ -C6 a-olefin copolymer.
Theterm "medium modulus" isused herein in referencetothe novel molded material to mean the calculated material density is in the range of 0.923 to 0.95 g/cc. The term "calculated material density" is used herein to mean the density of the material when calculated from the known weight fractions and the measured annealed densities of the 25 component polymers or layers.
The density of the polymers used to make the medium moduius molded material of the present invention is measured in accordance with ASTM D-792 and is reported as grams/cubic centimeter (g/cc). The measurements reported in the Examples below are determined after the polymer samples have been annealed for 1 hour at 100~C and 4 hours at 30 23~C and 50 percent relative humidity.
Melt index measurements are performed according to ASTM D-1238, Condition 190~C/2.16 kilogram (kg) and Condition 190~C/5 kg, and are known as 12 and 15, respectively.
Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecularweight, the lowerthe melt index, although the relationship is not linear. Melt 35 index is reported as 9/10 minutes. Melt index determinations can also be performed with even higherweights, such as in accordance with ASTM D-1238, Condition 190~C/10 kg and Condition 190~C/21.6 kg, and are known as l10and 121 6, respectively.

W O 96/35750 PCT~US95107643 The term " melt fiow ratio" as defined herei n i n the conventional sense as theratio of a higher weight melt index determination to a lower weight determination. For measured l1o and 12 melt index values, the melt flow ratio is conveniently designated as i10/12 For 12~ .6 and 11o valuesr the ratio is designated 121 6/l10. Other melt flow ratios are occasionally 5 used respecting polyethylene compositions, such as, for example, l5/12 based an 15 and lz melt i ndex measurements. In general, lz1 6/l 10 and 15/12 determinations provide si mi lar melt flow valuesandl10/12valuesiareusuallygreaterthanl21,6/110vaiuesbyafactorofabout4.4andthis factor is used for purposes of this invention in calculating certain values in the Examples.
The crystal linity, as mentioned in Table 1 below is measured according to ASTM
10 D3417-75, the heat of 1Fusion is determi ned from the second heati ng cycle by measuri ng the area under the fusion erldotherm by drawing a baseline from the point at -20~C to the point at Peak temperature ~ 2()~C. The heat of fusion is divided by 292 J/g and multiplied by 100 to obtain the percent crystallinity. The tensile properties of the molded materials are measured in accordance with ASTM D 638-76 and are reported in MPa for the Yield and Ultimate tensile strengths and in percert1: for the Elongation. The impact properties, specifically the impact strength, of the molde~d material is evaluated by means of Izod Impact values and the critical strain energy release rate Gc. The Izod impact values are measured in accordance with ASTM D-256. The critical strain energy release rate Gc is measured using the Charpy Test, in accordance with the procedure described by E. Plati and J.G. Williams in Polymer Engineering and Science, 20 June,1975, Vol 15, No.6,, pp. 470 to 477. The PEnsylvania Notch Test (PENT) is a Slow Crack Growth test, performe~d following the procedure described by X. Lu and N. Brown, Polymer Testing 11 (1992),pages309to319;thetestwasconductedundera2.4MPastressat80~C. TheSmal I Scale Steady State (S4) test is an im pact test for pi pes descri bed by P. Vanspeybroek i n:
Proceedings Plastic Pipes Vlll, Eindhoven (The Netherlands), Sept.1992, The Plastics and Rubber 25 Institute,p.D1/61-14. Inthistesttheclackisinitiatedbytheimpactofagas-gunfiredchisel on a well supported and not pressurized initiation zone. This crack is injected in the pressurized propagation zone in an ,external containment against flaring and decompression and providing controlled local environmen1:. The reported Critical Pressures Pc,s4 are the operating pressures at which a crack propagates instead of arrests and is given at different temperatures.
The medium modulus, molded polyethylene material of the present invention has a calculated material density in the ranye of 0.923 g/cc to 0.95 g/cc, especially, 0.926 g/cc to 0.948 g/cc, and more esipecially, 0.93 g/cc to 0.946.
The thickn ess of the material is greater than about 0.23 mm, preferably i n therange of 0.5 mm to 50 mm, and more preferably, in the range of 3 mm to 30 mm.
At ambient temperatures, these novel materials preferably have Izod Impact values and a critical strain energy release rate Gcat least 30 percent greater, more preferably at least 50 percent greater, than the Izod Impact val ues and Gc of a comparative prior art W O 96~5750 PCTrUS95/07643 polyethylene material having about the same material density, melt index, yield strength and material thickness.
The composition comprising the components (A) and (B) described in more detail below can be molded to pipes, tubes, bars, sheets or materials of other shapes, such as 5 automotive parts, having a material thickness of greater than about 0.23 mm. The molded material is particularly useful in applications where molded materials with a good property balance, that means with good di mensional stabi l ity, that is stiffness, and with good i mpact strength, that is toughness, are needed.
The high molecular weight linear ethylene polymers, Component (A), for use in 10 preparing the medium modulus, molded polyethylene material of the instant invention are a known class of compounds which can be produced by any well-known particle-form polymerization process, such as slurry polymerization and gas phase polymerization.
Preferably, the high molecular weight li near ethylene polymers are produced using wel 1-known Phillips or Zieglertype coordination catalysts, although metallocene catalyst systems can also be used. Although preferred, with conventional Ziegler type catalysts, slurry polymerization processes are generally limited to polymer densities greater than about 0.940 g/cc and especial Iy I imited to polymer densities greater than about 0.935 g/cc, that is, about 0.935 g/cc is the practical lower commercial I i mit for sl urry polymerization.The high molecular weight linear ethylene polymer can be an ethylene 20 homopolymer or a copolymer of ethylene with at least one a-olefin of from 3 to 20 carbon atoms. However, preferably, the high molecular weight linear polymer is a copolymer with at least one C3-C20 a-olefin, such as 1-propylene, 1-butene, 1-isobutylene, 4-methyl-1-pentene, 1-hexene, 1 -heptene and 1 -octene. Most preferably, the high molecular weight linear ethylene polymer is an ethylene/l-butene copolymer prepared by a low pressure slurry polymerization 25 process. The novel molded material comprises from 60 to 99 weight percent high molecular weight linear ethylene polymer, generally 60 to 9S weight percent, preferably 60 to 92.5 weight percent, more preferably 65 to 90 weight percent, and most preferably 70 to 85 weight percent.
Component (A) can also be a blend of linear ethylene polymers. Such blends can 30 be prepared in-situ (for example, by having a mixture of catalysts in a single polymerization reactor or by using different catalysts in separate reactors connected in parallel or in series) or by physical blending of polymers.
The high molecular weight linear ethylene polymer has an 15 melt index in the range of 0.1 9/10 minutes to 3 g/10, preferably, 0.1 9/10 minutes to 2 9/10 minutes, more 35 preferably, 0.15 9/10 minutesto 1 9/10 minutes and more preferably, 0.15 g/10 minutesto 0.5 9/10 minutes. Additionally, the linear polymer preferably has a bimodal molecular weight distribution (MWD) and an 12~ lo ratio in the range of from 1 to 12, preferably in the range of W 096/3~750 PCT/U~ 7643 from3.5to10,morepreFerablyintherangeoffrom4to8,andmostpreferablyintherangeof from 4.5 to 6.
The high molecular weight linear ethylene polymer, which includes, but is not limited to, LLDPE, LMDPI (linear medium density polyethylene) and HDPE, and mixtures thereof, preferably has a density in the r ange of from 0.92 g/cc to 0.96 g/cc, more preferably, in the range of from 0.93 !3~cc to 0.96 g/cc, and most preferably, in the range of from 0.935 g/cc to 0.958 g/~c.
The substantially linear ethylene/a-olefin polymers used in the present invention Component (B), are a unique class of compounds that are defined in US 5,272,236 and U.S.
10 Patent 5,278,272 by Lai et al. Lai et al. teach that such polymers are preferably prepared by a continuous, solution phase polymerization process using the constrained geometry catalyst discovered by Stevens et lal. U.S. Patent 'i,055,438. The substantially linear ethylene/a-olefin interpolymers contain etllylene interpolymerized with at least one C3-C20 a-olefin, such as 1 -propylene,1-butene,1-isobutylene,1-hexene,4-methyl-1-pentene,1-hepteneand 1-octene,as well as other monomer types such as styl~ene, halo- or alkyl-substituted styrenes, tetrafluoro-ethylene, vinyl benzocyclobutane,1,4-hexadiene, 1,7-octadiene, and cycloalkenes, for example, cyclopentene, cyclohexene and cyclooctene. Although the substantially linear ethylene/a-olefin interpolymer can be a terpolymer where at least two a-olefin monomers are polymerized with ethylerle, preferably the interpolymer is a copolymer with one a-olefin 20 monomer copolymerized with ethylene and most preferably the substantially linear ethylene/a-olefin interpolymer is a copolymer of ethylene and 1-octene.
The substantially linear ethylene/a-olefin interpolymers used in the present invention are not in the same class as homogeneous linear ethylene/a-olefin copolymers, nor heterogeneous linear ethylene/a-olefin polymers, nor are they in the same class as traditional z5 highly branched low density polyethylene. The substantially linear ethylene/a-olefin polymer useful in this invention are indeed a unique class of polymers which have excellent processability, even thou~3h they have relatively narrow molecular weight distributions (typically, about 2). Everl more surprisingly, as described in US Patent 5,278,272 by Lai et al., the melt flow ratio (l l o/12) ol 1:he substantial Iy I i near ethylene/tl-olefi n i nterpolymers can be varied 30 essentially i ndependently of the polydispersity index (that is, the moiecular weight distribution, MW/Mn). As figure 1 illustrates, the rheological behavior of substantially linear ethylene polymers constitutes a dramatic contradisti nction over to a homogeneous li near ethylene/a-olefin polymer and to cconventional heterogeneous linear polyethylene in that both heterogeneous linear and homogeneous linear ethylene polymers have rheological properties 35 such that the l 1 o/12 val ue only i ncreases as the polydispersity i ndex i ncreases.
Substantiall y linear ethylene/a-olefin polymers (SLEP) are homogeneous polymershaving long chain branching. The long chain branches have the same comonomer distribution as the polymer backbone and can be as long as about the same length as the length of the g W 096/35750 PCTnUS9S107643 polymer backbone. The polymer backbone is substituted with 0.011ong chain branches/1000 carbons to 3 long chain branches/1000 carbons, more preferably from 0.01 Iong chain branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0.051ong chain branches/1000 carbonsto 1 long chain branches/1000 carbons.
Long chain branching is defined herein as a chain length of at least 6 carbons, above which the length cannot be disti nguished usi ng 1 3C nuclear magnetic resonance spectroscopy. The long chain branch can be as long as about the same length as the length of the polymer backbone to which it is attached.
The presence of long chain branching can be determined in ethylene 10 homopolymers by usi ng 1 3C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method described by Randall (Rev. Macromol. Chem. Phvs., C29, V.2&3, p. 285-297).
As a practical matter, current 1 3C nuclear magnetic resonance spectroscopy cannot determine the length of a long chain branch in excess of six carbon atoms. However, there are other known techniques useful for determining the presence of long chain branches in ethylene polymers, including ethylene/1-octene interpolymers. Two such methods are gel permeation chromatography coupled with a low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with a differential viscometer detector (GPC-DV). The use of these techniques for long chain branch detection and the underlying theories have been well documented in the literature. See, for example, Zimm, G.H. and 20 Stockmayer,W.H.,J.Chem.Phys., 17,1301 (1949)and Rudin,A.,ModernMethodsofPolymer Characterization,JohnWiley&Sons,NewYork(1991)pp.103-112,bothofwhichare incorporated by reference.
A. Willem deGroot and P. Steve Chum, both of The Dow Chemical Company, at the October 4,1994, conference of the Federation of Analytical Chemistry and Spectroscopy 25 Society (FACSS) in St. Louis, Missouri, presented data demonstrating that GPC-DV is a useful technique for quantifying the presence of long chain branches in substantially linear ethylene interpolymers. In particular, deGrootand Chum found thatthe level of long chain branches in substantial Iy I i near ethylene homopolymer samples measured usi ng the Zim m-Stockmayer equation correlated well with the level of long chain branches measured using 1 3C NMR.
Further, deGroot and Chum found thatthe presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, as such, one can account for the molecuiar weight increase attributable to octene short chain branches by knowing the mole percent octene in the sample. By deconvoluting the contribution to molecular wei ght increase attri butable to 1 -octene short chai n branches, deGroot and Chum 35 showed that GPC-DV may be used to quantify the level of long chai n branches in substantial Iy linearethylene/octene copolymers.
deGroot and Chum also showed that a plot of Log (12, Melt Index) as a function of Log (G PC Weight Average Mol ecu lar Wei g ht) as determ i ned by G PC-DV i l l ustrates that the I ong . CA 02220439 1997-11-06 W 096135750 PCT/u~5S~'~7643 chain branching aspects (but not the extent of long branching) of substantially linear ethylene polymers are comparable to that of high pressure, highly branched low density polyethylene (LDPE) and are clearly distinct from ethylene polymers produced using Ziegler-type catalysts such as titanium compllexes and ordinary homogeneous catalysts such as hafnium and 5 vanadium complexes.
For ethylene/a-olefi n i nterpolymers, the long chai n branch is longer than theshort chain branch that results from th~e incorporation of the a-olefin(s) into the polymer backbone. The empiricall effect of the presence of long chain branching in the substantial linear ethylene/a-olefin interp~olymers used in the invention is manifested as enhanced rheological 10 properties which are quantified and expressed herein in terms of gas extrusion rheometry (GER) resultsand/or melt flow, 11o/l2t increases.
The term '' linear" means that the polymer lacks measurable or demonstrable longchain branches, that is, the polymer is substituted with an average of less than 0.01 Iong branch/1 000 carbons.
The "rheological processing index" (Pl) is the apparent viscosity (in kpoise) of a polymer measured by a ~3as extrusion rheometer (GER). The gas extrusion rheometer is described by M. Shida, R. N. Shroff and l..V. Cancio in Polvmer Enc~ineerinq Science, Vol. 17, No.
1 1, p. 770 (1977), and in " Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold Co. (1982) on pp. 97 to 99, both publications of which are incorporated by 20 reference herein in their entirety. GER experiments are performed herein at a temperature of 1 90~C, at nitrogen pressu res between 250 to 5500 psig using a 3.81 cm diameter die and a 20:1 UD rheometerwith an ,entrance angle of 180~C. The processing index is measured herein at 3,000 psig.
Forthe sub!stantially linear ethylene/a-olefin interpolymers used herein, the Pl is 25 the apparent viscosity (in kpoise) of a material measured by GER at an apparent shear stress of 2.15 x 106dyne/cm2. The substantially linear ethylene/a-olefin interpolymers used herein preferably have a Pl in the range of 0.01 kpoise to 50 kpoise, preferably 15 kpoise or less. The substantially linear ethylene/a-olefin interpolymers used herein have a Pl less than or equal to 70 percent of the Pl of a comparative linear ethylene polymer (either a Ziegler polymerized 30 polymeroralinearunifoimlybranchedpolymerasdescribedbyElstoninUSPatent3,645,992) at about the same l~ ancl I\Aw/Mn An apparent shear stress versus apparent shear rate plot can be used to identifythe melt fracture phenomena. According to Ramamurthy in the ~ournal of Rheology, 30(2), 337 to 357, 1986, above a certai n critical flow rate, the observed extrudate irregularities may be 35 broadly classified into tVI/O main types: surface melt fracture and gross melt fracture.
Surface mel t fracture occurs under apparently steady flow conditions and rangesin detail from loss of specular film gloss to the more severe form of "sharkskin. " In this disclosure, the onset of surface melt fracture (OSMF) is characterized at the beginning of losing . CA 02220439 1997-11-06 W 0961357S0 PCTnUS95/07643 extrudate gloss at which the surface roughness of the extrudate can only be detected by 40x magnification. The critical shear rate at the onset of surface melt fracture for the substantially linear ethylene/a-olefin interpolymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a comparative linear ethylene polymer (either a Ziegler 5 polymerized heterogeneously branched polymer or a homogeneously branched polymer as described by Elston in US Patent 3,645,992) having essentially the same 12 and MWlMn.
Preferably, the critical shear stress at onset of surface melt fracture for the substantially linear ethylenela-olefin interpolymers is greater than 2.8x106 dyneslcm2.
Gross melt fracture occurs at unsteady extrusion flow conditions and ranges in 10 detail from regular (alternating rough and smooth, helical, etc.) to random distortions. For commercial acceptability, (for example, in molded parts), surface defects should be minimal, if not absent, for good qual ity and properties. The critical shear rate at the onset of surface melt fracture (OSM F) and the onset of gross melt fracture (OGMF) wi l l be used herel n based on the changes of surface roughness and configurations of the extrudate. For the substantially linear ethylene/a-olefin interpolymers, the critical shear stress at onset of gross melt fracture is preferablygreaterthan 4X106 dynes/cm2.
To more fully characterize the rheological behavior of the unique substantially linear ethylene/a-olefin interpolymers, S. Lai and G.W. Knight introduced (ANTEC '93 Proceedings, lNSlTETM Technology Polyolefins (ITP) - New Rules in the Structure/Rheology 20 Relationship of Ethylene a-Olefin Copolymers, New Orleans, La., May 1993) another rheological measurement, the Dow Rheology Index (DRI), which expresses a polymer's "normalized relaxation time as the result of long chain branching." DRI ranges from 0 for polymers which do not have any measurable long chain branching (for example, "TAFMER" and " EXACT"
products sold commercially by Mitsui Chemical and Exxon Chemical Company, respectively) to 25 about 15 and is independent of melt index. In general, for low to medium density ethylene polymers (particularly at lower densities) DRI provides improved correlations to melt elasticity and high shear flowability relative to correlations of the same attempted with melt flow ratios.
For the substantial Iy li near ethylene/cL-olefin polymers used i n this i nvention, DRI is preferably at least 0.1, and especially at least 0.5, and most especially at least 0.8. DRI can be calculated 30 from the equation:
DRI = (3652879 ~ ~O 1.00649/ r1O - 1)/10 where lo is the characteristic relaxation time of the material and rlO is the zero shear viscosity of the materi al . Both ~O a nd rlO are the " best fit" val ues to the Cross equation, that is rl/rlO = 1/(1 ~ (y~O) 1-n) where n is the power law index of the material, and rl and y are the measured viscosity and shear rate, respectively. Baseline determination of viscosity and shear rate data are obtained using a Rheometric Mechanical Spectrometer (RMS-800) under dynamic sweep mode from 0.1 W 096/3S750 PCTrUS95/07643 to 100 radians/second at 190~Cand a Gas Extrusion Rheometer(GER) atextrusion pressures from 1,000 psi to 5,000 psi (6.89 to 34.'i MPa), which corresponds to shear stress from 0.086 to 0.43 MPa, using a 3.81 centimeterdiameterdie and 20:1 UD rheometerat 190~C. Specific materialdeterminatialn~scanbeperformedfrom 140to190~Casrequiredtoaccommodatemelt5 index variations.
Substan1ially linear ethylene/a-olefin interpolymers are considered to be " homogeneous" in composition distri bution si nce substantial Iy al I of the polymer molecules have the same ethylene-to-comonomer ratio. Moreover, the substantially linear ethylen polymers have a narrovv short chain (homogeneous) branching distribution, as defined by US
10 Patent3,645992. The~istributionofcomonomerbranchesforthesubstantiallylinear ethylene/q-olefin interpolymers is characterized by its SCBDI (Short Chain Branch Distribution Index) or CDBI (Composition Distribution Branch Index) and is defined as the weight percent of - the polymer molecules having a comonomer content within 50 percent of the median total molar comonomer content. The CDBI of a polymer is readily caiculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (abbrevia1:ed herein as "TREF"). The SCBDI or CD81 for the substantially I inear ethylene/a-olefi n i nterpolymers used i n the present i nvention is preferably greater than 30 percent, especially greater than 50 pen:ent.
Thesubsl:zntiallylineare~hylene/a-olefinpolymersused inthisinvention 20 essentially lack a measu rable " high density" fraction, as measured by the TREF technique.
Preferably, the substantially linear ethylene/a-olefin interpolymers do not contain a polymer fraction with a degree cf branchi ng less than or equal to 2 methyls/1000 carbons. The " high density polymer fractk~n" can also be described as a polymer fraction with a degree of branchi ng less than 2 methyls/1000 carbons.
The molecular weight and molecular weight distribution, MW/Mn ratio, of substantially linear ethylene/a-olefin interpolymers can be analyzed by gel permeation chromatography (GPC) on a Waters 150 high temperature chromatographic unit equipped with differential refractometer and three columns of mixed porosity. The columns are supplied by Polymer Laboratorie~ and are commonly packed with pore sizes of 103,104,105 and 1 o6A.
The solvent is 1,2,4-trichlorobenzene. from which 0.3 percent by weight solutions of the samples are prepared for injection. The flow rate is 1.0 milliliters/minute, unit operating temperature is 140~Cand the injection size is 100 microliters.
The molecu lar weight determi nati on with respect to the polymer back-bone is deduced by using narro~,v molecular weight distribution polystyrene standards (from Polymer 35 Laboratories) in conjunction with their elution volumes. The equivalent polyethylene molecular weights are Id~etermined by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Ward in Journal of Polymer Science, Polymer Letters, Vol . 6, p. 621,1968) to derive the fol lowi ng equation:

W 096/3~750 PCTnUS95/07643 Mpolyethylene = a (Mpoiystyrene)b-I n this equati on, a = 0.4316 and b = l Ø Wei ght average molecul ar wei ght, Mw, is calculated in the usual manner accordi ng to the following formula: Mw = 2 wj* M j, where w;
and Mj are the weight fraction and molecular weight, respectively, of the jth fraction eluting 5 from the GPC column.
For the substantially linear ethylene/a-olefin interpolymers used in the presentinvention, the MW/Mn is preferably less than 3, especially from 1.5 to 2.5.
The novel molded material comprises from 1 to 40 weight percent, based on the combined weight of components (A) and (B), of the substantially linear ethylene/a-olefin 10 i nterpolymer, general Iy from 5 to 40 weight percent, preferably from 7.5 to 40 weight percent, more preferably from 10 to 35 weight percent, and most preferably from 15 to 30 weight percent.
The substantially linear ethylene/a-olefin interpolymer used to prepare the molded material of the present invention has an 12 melt index in the range of 0.3 g/10 minutes to 3 9/10, preferably, 0.3 9/10 minutes to 2.5 g/10 minutes and, more preferably,0.4 9/10 minutesto 2 9/10 minutes. The substantially linear ethylene/a-olefin interpolymer has a density in the range of 0.85 g/cc to 0.92 g/cc, preferably, in the range of 0.85 g/cc to 0.916 g/cc, more preferably, in the range of 0.86 g/ccto 0.91 g/cc., and most preferably in the range of 0.86 g/cc to 0.89 g/cc. The 11o/12 ratio of the substantially linear ethylene/a-olefin interpolymers is in the 20 range from 5.63 to 30, preferably less than 20, especially less than 15, and most especial Iy less than 10.
Component (B) can be a blend of substantially linear ethylene/a-olefin interpolymers. Component (B) may be blended with at least one heterogeneous or homogeneous linear ethylene polymer (C) which is selected from U LDPE or LLDPE, preferably 25 wlth a heterogeneous ULDPE. The total weight of components (B) and (C) preferably is up to about 40 weight percent, more preferably up to about 35 weight percent, most preferably up to about 30 weight percent, based on the combined weight of components (A), (B) and (C).
Heterogeneously branched U LDPE and LLDPE are well known and commercially available materials. They are typically prepared using Ziegler-Natta catalysts in solution or gas 30 phase polymerization processes Anderson et al., U.S. Patent 4,076,698, is illustrative. These traditional Ziegler-type linear polyethylenes are not homogeneously branched and they do not have any long-chain branching. Heterogeneously branched ULDPE and LLDPE typically having molecularweightdistributions, MW/Mn, intherangeoffrom 3.5to4.1.
Homogeneouslybranched ULDPEand LLDPEarealsowell known. Elston 35 disclosure in U.S. Patent 3,645,992 is illustrative. Homogeneously branched ULDPE and LLDPE
can be prepared in conventional polymerization processes using Ziegler-type catalysts such as, for example, zirconium and vanadium catalyst systems as well as using metallocene catalyst systems such as, for example, those based on hafnium. Ewen et al. disclosure in U.S. Patent W 096~357~0 PCT~US95/07643 4,937,299 and Tsutsui et al disclosure in U.S. Patent 5,218,071 are illustrative. The disclosures of Elston Ewen et al. and Tsutsui et al. This second class of linear polyethylenes are homogeneously branched polymers, and like traditional Ziegler-type heterogeneous linear polyethylenes, they do not have any long-chain branching. Homogeneously branched ULDPE
5 and LLDPE typical havint3 molecular weight distributions, MWlMn~ of about 2. Commercial examples of homogeneously branched linear polyethylenes include those sold by Mitsui Petrochemical Industries under the desi3nation "TAFMER" and by Exxon Chemical Company u nder the designati on " E XACT" .
The molded polyethylene material of the present invention can be produced by 10 known processes, for example by casting processes, compression molding or, preferably, by extrusion .
In a typical ~ xtrusion process, a poiyethylene composition is introduced into ascrew extruder wherein i1: is melted and fomvarded through the extruder under pressure. the molten polymer composi1:ion is forced through a flat or annular die to form a molten sheet or tube. Theextrudertemperature is preferably inthe rangefrom 160~Cto250~C, more preferably from 170~C to .210~C. It is kno~Nn how to produce the material of the desi red thickness.
Both monol.3yer and multilayer molded polyethylene materials can be prepared byextrusion and the ma~erials of the prejent invention can be monolayer or multilayer 20 structures. Multilayer molded polyethylene materials can be prepared by any known technique in the art, including, for example, coextrusion, lamination or combinations of both. However, the preferred medium modulus, molded polyethylene material of the present invention is a monolayer structure.
Components (A) and (B), an~d optional Component (C), used to prepare the 25 molded material of this invention, can be individually blended (that is, where a component itself is a polymer blend of two or more subcomponent polymers) or admixed together by any suitable means known in the art. Suitable means are thoughtto include tumble dry-blending the cornponents together prior to charging the extruder, weight-feeding the components directly into the extruder, melt-blending the components via compound or side-arm extrusion 30 prior to introduction into the extruder, multiple reactor polymerization of the components with reactors in series or i n parallel and optionally with different catalyst and/or monomer types in each reactor, or the like as well as combinations thereof.
Additives, such as antioxidants (for example, hindered phenolics, such as Irganox~
1010Orlrganox~1076suppliedbyCibaGeigy),phosphites(forexample,lrgafos~168also 35 supplied by Ciba Geigy), cling additives (for example, PIB), stearates, Standostab PEPQ~
(supplied by Sandoz), pigrn~ents, colorants, such as carbon black and fillers can also be included in the molded material of the present invention, or the polymer compositions used to make the same, to the extent that such additives or ingredients do not interfere with the improved . CA 02220439 1997-11-06 W 096/357S0 PCTnUS95/07643 impact strength discovered by Applicants. Although generally not required, the molded materiai of the present invention can also contain additives to enhance antiblocking and coefficient of friction characteristics including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate, and clay, as well as primary, secondary and substituted fatty 5 acid amides, release agents, silicone coatings, etc. Still other additives, such as quaternary ammonium compounds alone or in combination with ethylene-acrylic acid (EAA) copolymers or other functional polymers, can also be added to enhance the antistatic characteristics of the polyethylene material of this invention.
Advantageously, because of the improved strength properties of the novel 10 polyethylenematerial,recycledandscrapmaterialsaswellasdiluentpolymerscanbe i ncorporated or admixed into the polyethylene compositions used to make the novel molded polyethylene material at higher loadings than is typically possible with prior art polyethylene compositions and still provide or maintain the desired performance properties. Suitable diluent materials include, for example, elastomers, rubbers and anhydride modified polyethylenes (for example, polybutylene and maleic anhydride grafted LLDPE and HDPE) as well as with high pressure polyethylenes such as, for example, low density polyethylene (LDPE), ethylene/acrylic acid (EAA) interpolymers, ethylene/vinyl acetate (EVA) interpolymers and ethylene/methacrylate (EMA) interpolymers, and combinations thereof.
ExamPles The following Examples illustrate some of the particular embodiments of the present invention, butthe following should not be construed to mean the invention is limited only to the particular embodiments shown. U nless otherwise mentioned, all parts and percentages are by weight.
Examples 1 to 5 and Comparative Examples A to J
Compression molded bars of various thicknesses were produced as follows:
Polymers and polymer blends of the compositions listed i n Table I below were extruded on a Leistritz ZSE65 counter-rotating twin screw extruder after dry blending and adding 1000 ppm of each of IrganoxTM 1010, IrgafosTM 168, zi nc stearate and calcium stearate. The tem perature settingsofthedifferentzoneswere180/190t200/200/200t210/210~C. Themelttemperaturewas approximately 212~C at a screw speed of 40 RPM (revolutions per minute) and an output rate of approximately 25.4 kg/hr. The specific energy was 0.254 kWh/kg.
The extruded pellets were compression molded on a Fonti jne hot press for 5 mi nutes at 3 ton ram force and for 6 mi nutes at 28 ton ram force at a temperature of 190~C for tensile and Izod impact measurements. The procedure for preparing the samples for the PENT
and Gc measurements was as follows: 520 g of material was placed into a 12 mm thick steel mould which was isolated atthe sides by a polytetrafluoroethylene-coated frame, the sample was heated for 3 minutes at 160~C without pressure, followed by 3 minutes at 10.6 ton ram force,1 minute without pressure,1 minute at 10.6 ton ram force and 1 minute without W 096135750 1~1/U~5/07643 pressure. the temperature was increased to 180~C and a ram force of 10.6 ton was applied for 11 minutes. Two one n1i nute cycles of pressure release and pressurizing at 10.6 ton ram force were applied. After 1 minute of pressure release, the sample was pressurized again at 2.6 ton ram force and allowed to cool slowly overnight. From this sheet the test specimens were 5 machined with the required dimensions. Forthe Izod Impact measurements bars of 63.5 mm x 12.7 mm x 4 mm are used; the Gc measLlrements are conducted on bars of 125 mm x 10 mm x 10 mm; and the PENT test v,ras made with bars of 50 mm x 25 mm x 10 mm.
The polymlers used in the various formulations are:
1. HDPE 1 (Component A) is a high molecular weight HDPE resin having a melt index 15 = 0.28 gt1 Omin., a density of 0.952 g/cm3, and a melt flow ratio 121/15 of 23 (Comonomer: 1-butene).
2. HDPE 2 (Component A) is a high molecular weight HDPE resin having an 15 of 0.75 g/10 min. and a density of 0.952 g/cm3 (Comonomer: 1-butene).
3. SLEP 1 is a substantially linear ethylene-octene copolymer having a meit index 12 of 0.82 g/'l () min., a density of 0.87 g/cm3, a melt flow ratio l1o/12 of 7.9, MW/Mn of 1.98, a Critical Shear Rate of 503 s-l and a Critical Shear Stress of 3 0 ~ 106 dyne/cm2, 4. SLEP 2 is a substantially linear ethylene-octene copolymer having an 12 of 1.0 g/10 min., a denf;ity of 0.902 g/cm3, a meltflow ratio 11o/l2 of 9.52, MW/Mn of 2.19, a Critical She,ar Rate of 1386 s-1 and a Critical Shear Stress of 4.3 * 106 dyne/cmZ.
5. VLDPE is an ethylene-octene copolymer having an 12 of 1 g/10 mi n., a density of 0.907 g/cm ~, a melt flow ratio 11o/12 of 9.4 and MW/Mn of 3.5.

6. LLDPE is an ethylene-octene copolymer, having an 12 of 0.94 g/10 min., a density of 0.92 g/crrl3, a melt flow ratio 11o/l2 of 8 6 and MW/Mn of 3-3 25 7 Mitsui TafmerTM P-0480 Ul.DPE is an ethylene-propylene copolymer having an 12 = 1 g/10 min., a density of 0.87 g/cm3 and a melt fiow ratio 11O/I2 of 5-9-8. Elastomer: IJnion Carbide l~lexomerTM GERS-1085 is used which is an ethylene-butene copolymer with a narrow molecular weight distribution. The elastomer has a density of 0.884 g/cm3 and a Mooney viscosity ML (1 + 4) 125~C of 30.
30 9- PolysarTM 13utyl 100 is a Bu1:yl rubber having a density of 0.92 g/cm3 and a Mooney viscosity M L 8 (125~C) of 45.
10. PolysarTM 13utvl 301 isa Butyl rubberhavingadensityofO.92g/cm3anda Mooney viscosity M LB ( 1 25~C) of 51.
11. EPM rubber having a density (specific gravity) of 0.86 g/cm3 and a Mooney viscosityMLI~1 1 4) 125~Cof25; itiscommerciallyavailablefrom Exxon underthe trademark ~'istalon 504.

W 096/35750 PCTrUS95/07643 12. EDPM rubber having a density of 0.86 g/cm3 and a Mooney viscosity ML(1 + 4) 125~C of 25; it is commercially available from Exxon underthe trademark Vistalon2504.
Polymers 1 - 6 are supplied by The Dow Chemical Company.

Table I
(Comp.) A 1 2 3 Example Composition 100%95% HDPE190% HDPE190% HDPE1 HDPE15% SLEP110% SLEP210% SLEP1 15 [g/1 Orr~inl 0.28 0.28 0.43 0.33 6.50 7.19 9.40 7.57 [g/1 Omin]
Ratiol21 6/1523.2 25.7 23.2 22.9 Crystallinity71.2 67.1 61.7 [%]
Density measØ95110.94660.9460 0.9445 [g/cm3] calc. ---- 0.9467 0.9460 0.9424 Yield strength 23.3 21.2 21.4 19.7 [MPa]
20 Ultim.Tens. 38.1 40.7 40.8 36.6 sl, eny lh [MPa]
Elongation 855 909 923 840 [%]
Izod Impact 246 391 383 831 25 [J/m] 200C
OoC 205 304 287 830 Gc [kJ/m2] 11.9 17.1 16.6 29.0 20~C
30 PENT [min] 2204 6248 2829 10872 ~ensity meas. = measured density Densitycalc. = calculateddensity . CA 02220439 1997-11-06 W O 96135750 PCT/U~7643 Table I (continued 1) (Comp.) ~3 C 4 D
Example Composition82~/~ HDPE187~/~ HDPE180% HDPE174% HDPE1 18% LLDPE13% VLDPE 20% SLEP1 36% VLDPE
15 ~g/1 Omin] 0.41 0.39 0.46 0.69 1216 9.00 8.85 8.60 12.90 [9/1 Omin]
Ratio121 ~1522.0 22.7 18.7 18.7 Crystallinity 58.7 61.3 57.9 60.4 [%~
Density meas. 0.9447 0.9451 0.9348 0.9345 [g/cm3] calc. 0.9453 0.9451 0.9339 0.9347 Yield strength 20.6 20.6 15.9 15.8 [MPa]
Ultim. Tens.39.4 30.5 36.1 36.6 strength [MPa]
Elongation 908 761 868 926 [%]
Izod Impact 309 379 815 705 [J/m] 20~C (no break) 0~C 233 263 864 689 (no break) Gc[kJ/m2] 14.4 15.6 49.1 29.0 PENT [min] 11169 12003 933 >78000 (yielding) ~ensitymeas. = rneasured density Densitycalc. = <:akulateddensity W 096/35750 PCTrUS95/07643 Table I (continued 2) (Comp.) 5 E F G
Example Composition 80% HDPE290% HDPE1 88% HDPE1 91% HDPE1 20% SLEP110% ULDPE12% Elastomer 9% Butyl 100 15[g/10min]1.18 0.42 0.44 0.35 .6 22.05 8.77 9.42 8.59 [g/1 Omi n]
Ratio Iz1 6/15 18.7 21.0 21.4 24.5 Crystallinity 56.6 65 66 68 [%]
Density meas. 0.9340 0.9416 0.9443 0.9476 [g/cm3] calc. 0.9339 0.9423 0.9425 0.9482 Yield ~l~enylil 16.2 19.48 19.92 19.56 [MPa]
Ultim. Tens.35.5 33.48 35.45 29.87 strength [MPa]
Elongation 918 943 868 806 [%]
Izod Impact 740 579 553 302 [J/m] 20~C
ooc 571 413 155 Gc [kJ/m2] 33.2 20.58 18.77 7.9 20~C
0~C 17.09 14.63 6.33 -200C 7.31 6.34 4.32 PENT [min] 45 108 2337 1959 ~ensitymeas. = measureddensity Densitycalc. = calculateddensity W O 96~5750 PCTrUS95107643 Table I (continued 3) (Comp.~1 H
Example Composition91% HDPE1 91% HDPE191% HDPE1 9% Butyl 301 9% EPM 9~/0 EDPM
15 [g/1 Omin] 0.32 0.38 0.37 Iz1.6 8.21 8.87 8.76 [9/10min]
Ratio 121 6/15 25.7 23.3 23.7 Crystallinity 66 70 66 [o/o ]
Density meas. 0.9495 0.9435 0.9438 [g/cm3] calc. 0.~482 0.9421 0.9421 Yield strength 22.18 20.14 19.47 [MPa]
Ultim. Tens.37.54 35.02 23.78 strength [MPa]
Elongation 863 909 647 [%]
Izod Impact4.20 448 530 [J/m] 20~C
0~C 1~49 632 615 -20~C ~1 325 147 Gc [kJ/m2] 8.46 10.3 17.26 20~C
0~C 6.2 6.51 13.49 -200C 4.57 4.24 5.37 PENT [min] 1956 2781 885 Density meas. ~ measured den!;ity Densitycalc. = calculateddensity f 35 W 096~5750 PCTrUS95/07643 Table I lists both measured and calculated sheet density and measured melt indexes and melt flow ratios.
Table I illustrates the effect of modifying high molecularweight (HMW) HDPE
with SLEP 1 at a level of 10 percent SLEP 1 (Example 3). The Izod impact value and the critical 5 strainenergyreleaserateGcareaboutthreetimesashighasthevaluesofHDPEalone (Comparative Example A). For similar stiffness or yield strength, blends of HMW HDPE with LLDPE or VLDPE (Comparative Examples B and C) give only small improvements versus the HDPE
alone. The bars of Comparative Examples B and C have essentially the same density and thickness and a similar melt index 15 asthe bars of Example 3, but much lower Izod impact 10 values and much lower Gc values than the bars of Example 3. For a yield strength of 21.2 MPa both the blends of Examples 1 and 2 give similar Izod impact properties and Cc values. The slow crack growth parameter PENT, however, is twice as high with the blend of Example 1 versus the blend of Example 2. Differences between the Examples 3 and 5, especially in the PENT result, can be attributed to the higher Mw of the high density component A i n the former blend .
The comparison between Examples 1 and 2 illustrate that, within the preferred density range of 0.86 g/cc to 0.91 g/cc for the substantially linear ethylene / a-olefin, (SLEP), those SLEP's are preferred which have a density of from 0.86 g/cc to 0.89 g/cc.
The compression molded bars of Example 3 have an Izod Impact value which is at least 15 percent higher than the Izod Impact value of all Comparative Examples. With the 20 exception of Comparative Example D (which has a low yield strength~, the Izod impact of all Comparative Examples is even at least 30 percent lower than the Izod Impact val ue of Example 3. Furthermore, the molded bars of Example 3 show excel lent results i n the Gc test (critical strain energy release rate).
Furthermore, the compression molded bars of Examples 1 and 2 have a higher 25 stiffness (yield strength) and a higher Gc value than Comparative Exampies B and C, whereas theirlzodimpactishigherthanthelzodimpactofComparativeExampleBandsimilartothe Izod impact of comparative example C. Examples 1 and 2 are not comparable with Comparative Examples D, E, F, G, I and J because the yield strength of Comparative Examples D, E, F, G, I and J
is considerably lower than the yield strength of Examples 1 and 2. Examples 1 and 2 do not 30 show a better Izod Impact value than comparative example H but a considerably better Gc value and PENT value.
Example 3, having a similar yield strength as Comparative Examples E, F, G, I and J, show higher Izod impact, Gc and PENT values than these Comparative Examples.
Examples 6 and 7 To produce the pipes of Examples 6 and 7 respectively, the resin blends of Examples 1 and 3 respectively were used which, however, additionally contained 2.25 percent of carbon black. A pipe having a diameter of 125 mm and a wall thickness of 11.4 mm (Standard Dimension Ratio of 1 1 ) was produced on a Weber 90 (90 mm extruder) equipped W 096/35750 PCTrUS95/07643 with a Gneuss rotatinq melt filter and fitted with the appropriate standard mandrel and pipe die. Themelttemperaturerangesfrorn190~Cto210~Cat126rpmoftheextruder. The extruder output was 430 kg/hr at a die pressure of 165 to 170 bar, this corresponds to a pipe production output of 1 753 m/min The extruded pipe was vacuum calibrated and water 5 cooled~
The criticcll pressures PC s4 measured in the Small Scale Steady State (54) rapid crack growth tests are as follows:

Temperature Example 6 Example 7 0~C > 10bar > 10bar -10~C > 10bar > 10bar -15~C ~ 10bar ~ 8bar For commercially available polyethylene gas pipes of a diameter of 110 mm and a walI thickness of 10 mm (Standard dimension ratio of 1 1 ) the following values were reported by P. Vanspeybroek (P Vanspeybroek, Proceedings of P!astic Pipes V!!!, Eindhover" The Netherlands, Sept. 199:2" The Plastics and Rubber Institute, p. D1/6 - 1-14):
20 Pc,s4: 2.5 bar (at 0~C) 1 8 bar (at -1 0~C) 1.8 bar (a t 1 5~C)

Claims (12)

1. A medium modulus, molded polyethylene material characterized as having a thickness greater than 0.23 mm which comprises:
(A) from 60 to 99 weight percent, based on the combined weight of components (A) and (B), of at least one high molecular weight linear ethylene polymer having a density in the range of 0.92 to 0.96g/cc and an l5 melt index in the range of 0.1 to 3g/10 minutes, and (B) from 1 to 40 weight percent, based on the combined weight of components (A) and (B), of at least one substantially linear ethylene/.alpha.-olefin interpolymer characterized as having:
i. a melt flow ratio, l10/l2, ~ 5.63, ii. a molecular weight distribution, Mw/Mn, defined by the equation:
Mw/Mn~(l10/l2)-4.63, and iii. a critical shear rate at onset of surface melt fracture at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having essentially the same l2 and Mw/Mn, wherein the substantially linear ethylene/.alpha.-olefin polymer is further characterized as containing at least one .alpha.-olefin monomer and having a density in the range of 0.85 to 0.92 g/cc and an l2 melt index in the range of 0.3 to 3 g/10 minutes.
2. The material of Claim 1 wherein said material comprises from 60 to 95 weight percent of said component (A) and from 5 to 40 weight percent of said component (B), based on the combined weights of components (A) and (B).
3. The material of Claim 1 or Claim 2 wherein said material is a pipe, tube, bar, wire coating, sheet, an automotive part or a container.
4. The material of any one of Claims 1 to 3 wherein its thickness is in the range of 0.5mm to 50mm.
5. The material of any one of Claims 1 to 4 wherein said high molecular weight linear ethylene polymer is an interpolymer of ethylene and at least one .alpha.-olefin, the .alpha.-olefin being 1-propylene, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene.
6. The material of any one of Claims 1 to 5 wherein said substantially linear ethylene/.alpha.-olefin polymer is further characterized as having from 0.01 long chain branches/1000 carbons to 3 long chain branches/1000 carbons along the polymer backbone.
7. The material of any one of Claims 1 to 6 wherein said substantially linear ethylene/.alpha.-olefin polymer is an interpolymer of ethylene and at least one .alpha.-olefin, the .alpha.-olefin being 1-propylene, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene.
8. The material of any one of Claims 1 to 7 wherein said high molecular weight linear ethylene polymer has an l5 melt index in the range of 0.15 g/10 min. to 0.5 g/10 min.
9. The material of any one of Claims 1 to 8 wherein said substantially linear ethylene polymer has an l2 melt index in the range of 0.3 g/10 minutes to 2.5 g/10 minutes.
10. The material of any one of Claims 1 to 9 wherein said substantially linearethylene polymer has a density in the range of 0.855 g/cc to 0.918 g/cc.
11. A method for preparing the medium modulus molded polyethylene material of any one of Claims 1 to 10 comprising the steps of:
(1) providing an extrudable thermoplastic composition containing (A) from 60 to 99 weight percent, based on the combined weights of components (A) and (B), of at least one high molecular weight linear ethylene polymer having a density in the range of 0.92 to 0.96 g/cc and an l5 melt index in the range of 0.1 to 3 g/10 minutes, and (B) from 1 to 40 weight percent, based on the combined weights of components (A) and (B), of at least one substantially linear ethylene/.alpha.-olefin interpolymer characterized as having:
i. a melt flow ratio, l10/l2, ~ 5.63, ii. a molecular weight distribution, Mw/Mn, defined by the equation:
Mw/Mn ~ (l10/l2)-4.63,and iii. a critical shear rate at onset of surface melt fracture at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having essentially the same l2 and Mw/Mn, wherein the substantially linear ethylene/.alpha.-olefin interpolymer is further characterized as containing at least one .alpha.-olefin monomer and having a density in the range of 0.85 to 0.92g/cc and an l2 melt index in the range of 0.3 to 3 g/10 minutes, optionally pelletizing the composition, (2) introducing said optionally pelletized composition of step (1) into an extrusion apparatus, and (3) extruding said composition of step(1) to form a material with a thickness greater than 0.23 mm, and (4) conveying said material formed in step (3) for subsequent use down-line of the extrusion apparatus of step (2) or collecting said material formed in step (3) for subsequent use off-line.
12. A pipe or tube produced by the method of Claim 11.
CA 2220439 1994-05-09 1995-06-16 Medium modulus molded material comprising substantially linear polyethylene and fabrication method Abandoned CA2220439A1 (en)

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Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5792534A (en) 1994-10-21 1998-08-11 The Dow Chemical Company Polyolefin film exhibiting heat resistivity, low hexane extractives and controlled modulus
US6506866B2 (en) * 1994-11-17 2003-01-14 Dow Global Technologies Inc. Ethylene copolymer compositions
US5770318A (en) * 1995-01-13 1998-06-23 Norton Performance Plastics Corporation Thermoplastic seal and wrapping film
US6204349B1 (en) * 1995-06-22 2001-03-20 Mitsubishi Chemical Corporation Pipe made of polyethylene resin
JPH09309926A (en) * 1996-05-17 1997-12-02 Dow Chem Co:The Production of ethylene copolymer
US6485662B1 (en) * 1996-12-03 2002-11-26 Union Carbide Chemicals & Plastics Technology Corporation Process for preparing a simulated in situ polyethylene blend
FI111166B (en) * 1997-01-10 2003-06-13 Borealis Polymers Oy Extrusion coating
KR100551854B1 (en) * 1997-06-20 2006-02-13 다우 글로벌 테크놀로지스 인크. Ethylene polymer compositions and article fabricated from the same
US6147179A (en) * 1997-06-25 2000-11-14 Eastman Chemical Company Monolayer film
BE1011282A3 (en) * 1997-07-14 1999-07-06 Solvay Composition based on polyethylene and method for manufacturing shaped objects from the composition.
US6451916B1 (en) 1997-07-21 2002-09-17 The Dow Chemical Company Midland Broad MWD, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom
US6197887B1 (en) 1997-09-12 2001-03-06 Eastman Chemical Company Compositions having particular utility as stretch wrap cling film
US6204335B1 (en) 1997-09-12 2001-03-20 Eastman Chemical Company Compositions of linear ultra low density polyethylene and propylene polymers and films therefrom
US6070394A (en) * 1997-09-12 2000-06-06 Eastman Chemical Company Lownoise stretch wrapping process
US6153702A (en) 1997-09-12 2000-11-28 Eastman Chemical Company Polymers, and novel compositions and films therefrom
KR20010024063A (en) 1997-09-19 2001-03-26 그래햄 이. 테일러 Narrow mwd, compositionally optimized ethylene interpolymer composition, process for making the same and article made therefrom
EP1162211B2 (en) * 1999-06-17 2011-08-24 Mitsui Chemicals, Inc. Ethylene (co)polymers and uses thereof
EP1213523A4 (en) * 2000-06-22 2006-04-12 Idemitsu Kosan Co Pipe made of ethylene polymer
US7135526B2 (en) 2001-06-22 2006-11-14 Univation Technologies, Llc Very low density polyethylene and high density polyethylene blends
JP2004501243A (en) * 2000-06-22 2004-01-15 エクソンモービル・ケミカル・パテンツ・インク Very low density polyethylenes produced using metallocene
EP1225201A1 (en) * 2001-01-12 2002-07-24 ATOFINA Research High shrink polyethylene films
KR100898436B1 (en) * 2001-03-16 2009-05-21 다우 글로벌 테크놀로지스 인크. Method of making interpolymers and products made therefrom
CN1301292C (en) * 2001-08-17 2007-02-21 陶氏环球技术公司 Bimodal polyethylene pipe composition, article made therefrom and application thereof
KR100872219B1 (en) * 2001-08-31 2008-12-05 다우 글로벌 테크놀로지스 인크. Multimodal polyethylene material
US20030113496A1 (en) * 2001-12-17 2003-06-19 Harris Michael G. Polyethylene melt blends for high density polyethylene applications
KR100792111B1 (en) 2001-12-21 2008-01-04 삼성토탈 주식회사 Polyethylene Resin Composition For Pipe With High Creep Resistance
US6822051B2 (en) * 2002-03-29 2004-11-23 Media Plus, Inc. High density polyethylene melt blends for improved stress crack resistance in pipe
KR100655973B1 (en) 2005-10-28 2006-12-04 현대자동차주식회사 Method of measurement for scrap contents in talc-polypropylene composite using rheological analysis technique
US7803629B2 (en) 2006-06-27 2010-09-28 Chevron Phillips Chemical Company, Lp Method for employing SEC-FTIR data to predict mechanical properties of polyethylene
WO2008054637A1 (en) * 2006-10-30 2008-05-08 Dow Global Technologies Inc. Adhesive films
CN101688032A (en) * 2007-05-09 2010-03-31 陶氏环球技术公司 Ethylene-based polymer compositions, methods of making the same, and articles prepared therefrom
CN101891912A (en) * 2010-07-29 2010-11-24 任意 High-strength and high-modulus polyethylene film and continuous solid-state extrusion overstretching production method thereof
CN103865142A (en) * 2012-12-11 2014-06-18 神华集团有限责任公司 Crosslinkable polyethylene co-mixed composition
CA2800056A1 (en) * 2012-12-24 2014-06-24 Nova Chemicals Corporation Polyethylene blend compositions
KR20150100694A (en) * 2012-12-27 2015-09-02 다우 글로벌 테크놀로지스 엘엘씨 Catalyst systems for olefin polymerization

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA849081A (en) * 1967-03-02 1970-08-11 Du Pont Of Canada Limited PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES
DE2534635C3 (en) * 1975-08-02 1978-03-16 Allgemeine Synthetische Gesellschaft Etablissement, Vaduz
JPS6358174B2 (en) * 1979-12-26 1988-11-15 Nippon Oil Co Ltd
JPS6329701B2 (en) * 1980-09-26 1988-06-15 Showa Denko Kk
US4438238A (en) * 1981-01-30 1984-03-20 Sumitomo Chemical Company, Limited Low density copolymer composition of two ethylene-α-olefin copolymers
US4461873A (en) * 1982-06-22 1984-07-24 Phillips Petroleum Company Ethylene polymer blends
US5102611A (en) * 1990-05-18 1992-04-07 Phillips Petroleum Company Process for making smooth plastic tubing
JP3045548B2 (en) * 1990-12-28 2000-05-29 日本石油化学株式会社 Polyethylene composition
CA2078366A1 (en) * 1991-09-18 1993-03-19 Joel L. Martin Polyethylene blends
US5272236A (en) * 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5278272A (en) * 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5395471A (en) * 1991-10-15 1995-03-07 The Dow Chemical Company High drawdown extrusion process with greater resistance to draw resonance
DE69322082T2 (en) * 1992-04-20 1999-06-17 Exxon Chemical Patents Inc Copolymers of ethylene with branched olefins
US5284613A (en) * 1992-09-04 1994-02-08 Mobil Oil Corporation Producing blown film and blends from bimodal high density high molecular weight film resin using magnesium oxide-supported Ziegler catalyst
US5408004A (en) * 1993-08-17 1995-04-18 The Dow Chemical Company Polyolefin blends and their solid state processing

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