Source: https://patents.google.com/patent/US8101687
Timestamp: 2018-03-17 19:09:22
Document Index: 227136479

Matched Legal Cases: ['Application No. 10', '§371', 'Application No. 60', 'Application No. 02759487', 'Application No. 02759487', 'Application No. 02', 'Application No. 02', 'Application No. 02', 'Application No. 02']

US8101687B2 - Multimodal polyethylene material - Google Patents
US8101687B2
US8101687B2 US11634503 US63450306A US8101687B2 US 8101687 B2 US8101687 B2 US 8101687B2 US 11634503 US11634503 US 11634503 US 63450306 A US63450306 A US 63450306A US 8101687 B2 US8101687 B2 US 8101687B2
US11634503
US20070112160A1 (en )
Julien Damen
The present invention relates to a polyethylene resin having a multimodal molecular weight distribution, said resin being further characterized in that it has a density in the range of from about 0.925 g/ccm to about 0.950 g/ccm, a melt index (I2) In the range of from about 0.05 g/10 min to about 5 g/10 min, and in that it comprises at least one high molecular weight (HMW) ethylene interpolymer and at least a low molecular weight (LMW) ethylene polymer, and a composition comprising such resin. Also provided is a shaped article comprising said resin or composition, in particular a pipe.
The present application is a continuation application of U.S. Application No. 10/484,906, filed Aug. 10, 2004, now U.S. Pat. No. 7,250,473, which is a 35 U.S.C. §371 National Stage of International Application No. PCT/US02/27503, filed on Aug. 28, 2002, which claims the benefit of U.S. Provisional Application No. 60/316,401, filed Aug. 31, 2001; each application is incorporated herein, in its entirety, by reference.
In view of the potentially disastrous consequences of material failures, acceptance of any plastic pipe for water or gas distribution is subject to product standards and performance requirements set forth in norms, for example, DIN (German Instrustrial Norm or “Deutsche Industrie Norm”) or norms defined by ISO (International Organization for Standardization, Geneva, Switzerland). For example, state of the art polyethylene materials sold into pipe applications, such as pressure pipes or irrigation pipes, meet the so-called PE80 or PE100 ratings (PE stands for polyethylene). Pipes manufactured from polyethylenes classifying as PE80-type or PE100-type resins must withstand a minimum circumferential stress, or hoop stress, of 8 MPa (PE80) or 10 MPa (PE100) at 20° C. for 50 years. PE100 resins are high density polyethylene (HDPE) grades typically having a density of at least about 0.950 g/ccm3 or higher.
Their relatively poor Long Term Hydrostatic Strength (LTHS) at high temperatures has been an acknowledged disadvantage of traditional polyethylenes which rendered these materials unsuitable for use in piping with exposure to higher temperatures, such as domestic pipe applications. Domestic pipe systems typically operate at pressures between about 2 and about 10 bar and temperatures of up to about 70° C. with malfunction temperatures of about 95-100° C. Domestic pipes include pipes for hot and/or cold water in pressurized heating and drinking water networks within buildings as well as pipes for snow melt or heat recovery systems. The performance requirements for the various classes of hot water pipes, including underfloor heating, radiator connectors and sanitary pipes are specified, for example, in International Standard ISO 10508 (first edition Oct. 15, 1995, “Thermoplastic pipes and fittings for hot and cold water systems”).
There still is the need for new polyethylene materials which offer an advantageously balanced combination of thermal, mechanical and processing properties. In particular, there still is the need for new polyethylene materials, which afford superior high temperature resistance (e.g., in the range of operating temperatures from about 40° C. to about 80° C. and test temperatures of up to about 110° C.), high stress resistance, good tensile and impact performance and excellent processability without having to be crosslinked. It is an object of the present invention to meet these and other needs.
The term “comprising” as used herein means “including”.
The term “interpolymer” is used herein to indicate polymers prepared by the polymerization of at least two monomers. The generic term interpolymer thus embraces the terms copolymer, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, such as terpolymers.
Unless indicated to the contrary, all parts, percentages and ratios are by weight. The expression “up to” when used to specify a numerical range includes any value less than or equal to the numerical value which follows this expression. The expression “from to” when used to specify a numerical range includes any value equal to or higher than the numerical value which follows this expression. In these contexts, the word “about” is used to indicate that the specified numerical limit represents an approximate value which may vary by 1%, 2%, 5% or sometimes 10%.
“HMW” stands for high molecular weight, “LMW” stands for low molecular weight.
The abbreviation “ccm” stands for cubic centimeters.
Unless expressly specified otherwise, the term “melt index” means the I2 melt index, as determined in accordance with ASTM D1238 under a load of 2.16 kg and at a temperature of 190° C.
Unless specified otherwise, the term “alpha-olefin” (α-olefin) refers to an aliphatic or cyclo-aliphatic alpha-olefin having at least 4, preferably from 4 to 20 carbon atoms.
For example, a bimodal MWD can be deconvoluted into two components: the HMW component and the LMW component. After deconvolution, the peak width at half maxima (WAHM) and the weight average molecular weight (Mw) of each component can be obtained. Then the degree of separation (“DOS”) between the two components can be calculated by the following equation:
wherein Mw H and Mw L are the respective weight average molecular weight of the HMW component and the LMW component; and WAHMH and WAHML are the respective peak width at the half maxima of the deconvoluted molecular weight distribution curve for the HMW component and the LMW component. The DOS for the bimodal resins according to the invention is at least 0.01 or higher, preferably higher than about 0.05, 0.1, 0.5, or 0.8.
Homogeneous ethylene interpolymers for use in the present invention encompass ethylene-based interpolymers in which any comonomer is randomly distributed within a given interpolymer molecule and wherein all of the interpolymer molecules have substantially the same ethylene/comonomer ratio. Homogeneous ethylene interpolymers are generally characterized as having an essentially single melting (point) peak between −30° C. and 150° C., as determined by differential scanning calorimetry (DSC). Typically, homogeneous ethylene interpolymers also have a relatively narrow molecular weight distribution (MWD) as compared to corresponding heterogeneous ethylene interpolymers. Preferably, the molecular weight distribution defined as the ratio of weight average molecular weight to number average molecular weight (Mw/Mn), is less than about 3.5. Furthermore, the homogeneity of the ethylene interpolymers is reflected in a narrow composition distribution, which can be measured and expressed using known methods and parameters, such as SCBDI (Short Chain Branch Distribution Index) or CDBI (Composition Distribution Breadth Index). The SCBDI of a polymer is readily calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (typically abbreviated as “TREF”) as described, for example, in Wild et al, Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), in U.S. Pat. No. 4,798,081 (Hazlitt et al.), or in U.S. Pat. No. 5,089,321 (Chum et al.), the disclosures of all of which are incorporated herein by reference. CDBI 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 SCBDI or CDBI for the homogeneous ethylene/alpha-olefin interpolymers used in the present invention is typically higher than about 50 percent.
The substantially linear ethylene interpolymers (SLEPs) are homogeneous interpolymers having long chain branching, meaning that the bulk ethylene interpolymer is substituted, on average, with about 0.01 long chain branches/1000 total carbons to about 3 long chain branches/1000 total carbons (wherein “total carbons” includes both backbone and branch carbon atoms). Preferred polymers are substituted with about 0.01 long chain branches/1000 total carbons to about 1 long chain branches/1000 total carbons, more preferably from about 0.05 long chain branches/1000 total carbons to about 1 long chain branched/1000 total carbons, and especially from about 0.3 long chain branches/1000 total carbons to about 1 long chain branches/1000 total carbons. The presence of long chain branches in such ethylene interpolymers can be determined according to methods known in the art, such as 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 substantially linear ethylene polymers are a unique class of compounds which has been described in numerous publications, including e.g., U.S. Pat. No. 5,272,236, U.S. Pat. No. 5,278,272, and U.S. Pat. No. 5,665,800, each of which is incorporated herein by reference. Such SLEPs are available, for example, from The Dow Chemical Company as polymers made by the INSITE™ Process and Catalyst Technology, such as AFFINITY™ polyolefin plastomers (POPs).
In general, the continuous polymerization required to manufacture substantially linear ethylene polymers may be accomplished at conditions well known in the art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0 to 250° C. and pressures from atmospheric to 1000 atmospheres (100 MPa). Suspension, solution, slurry, gas phase or other process conditions may be employed if desired.
Heterogeneous ethylene-based polymers encompass ethylene/α-olefin interpolymers characterized as having a linear backbone and a DSC melting curve having a distinct melting point peak greater than 115° C. attributable to a high density fraction. Such heterogeneous interpolymers typically have a broader molecular weight distribution than comparable homogeneous interpolymers. Typically, heterogeneous ethylene interpolymers have a CDBI of about 50% or less, indicating that such interpolymers are a mixture of molecules having differing comonomer contents and differing amounts of short chain branching. The heterogeneous ethylene polymers that can be used in the practice of this invention include those prepared with a coordination catalyst at high temperature and relatively low pressure. Ethylene polymers and copolymers prepared by the use of a (multi-site) coordination catalyst, such as a Ziegler-Natta catalyst or a Phillips catalyst, are generally known as linear polymers because of the substantial absence of branch chains of polymerized monomer units pendant from the backbone.
The present invention also provides compositions comprising the multimodal polyethylene resin of the invention and at least one other additional component. Preferably, such additional component is added to the multimodal polyethylene resin of the invention. Suitable additional components include, for example, other polymers, fillers or additives—with the proviso that these additional components do not adversely interfere with the desired advantageous properties of the multimodal polyethylene resin of the invention. Rather, the additional components are selected such as to support the advantageous properties of the multimodal ethylene resin of the invention and/or to support or enhance its particular suitability for a desired application. Other polymers comprised in the composition of the invention means polymers which do not qualify as a HMW interpolymer or a LMW polymer as defined herein. Advantageously, such polymers are compatible with the multimodal polyethylene resin of the invention. Preferred additional components are non-polymeric. Additives include processing aids, UV stabilizers, antioxidants, pigments or colorants. Most preferred are compositions comprising a preferred, more preferred or most preferred multimodal polyethylene resin of the invention.
The multimodal polyethylene resins and compositions according to the present invention are particularly suitable for durable application, especially pipes—without the need for cross-linking. Pipes comprising at least one multimodal polyethylene resin as provided herein are another aspect of the present invention and include monolayer pipes as well as multilayer pipes, including multilayer composite pipes. Typically, the pipes of the invention comprise the multimodal polyethylene resin in form of a composition (formulation) which also contains a suitable combination of additives, e.g. an additive package designed for pipe applications, and/or one or more fillers. Such additives and additive packages are known in the art.
The resins and compositions provided by the present invention are particularly suitable for use in domestic and technical pipe applications required to be operable at higher temperatures, e.g. above 40° C., in particular in the range of from above 40° C. to about 80° C. Such pipe applications include, for example, hot water pipes, e.g. for drinking and/or sanitary purposes and underfloor heating pipes. Such pipes may be monolayer or multilayer pipes. Preferred pipes according to the invention meet the performance requirements as defined in the norms for hot water pipes, e.g. in ISO 10508. The multimodal polyethylene resin according to the present invention enables pipes combining an excellent high temperature performance, as reflected e.g. in an excellent Long Term Hydrostatic Strength at higher temperatures (well above 20° C.) with good flexibility. Good flexibility facilitates e.g. pipe installation. The pipes can be produced without cross-linking, which allows improved processing economics and subsequent welding.
For plastic pipe applications, circumferential (hoop) stress performance as set forth in ISO 9080 and ISO 1167 is an important requirement. The long term behaviour or lifetime of plastic pipes can be predicted based on creep rupture data and curves which establish the allowable hoop stress (circumferential stress) which a pipe can withstand without failure. Typically, for long term predictive performance testing, candidate pipe materials are subjected to various pressures (stresses) and the lifetime at a given temperature is determined. For extrapolations to a lifetime of 50 years, e.g. at 20° C. to 70° C., testing is also performed at higher temperatures. The measured lifetime curves at each temperature typically comprise a high stress, lower lifetime ductile failure mode and a lower stress, longer lifetime brittle failure mode. A schematic representation of typical lifetime curves is found at page 412, FIG. 5, of the publication by J. Scheirs et al., TRIP 4 (12), 1996, pages 408-415. The curves can be divided into three stages, stage I representing the ductile failure stage, stage II (knee) representing a gradual change in failure mode from ductile to brittle, and stage III representing the brittle failure stage. Of particular interest are stages II and III, because these stages control the lifetime of a pipe in practice. The pipes of the present invention show an excellent hoop stress performance particularly at higher temperatures.
Melt indices are expressed as I2 (determined according to ASTM D-1238, condition E, 190° C./2.16 kg). The ratio of I10 (measured according to ASTM D-1238, Condition N, 190° C./10 kg) to I2 is the melt flow ratio and designated as I10/I2.
Yield stress [MPa]: 21
Yield strain [%]: 13
Maximum tensile stress [MPa] 36
Maximum elongation [%] 760
Stress at break [MPa] 36
Strain at break [%] 760
Flexural modulus [MPa] 955
Hardness D 61
Izod at 20° C. [J/m] 238
Izod at −40° C. [J/m] 8
Monolithic pipes made from the above resin are subjected to hydrostatic pressure testing using the test method described in ISO 1167 (1996) and water as the internal and external test medium. The pipes have nominal dimensions of 16 mm×2 mm.
Temperature Hoop Stress Failure time
[° C.] [MPa] [h]* Failure Mode*
20 10.57 >3096
20 10.54 >10344
20 10.44 >10344
20 10.40 >4056
20 10.32 >4056
80 5.65 656 ductile
80 5.59 1245 ductile
80 5.52 >5952
80 5.49 >3600
80 5.45 >3600
80 5.42 >5952
80 5.35 >4056
80 5.34 >3600
80 5.30 >5952
80 5.25 >3600
110 2.91 >3912
110 2.89 >3912
110 2.84 >2616
110 2.79 >3912
110 2.47 >11976
110 2.11 >11976
*“>” indicates that the specimen is still under test without failure. In such cases, no failure mode can be indicated.
The pipes made from the bimodal polyethylene resin show an excellent hoop stress performance, especially at high(er) temperatures. Surprisingly, no knee (stage II) reflecting a change in failure mode from ductile to brittle is manifest, yet. Test results already go beyond the control points for PE-RT according to DIN 16883 (1.9 MPa/8760 h at 110° C.) and PEX according to ISO 10146 (2.5 MPa/8760 h at 110° C.).
wherein the at least one high molecular weight interpolymer is a homogeneous ethylene interpolymer that has a single melting point between −30° C. and 150° C., and a CDBI greater than 50 percent; and the at least one low molecular weight ethylene polymer is a heterogeneous ethylene interpolymer that has a linear backbone, a DSC melting point greater than 115° C. attributed to a high density fraction, and a CDBI of 50 percent or less.
wherein the at least one high molecular weight interpolymer is a homogeneous ethylene interpolymer that has a single melting point between −30° C. and 150° C., and a CDBI greater than 50 percent; and wherein the at least one low molecular weight ethylene polymer is a heterogeneous ethylene interpolymer that has a linear backbone, a DSC melting point greater than 115° C., attributable to a high density fraction, and a CDBI of 50 percent or less.
US11634503 2001-08-31 2006-12-06 Multimodal polyethylene material Active US8101687B2 (en)
US31640101 true 2001-08-31 2001-08-31
PCT/US2002/027503 WO2003020821A1 (en) 2001-08-31 2002-08-28 Multimodal polyethylene material
US10484906 US7250473B2 (en) 2001-08-31 2002-08-28 Multimodal polyolefin pipe
US11634503 US8101687B2 (en) 2001-08-31 2006-12-06 Multimodal polyethylene material
US10484906 Continuation
PCT/US2002/027503 Continuation WO2003020821A1 (en) 2001-08-31 2002-08-28 Multimodal polyethylene material
US20070112160A1 true US20070112160A1 (en) 2007-05-17
US8101687B2 true US8101687B2 (en) 2012-01-24
ID=23228883
US10484906 Active US7250473B2 (en) 2001-08-31 2002-08-28 Multimodal polyolefin pipe
US11634503 Active US8101687B2 (en) 2001-08-31 2006-12-06 Multimodal polyethylene material
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