Title of Invention	A LINER
Abstract	The present invention relates to a flexible, protective, integral liner comprising at least one first polymer which is a homogeneous linear or substantially linear ethylene/a.-olefin interpolymer having a density of from 0.850 g/cm3 to 0.920 g/cm3, and at least one second polymer which is an ethylene/a.-o}olefin interpolymer having a density of from 0.905 g/cm3 to 0.935 g/cm3; provided that the density of the second polymer is at least 0.002 g/cm3 greater than the density of the first polymer. In preferred embodiments, the liner will further comprise an ignition resistance additive. The liners of the invention exhibit an excellent balance of flexibility and strength, and, when an ignition resistance additive is employed, excellent ignition resistance.

Title of Invention

A LINER

Abstract

The present invention relates to a flexible, protective, integral liner comprising at least one first polymer which is a homogeneous linear or substantially linear ethylene/a.-olefin interpolymer having a density of from 0.850 g/cm3 to 0.920 g/cm3, and at least one second polymer which is an ethylene/a.-o}olefin interpolymer having a density of from 0.905 g/cm3 to 0.935 g/cm3; provided that the density of the second polymer is at least 0.002 g/cm3 greater than the density of the first polymer. In preferred embodiments, the liner will further comprise an ignition resistance additive. The liners of the invention exhibit an excellent balance of flexibility and strength, and, when an ignition resistance additive is employed, excellent ignition resistance.

Full Text	Liner Compositions The subject invention pertains to liner compositions. In particular, the subject invention pertains to liner compositions which comprise a first layer and at least one second layer, wherein the first layer comprises at least one homogeneous linear or substantially linear ethylene/a-olefin interpolymer. Liner compositions have been historically utilized in a variety of application, such as pond liners, roofing membranes, tunnel liners, etc. Such applications typically require a balance of flexibility and impact resistance. In certain of these applications, it is necessary that the liner further comply with certain flame retardancy criteria. Due to its flexibility and ability to incorporate flame retardants, flexible PVC has found utility in tunnel liner applications. However, PVC is disadvantageous in that it utilizes a plasticizer, which tends to migrate with time and cause a decrease in flexibility; and, in that it exhibits poor low temperature flexibility. EP 508415-A2 discloses polymeric blends of a propylene homopolymer or copolymer, very low density polyethylene, a modified polymer, and a flame retardant filler. However, as characterized by EP 646623-A2, the compositions do not exhibit high weldability coupled with compliance with the flame retardance test set forth in DIN 4102 Bl, both of which are traditionally requirements for use in tunnel liner applications. EP 646623-A2 discloses polymer compositions useful in tunnel liners, which comprise a blend of two very low density polyethylenes and a flame retardant composition. Exemplified is a blend of a very low density polyethylene having a density of 0.900 g/cm3 and a melt index (I2) of 0.7 g/10 minutes with a very low density polyethylene having a density of 0.885 g/cm3 and a melt index (Ij) of 2.5 g/lO minutes. While very low density polyethylene does exhibit somewhat enhanced flexibility as compared to higher density linear low density polyethylene materials, it would be desirable to prepare structures exhibiting a further degree of flexibility, while not sacrificing the good impact resistance which is characteristic of very low density polyethylene. Accordingly, the subject invention provides a flexible, protective, integral liner comprising: a, a first polymer component which in turn comprises at least one first ethylene/a-olefin interpolymer which is a homogeneous linear or substantially linear ethylene/a- olefin interpolymer having a density of from 0.850 g/cm3 to 0.920 g/cm3 b. a second polymer component which in turn comprises at least one second ethylene/a-olefin interpolymer having a density of from 0.905 g/cm3 to 0.935 g/cm3, provided that the density of the at least one second ethylene/a-olefin interpolymer is at least 0.002 g/cm3 greater than the density of the at least one first ethylene/a-olefin interpolymer, wherein the liner has a total thickness of 0.3 to 4 mm, and exhibits a flexural modulus, as determined in accordance with ISO 178, of no more than 150 MPa and an Impact Resistance at -10°C, as determined in accordance with ISO 6603, of at least 35 J/mm. In a preferred embodiment of the invention, the liner will further comprise an ignition resistance additive. In such embodiments, satisfactory flame retardancy (that is, ignition resistance of Bl, as determined in accordance with DIN 4102) will preferably be achieved without sacrificing the balance of properties described above. Even more preferably, the satisfactory flame retardancy will be achieved while employing low amount of the ignition resistance additive (that is, no more than 20 weight percent, more preferably no more than 15 weight percent, and most preferably no more than 10 weight percent of a halogenated ingition resistance additive; no more than 35 weight percent, more preferably no more than 30 weight percent non-halogenated ignition resistance additive) . The liners of the invention exhibit outstanding flexibility and mechanical properties, and can be processed on existing polyethylene manufacturing equipment. The liners of the invention which incorporate an ignition resistance additive will further exhibit excellent ignition resistance, will produce lower smoke emissions than flexible PVC liners, and will produce no burning drip while burning. The liners of the invention will be useful in a variety of applications. In particular, the liners of the invention will be usefully employed to prevent the intrusion of water into buildings or other structures, and thus, to prevent water damage to such buildings or structures. Exemplary applications include, but are not limited to, tunnel liners, pond liners, water barriers, roof liners (particularly for tiled roofs) and geological membranes. These and other embodiments are described in the following detailed description. The liner of the invention will comprise at least first and second ethylene/a-olef in interpolymers. The term "interpolymer" is used herein to indicate a copolymer, or a terpolymer, or a higher order polymer. That is, at least one other comonomer is polymerized with ethylene to make the interpolymer. The first and second ethylene/a-olefin interpolymers selected will achieve a balance of properties, for example, an average flexural modulus, as determined in accordance with ISO 178, of no more than 150 MPa, and an Impact Resistance at -10°C, as determined in accordance with ISO 6603, of at least 3 5 J/mm. The liner of the invention may comprise a monolayer structure, with the first and second ethylene/a-olefin interpolymers being present as a homogeneous blend, or may comprise at least two layers, with the first and second ethylene/a-olefin interpolymers being present in disparate layers. While the liner of the invention may be a monolayer, it will preferably comprise at least two layers (referred to herein as an A/B structure). Other structures having more than two layers are possible and will be desirable. One such multilayer structure will employ the same formulations in the layers of the faces of the liner and a different formulation in the interior layer (referred to herein as an A/B/A structure). Preferably, the first ethylene/a-olefin interpolymer will be present in the B layer and the second ethylene/a-olefin interpolymer will be present in the A layer. The first and second ethylene/a-olefin interpolymers will each be interpolymers of ethylene with at least one comonomer selected from the group consisting of C3-C20 a-olefins, non-conjugated dienes, and cycloalkenes. Exemplary C3-C20 α olefins include propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene. Preferred C3-C20 ^ -olefins include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene, more preferably 1-hexene and 1-octene. Exemplary cycloalkenes include cyclopentene, cyclohexene, and cyclooctene. The non-conjugated dienes suitable as comonomers, particularly in the making of ethylene/a-olefin/diene terpolymers, are typically non-conjugated dienes having from 6 to 15 carbon atoms. Representative examples of suitable non-conjugated dienes include: (a) Straight chain acyclic dienes such as 1,4-hexadiene; l, 5-heptadiene; and 1,6-octadiene; (b) Branched chain acyclic dienes such as 5-methyl-l,4-hexadiene; 3,7-dimethyl-1,6-octadiene; and 3,7-dimethyl-1,7-octadiene; (c) Single ring alicyclic dienes such as 4-vinylcyclohexene; l-allyl-4-isopropylidene cyclohexane; 3-allylcyclopentene; 4-allylcyclohexene; and 1-isopropenyl-4-butenylcyclohexene; (d) Multi-ring alicyclic fused and bridged ring dienes such as dicyclopentadiene; alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene; 5-methylene-6-methyl-2-norbornene; 5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-(3-cyclopentenyl)-2-norbornene; 5-ethylidene-2-norbornene; and 5-cyclohexylidene-2-norbornene, One preferred conjugated diene is piperylene. The preferred dienes are selected from the group consisting of 1,4-hexadiene; dicyclopentadiene; 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; 7-methyl-1,6 octadiene; piperylene; and 4-vinylcyclohexene. Preferably, the first ethylene/a-olefin interpolymer (that employed in the B layer of an A/B or an A/B/A structure) will be selected to impact flexibility to the liner of the invention. Preferably, the first ethylene/a-olefin interpolymer will have a density of at least 0.855 g/cm3, more preferably at least 0.860 g/cm3 even more preferably at least 0.865 g/cm3 and most preferably at least 0.870 g/cm3 Preferably, the first ethylene/a-olefin interpolymer will have a density of no more than 0.920 g/cm3, more preferably no more than 0.910 g/cm3, even more preferably no more than 0.900 g/cm3 and most preferably no more than 0,890 g/cm3 Preferably, the second ethylene/a-olefin interpolymer (that employed in the A layer of an A/B or an A/B/A structure) will be selected to impart abuse resistance to the liner of the invention. Preferably, the second ethylene/a-olefin interpolymer will have a density of at least 0.895 g/cm3 more preferably at least 0.900 g/cm3 even more preferably at least 0.905-g/cm3 Preferably, the second ethylene/a-olefin interpolymer will have a density of no more than 0.935 g/cm3 more preferably no more than 0.935 g/cm3, and most preferably no more than 0.920 g/cm3. It is noted that the second ethylene/a-olefin interpolymer will have a density which is at least 0.002 g/cm3 greater, more preferably at least 0.003 g/cm3 greater than that of the first ethylene/a-olefin interpolymer. The molecular weight of the ethylene/a-olefin interpolymers will be selected on the basis of attributes which are intended to be imparted to the liner by the presence of that interpolymer. It is well known that the molecular weight of the polymer will correlate with the melt index (Ij) of the polymer. Typically, the ethylene/a-olef in interpolymers utilized as the first and second ethylene/a-olef in interpolymers will have a melt index of at least 0.01, preferably at least 0.05, and more preferably at least 0.1 g/lO minutes. Typically, the ethylene/a-olef in interpolymers utilized as the first and second ethylene/a-olef in interpolymers will have a melt index of no more than 30, preferably no more than 20, and most preferably no more than 10 g/10 minutes. In the embodiment of the invention wherein the liner is a monolayer structure, the liner will comprise a blend of the first and second polymer components. In this embodiment, the blend of the first and second polymer components will in turn comprise the first ethylene/a-olef in interpolymer in an amount of at least 20, more preferably at least 25, and most preferably at least 30 weight percent; preferably no more than 70, more preferably no more than 75, and most preferably no more than 80 weight percent. Further, in this embodiment, the blend of the first and second polymer components will in turn comprise the second ethylene/a-olefin interpolymer an amount of at least 20, more preferably at least 25, and most preferably at least 30 weight percent; preferably no more than 80, more preferably no more than 75, and most preferably no more than 70 weight percent. In the case of a multilayer structure, each first layer (the B layer in A/B or A/B/A structures) will comprise at least 40 weight percent, more preferably at least 60 weight percent, and most preferably at least 87 weight percent of the first polymer component (which may be the first polymer alone or as present in a homogeneous mixture with a second thermoplastic polymer) . Each first layer will comprise no more than 99 weight percent, more preferably no more than 97 weight percent, and most preferably no more than 93 weight percent of the first polymer component. In the case of a multilayer structure, each second layer (the A layer of an A/B or an A/B/A structure) will comprise at least 40 weight percent, more preferably at least 60 weight percent, and most preferably at least 8 7 weight percent of the second polymer component. Each second layer will comprise no more than 99 weight percent, more preferably no more than 97 weight percent, and most preferably no more than 93 weight percent of the second polymer component. In addition to the first and second ethylene/a-olefin interpolymers utilized, either or both of the first and second polymer components may optionally comprise an additional thermoplastic polymer. When the additional thermoplastic polymer forms a part of the first polymer component, the additional thermoplastic polymer will preferably be an additional heterogeneous or homogeneous ethylene/a-olefin interpolymer having a density of from 0.855 to 0.920 g/cm3, more preferably from 0.870 to 0.890 g/cm3 and having a melt index (I2) of from 0.01 to 30, preferably from 0.1 to 10 g/10 minutes. When the additional thermoplastic polymer forms a part of the second polymer component, the additional thermoplastic polymer will preferably be an additional heterogeneous or homogeneous ethylene/a-olefin interpolymer having a density of from 0.855 to 0.92 0 g/cm3 more preferably from 0.860 to 0.880 g/cm3 and having a melt index (I2) of from 0.01 to 30, preferably from 0.1 to 10 g/10 minutes. While less preferred, the additional thermoplastic polymer may alternatively be a high pressure low density polyethylene or a polypropylene. In the case of monolayer structures, the blend of the first and second polymer components may comprise, for instance from 0 to 4 0 weight percent, preferably from 0 to 25 weight percent, and more preferably from 0 to 15 weight percent of the additional thermoplastic polymer. In the case of multilayer structures, the layer containing the first polymer component (the B layer in A/B and A/B/A structures), may utilize, as the first polymer component, either the first ethylene/a-olefin interpolymer alone or as a blend of the first polymer with from 5 to 75 weight percent, and more preferably from 15 to 65 weight percent, and most preferably from 25 to 60 weight percent of the additional thermoplastic polymer. Likewise, the layer containing the second polymer (the A layer in A/B or A/B/A structures) , may utilize, as the second polymer component, either the second polymer alone or as a blend of the second polymer with from 5 to 60 weight percent, preferably from 10 to 50 weight percent, and more preferably from 40 to 50 weight percent of the additional thermoplastic polymer. In the case of the multilayer structure, it is understood that the selection of the second polymer component of the second layer will be dependent on the selection of the first polymer .component of the first layer. That is, if the layer containing the first polymer component (the B layer in A/B or A/B/A structures) consists essentially of the first ethylene/a-olefin interpolymer, the second polymer component may consist essentially of the second ethylene/α-olefin interpolyraer, without sacrificing flexibility. However, if the first polymer component comprises a blend of the first ethylene/a-olefin interpolymer with an additional thermoplastic polymer (for instance, when the first polymer component is a blend of a substantially linear ethylene/a- olefin interpolymer (the first ethylene/a-olef in interpolymer) and a heterogeneously branched ethylene/a-olef in interpolymer (the additional thermoplastic polymer)), then the second polymer component shall also be designed to contain an additional thermoplastic polymer (for instance, when the second polymer component is a blend of a heterogeneously branched ethylene/a-olefin interpolymer (the second ethylene/a-olefin interpolymer) with a homogeneously branched ethylene/a-olef in interpolymer (the additional thermoplastic polymer)). Although the present invention is intended to encompass the structures of the preceding paragraph, for instance, when it is desired to "cut back" the first ethylene/a-olefin interpolymer with a less expensive additional thermoplastic polymer, from a performance standpoint, it is preferred that the first polymer component consist essentially of the first ethylene/a-olefin interpolymer. The liner of the invention will preferably comprise an ignition resistance additive, suitable to cause the liner to exhibit an ignition resistance of Bl, as determined in accordance with DIN 4102, incorporated herein by reference. Exemplary ignition resistance additives include halogenated ignition resistance additives and halogen-free intumescent systems. One preferred halogenated ignition resistance additive is as Luvogard MB81/PE, available from Lehmann & Voss, which is a brominated compound (83 percent bromine content), which utilizes antimony trioxide as a synergist. One preferred halogen-free intumescent system is ethylene-diamine-posphate (EDAP) or red phosphorus. When a halogenated ingition resistance additive is employed, it will preferably be provided in an amount of at least 1 weight percent, more preferably at least 3 weight percent, and most preferably at least 5 weight percent; preferably no more than 20 weight percent, more preferably no more than 15 weight percent, and most preferably no more than 10 weight percent. When a non-halogenated ignition resistance additive is employed, it will preferably be provided in an amount of at least 1 weight percent, more preferably at least 5 weight percent; preferably no more than 35 weight percent, more preferably no more than 3 0 weight percent. Preferably, the ignition resistance additive will be present in each layer of the liner. The liner of the invention will typically have a thickness of at least 0.3 mm, preferably at least 1.0 mm, and most preferably at least 1.5 mm; typically no more than 4 mm, preferably no more than 3 mm, and most preferably no more than 2.5 mm. The liner of the invention will have a flexural modulus of no more than 150 MPa (which, unless otherwise indicated, is reported as an average between the average machine and cross direction measurements) , as determined in accordance with ISO 178. Preferably, the liner of the invention will be characterized as having a flexural modulus in the machine direction which is within about 30 percent, more preferably within about 25 percent of that in the cross direction. Preferably, in the case of multilayer structures having three or more layers, such as, for example, A/B/A structures, the liner of the invention will have an average flexural modulus in the cross direction of no more than 150 MPa, preferably no more than 130 MPa. Preferably, in the case of multilayer structures having three or more layers, such as, for example, A/B/A structures, the liner of the invention will have an average flexural modulus in the machine direction of no more than 125 MPa, preferably no more than 110 MPa. Preferably, in the case of multilayer structures having two layers, for example, A/B structures, the liner of the invention will have an average flexural modulus of no more than 100 MPa, preferably no more than 90 MPa (when measured from side of the more flexible B layer). Preferably, in the case of multilayer structures having two layers, for example, A/B structures, the liner of the invention will have an average flexural modulus of no more than 100 MPa, preferably no more than 90 MPa (when measured from the side of the less flexible A layer) . In the more preferred embodiment, wherein the A and B layers each comprise a substantially linear ethylene polymer, the liner of the invention will preferably have a flexural modulus of no more than 100 MPa, preferably no more than 80 MPa, more preferably no more than 60 MPa, and most preferably no more than 50 MPa. When the liner is a multilayer structure, it may be characterized as having a thickness ratio, which is defined herein to mean the ratio of the thickness of the first layer (the B layer in an A/B or an A/B/A structure) to each second layer (the A layer(s) in an A/B or an A/B/A structure) of from 1:1 to 15:1, preferably from 5:1 to 12:1, and most preferably from 6:1 to 10:1. Heterogenous polymers are ethylene/a-olefin interpolymers characterized as having a linear backbone and a DSC melting curve having a distinct melting peak greater than 115°C attributable to a high density fraction. Heterogeneous interpolymers will typically have an M„/M„ greater than 3 (when the density of the interpolymer is less than about 0.960 g/cm3) and will typically have a CDBI less than or equal to 50, indicating that such interpolymers are a mixture of molecules having differing comonomer contents and differing amounts of short chain branching. The heterogeneous ethylene/a-olefin interpolymers that can be used in the practice of this invention will be prepared with a coordination catalyst, such as a Ziegler or Phillips catalyst, at a high temperature and a relatively low pressure. Heterogeneous ethylene/a-olefin interpolymers are linear polymers which are characterized as having an absence of long chain branches of polymerized monomer units pendant from the backbone. High density polyethylene (HDPE), generally having a density of 0.941 to 0.965 g/cm-^, is typically a homopolymer of ethylene, and it contains relatively few short chain branch chains relative to the various linear interpolymers of ethylene and an a-olefin. HDPE is well known, and is commercially available in various grades. Linear interpolymers of ethylene and at least one a- olefin of 3 to 12 carbon atoms, preferably of 4 to 8 carbon atoms, are also well known and commercially available. As is well known in the art, the density of a linear ethylene/a-olef in copolymer is a function of both the length of the a-olefin and the amount of such monomer in the copolymer relative to the amount of ethylene, the greater the length of the a- olefin and the greater the amount of a-olefin present, the lower the density of the copolymer. Linear low density polyethylene (LLDPE) is typically a copolymer of ethylene and an a-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms (for example, 1-butene, 1-octene, etc.), that has sufficient a-olefin content to reduce the density of the copolymer to. a density of from 0.915 to 0.935 g/cm3. When the copolymer contains even more a-olefin, the density will drop below about 0,915 g/cm3 and these copolymers are known as ultra low density polyethylene (ULDPE) or very low density polyethylene (VLDPE) . Heterogeneous ethylene/a-olefin interpolymers are available from The Dow Chemical Company as DOWLEXTM linear low density polyethylene and ATTANE™ ultralow density linear low density polyethylene. Heterogeneous linear ethylene/a-olefin interpolymers can be prepared via the solution, slurry or gas phase polymerization of ethylene and one or more optional a- olefin comonomers in the presence of a Ziegler Natta catalyst, by processes such as are disclosed in U.S. Patent No. 4,076,698 to Anderson et al., which is incorporated herein by reference. Preferably, heterogeneous ethylene polymers are typically characterized as having molecular weight distributions, M^,/M„, in the range of from 3.5 to 4.1. Relevant discussions of both of these classes of materials, and their methods of preparation are found in U.S. Patent No. 4,950,541 and the patents to which it refers, all of which are incorporated herein by reference. Homogeneous ethylene/a-olefin intezpolymers include both homogeneous linear and substantially linear ethylene/a-olef in interpolymers. By the term "homogenous", it is meant that any comonomer is randomly distributed within a given interpolymer molecule and substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer. The melting peak of homogeneous linear and substantially linear ethylene polymers, as obtained using differential scanning calorimetry, will broaden as the density decreases and/or as the number average molecular weight decreases. The homogeneous ethylene/a-olefin interpolymers useful in the invention are characterized as having a narrow molecular weight distribution (Mw/Mn) . For the homogeneous ethylene/a-olef ins useful in the practice of the invention, the M^/M^ is from 1.5 to 2.5, preferably from 1.8 to 2.2, most preferably about 2.0. Substantially linear ethylene interpolymers are homogeneous interpolymers having long chain branching. Due to the presence of such long chain branching, stibstantially linear ethylene interpolymers are further characterized as having a melt flow ratio (I10/I2) which may be varied independently of the polydispersity index, the molecular weight distribution Mw/Mn- This feature accords substantially linear ethylene polymers with a high degree of processability despite a narrow molecular weight distribution. It is noted that substantially linear interpolymers useful in the invention differ from low density polyethylene prepared in a high pressure process. In one regard, whereas low density polyethylene is an ethylene homopolymer having a density of from 0.900 to 0.935 g/cm3, the homogeneous linear and substantially linear interpolymers useful in the invention require the presence of a comonomer to reduce the density to the range of from 0.900 to 0.935 g/cm3. The long chain branches of substantially linear ethylene interpolymers have the same comonomer distribution as the interpolymer backbone and can be as long as about the same length as the length of the interpolymer backbone. When a substantially linear ethylene/a-olefin interpolymer is employed in the practice of the invention, such interpolymer will be characterized as substituted with from 0,01 to 3 long chain branches per 1000 carbons. Methods for determining the amount of long chain branching present, both qualitatively and quantitatively, are known in the art. For determining the presence of long chain branching, see, for example, U.S, Patent Nos. 5,272,236 and 5,278,272, each of which is incorporated herein by reference. As set forth therein, a gas extrusion rheometer (GER) may be used to determine the rheological processing index (PI), the critical shear rate at the onset of surface melt fracture, and the critical shear stress at the onset of gross melt fracture, as set forth below. The gas extrusion rheometer useful in the determination of rheological processing index (PI), the critical shear rate at the onset of surface melt fracture, and the critical shear stress at the onset of gross melt fracture, is described by M. Shida, R. N. Shroff, and L. V. Cancio in Polymer Engineering Science, Vol. 17, No. 11, p. 770 (1977), and in "Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold co, (1982) on pp. 97-99, each of which is incorporated herein by reference. GER experiments are performed at a temperature of 190°C, at nitrogen pressures between 250 and 5500 psig (between 1.72 and 37.9 MPa) using a 0.0754 mm diameter, 20:1 L/D die with an entrance angle of 180°. For substantially linear ethylene interpolymers, the PI is the apparent viscosity (in kpoise) of a material measured by GER at an apparent shear stress of 2.15 x 106 dynes/cm3 (0,215 MPa). Substantially linear ethylene interpolymers useful in the invention will have a PI in the range of 0.01 kpoise to 50 kpoise, preferably 15 kpoise or less. Substantially linear ethylene interpolymers have a PI which is less than or equal to 70 percent of the PI of a linear ethylene interpolymer (either a Ziegler polymerized polymer or a homogeneous linear ethylene interpolymer) having an l2f Mw/Mn, each of which is within 10 percent of that of the substantially linear ethylene interpolymer. An apparent shear stress versus apparent shear rate plot may be used to identify the melt fracture phenomena and to quantify the critical shear rate and critical shear stress of ethylene polymers. According to Ramamurthy, in the Journal of Rheology, 30(2), 1986, pp. 337-357, above a certain critical flow rate, the observed extrudate irregularities may be broadly classified into two main types: surface melt fracture and gross melt fracture. Surface melt fracture occurs under apparently steady flow conditions and ranges in detail from loss of specular film gloss to the more severe form of "sharksin." Herein, as determined using the above-described gas extrusion rheometer, the onset of surface melt fracture is characterized as the beginning of losing extrudate gloss at which the surface roughness of the extrudate can only be detected by magnification at 40 times. The critical shear rate at the onset of surface melt fracture for a substantially linear ethylene interpolymer is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture for a linear ethylene polymer having the same comonomer or comonomers and having an I2/ Mw/Mn and density within ten percent of that of the substantially linear ethylene polymer. Gross melt fracture occurs at unsteady extrusion flow conditions and ranges from regular (alternating rough and smooth, helical, etc.) to random distortions. The critical shear stress at the onset of gross melt fracture of substantially linear ethylene interpolymers, especially those having a density greater than 0.910 g/cm3, is greater than 4 x 10^ dynes/cm2 (0.4 MPa). The presence of long chain branching may further be qualitatively determined by the Dow Rheology Index (DRI), which expresses a polymer's "normalized relaxation time as the result of long chain branching." (See, S. Lai and G. W. Knight, ANTEC '93 Proceedings, INSITE™ Technology Polyolefins (SLEP)- New Rules in the Structure/Rheology Relationship of Ethylene a-Olefin Copolymers, New Orleans, La., May 1993. DRI values range from 0 for polymers which do not have any measurable long chain branching, such as TafmerTM products available from Mitsui Petrochemical Industries and Exact"^ products available from Exxon Chemical company) to about 15, and are independent of melt index. In general, for low to medium pressure 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. Substantially linear ethylene interpolymers will have a DRI of preferably at least 0.1, more preferably at least 0.5, and most preferably at least 0.8. DRI may be calculated from the equation; DRI = (3.652879 * TQI • 00649/ŋ0-1)/10 where TQ is the characteristic relaxation time of the interpolymer and TIQ is the zero shear viscosity of the interpolymer. Both TQ and r]^ are the "best fit" values to the Cross equation n/rio - 1/(1 + (y * Xo)l-n) in which n is the power law index of the material, and r\ 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 to 100 radians/second at 160° C and a gas extrusion rheometer (GER) at extrusion pressures from 1,000 to 5,000 psi (6.89 to 34.5 MPa), which corresponds a shear stress of from 0.086 to 0,43 MPa, using a 0.0754 mm diameter, 20:1 L/D die at 190°C. Specific material determinations may be performed from 140 to 190°C as required to accommodate melt index variations. For quantitative methods for determining the presence of long chain branching, see, for example, U.S. Patent Nos. 5,2 72,23 6 and 5,278,272; Randall (Rev. Macromol. Chem. Phys., C29 (2Sc3) , p. 285-297) , which discusses the measurement of long chain branching using °C nuclear magnetic resonance spectroscopy, Zimm, G.H. and Stockmayer, W.H., J. Chem. Phys., 17, 1301 (1949); and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112, which discuss the use of 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). 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 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 polymers. In particular, deGroot and Chum found that the presence of long chain branches in substantially linear ethylene polymers correlated well with the level of long chain branches measured using °C NMR. Further, deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, as such, one can account for the molecular weight increase attributable to octene short chain branches by knowing the mole percent octene in the sample. By deconvoluting the contribution to molecular weight increase attributable to 1-octene short chain branches, deGroot and Chum showed that GPC-DV may be used to quantify the level of long chain branches in substantially linear ethylene/octene copolymers. deGroot and Chum also showed that a plot of log(I2, melt index) as a function of log(GPC weight average molecular weight), as determined by GPC-DV, illustrates that the long chain branching aspects (but not the extent of long chain branching) of substantially linear ethylene polymers are comparable to those of high pressure, highly branched low density polyethylene (LDPE) and are clearly distinct from heterogeneously branched ethylene polymers produced using Ziegler-type catalysts (such as linear low density polyethylene and ultra low density polyethylene) as well as from homogeneous linear ethylene polymers (such as Tafmer""^ products available from Mitsui Petrochemical Industries and Exact*"^ products available from Exxon Chemical Company). Homogeneously branched linear ethylene/a-olefin interpolymers may be prepared using polymerization processes (for example, as described by Elston in USP 3,645,992, incorporated herein by reference) which provide a homogeneous short chain branching distribution. In his polymerization process, Elston uses soluble vanadium catalyst systems to make such polymers. However, others such as Mitsui Petrochemical Company and Exxon Chemical Company have used so-called single site catalyst systems to make polymers having a homogeneous linear structure. U.S. Patent No. 4,93 7,299 to Ewen et al. and U.S. Patent No. 5,218,071, to Tsutsui et al., each of which is incorporated herein by reference, disclose the use of catalyst systems based on hafnium for the preparation of homogeneous linear ethylene polymers. Homogeneous linear ethylene/a-olefin interpolymers are currently available from Mitsui Petrochemical Company under the trade name "Tafmer" and from Exxon Chemical Company under the trade name "Exact". Substantially linear ethylene/a-olefin interpolymers are available from The Dow Chemical Company as Affinity™ polyolefin plastomers. Substantially linear ethylene/a-olefin interpolymers may be prepared in accordance with the techniques described in U.S. Patent No. 5,272,236 and in U.S. Patent No. 5,278,272, each of which is incorporated herein by reference. The homogeneous linear and substantially linear ethylene/a-olefin interpolymers may be suitably prepared using a single site metallocene or a constrained geometry metal complex. Constrained geometry catalysts are disclosed in U.S. Application Serial No. 545,403, filed July 3, 1990 (EP-A-416,815); U.S. Application Serial No. 702,475, filed May 20, 1991 (EP-A-514,828) ; as well as US-A-5,470,993 , 5,374,696, 5,231,106, 5,055,43 8, 5,057,475, 5,096,867, 5,064,802, and 5,132,380. In U.S. Serial Number 720,041, filed June 24, 1991, (EP-A-514,828) certain borane derivatives of the foregoing constrained geometry catalysts are disclosed and a method for their preparation taught and claimed. In US-A 5,453,410 combinations of cationic constrained geometry catalysts with an alumoxane were disclosed as suitable olefin polymerization catalysts. Suitable activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to U. S. Serial No. 07/547,718), EP-A-520,732 (equivalent to U. S. Serial No. 07/876,268), WO 95/00683 (equivalent to U.S. Serial No. 08/82,201), and EP-A-520,732 (equivalent to U. S. Serial No. 07/884,966 filed May 1, 1992. Catalysts found to be particularly suitable in the preparation of substantially linear ethylene/a-olefin interpolymers include, for instance, the catalysts described in the Examples set forth below, as activated by trispentafluorophenylborane and triisobutylaluminum modified methylalumoxane cocatalysts. The molar ratio of metal complex: activating cocatalyst employed preferably ranges from 1:1000 to 2:1, more preferably from 1:5 to 1.5:1, most preferably from 1:2 to 1:1. In the preferred case in which a metal complex is activated by trispentafluorophenylborane and triisobutylaluminum modified methylalumoxane, the titanium:boron:aluminum molar ratio is typically frotn 1:10:50 to 1:0.5:0,1, most typically from about 1:3:5. A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1:100,000 to 1:10, more preferably from 1:50,00 0 to 1:20, and most preferably from 1:10,000 to 1:30. In most polymerization reactions the molar ratio of catalyst :polymerizable compounds employed is from 10- 12:1 to 10-1:1, more preferably from 10-91 to 10-5:1. At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere • Preferably/ therefore, the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen. The polymerization may be carried out as a batchwise or a continuous polymerization process, with continuous polymerization processes being required for the preparation of substantially linear polymers. In a continuous process, ethylene, comonomer, and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom. In general, the first polymer may be polymerized at conditions for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, reactor pressures ranging from atmospheric to 3500 atmospheres. The reactor temperature should be greater than 80°C, typically from 100°C to 250°C, and preferably from 100°C to 150°C, with temperatures at the higher end of the range, and the temperatures greater than 100°C favoring the formation of lower molecular weight polymers. In conjunction with the reactor temperature, the hydrogen:ethylene molar ratio influences the molecular weight of the polymer, with greater hydrogen levels leading to lower molecular weight polymers. When the desired polymer has an I2 of 1 g/10 min, the hydrogen:ethylene molar ratio will typically be 0:1. When the desired polymer has an I2 of 1000 g/10 min., the hydrogen:ethylene molar ratio will typically be from 0.45:1 to 0.7:1. The upper limit of the hydrogen:ethylene molar ratio is from 2,2 to 2.5:1. Generally the polymerization process is carried out with a differential pressure of ethylene of from 10 to 1000 psi (70 to 7000 kPa) , most preferably from 40 to 60 psi (30 to 300 kPa) . The polymerization is generally conducted at a temperature of from 80 to 250°C, preferably from 90 to 170°C, and most preferably from greater than 95°C to 140°C. In most polymerization reactions the molar ratio of catalyst rpolymerizable compounds employed is from 10-1 :l to lO-1:1 more preferably from 10-9 :1 to 10-5 :1, Solution polymerization conditions utilize a solvent for the respective components of the reaction. Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures. Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar-ETM, available from Exxon Chemicals Inc. ; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene. The solvent will be present in an amount sufficient to prevent phase separation in the reactor. As the solvent functions to absorb heat, less solvent leads to a less adiabatic reactor. The solvent-.ethylene ratio (weight basis) will typically be from 2.5:1 to 12:1, beyond which point catalyst efficiency suffers. The most typical solvent:ethylene ratio (weight basis) is in the range of from 5:1 to 10:1. The ethylene/a-olefin interpolymer may alternatively be prepared in a gas phase polymerization process, using the catalysts as described above as supported in an inert support, such as silica. The ethylene/a-olefin interpolymer may further be made in a slurry polymerization process, using the catalysts as described above as supported in an inert support, such as silica. As a practical limitation, slurry polymerizations take place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent. Likewise the a-olefin monomer or a mixture of different a-olefin monomers may be used in whole or part as the diluent. Most preferably the diluent comprises in at least major part the a-olefin monomer or monomers to be polymerized. A typical liner, with a total thickness of 2 mm, of the invention will be characterized as having a flexural modulus, as determined in accordance with ISO 178, of no more than 118 MPa as a mean value, preferably of no more than 8 0 MPa. The liners of the invention will be characterized as having an Impact Resistance at -lO^C, as determined in accordance with ISO 6603, of at least 35 J/mm, more preferably at least 50 J/mm. The following examples are provided to illustrate typical embodiments of the invention, and are not intended to serve as limits as to its scope, The following materials are employed in the preparation of the liners of the examples: Density is measured in accordance with ASTM D792 in which the samples are annealed at ambient temperature for 24 hours before the measurement is taken. Melt index (I2) is measured in accordance with ASTM D-123 8, at a temperature of 190°C, and using a weight of 2.16 kg (in the case of I2) and 5 kg (in the case of I5) . Ignition resistance is measured in accordance with DIN 4102. Modulus is determined in accordance with ISO 5272961. Yield and ultimate tensile strength, yield and ultimate elongation, and toughness are determined in accordance with ISO 5272961. Hardness Shore A and Hardness Shore D are determined in accordance with ISO 868. ISO Impact E is determined in accordance with ISO 18093. Impact at -10°C is determined in accordance with ISO 6603. Flexural modulus is determined in accordance with ISO 178. Modulus (man Young) is determined in accordance with ISO 178. Displacement, strain, stress, and load at yield are determined in accordance with ISO 178. Tear Propagation is measured in accordance with the following procedures. Load thickness at maximum load is measured in accordance with ASTM D-1004/DIN 53515. Energy at break point is measured in accordance with ASTM D-1004/ DIN 53515. Peak absolute is measured in accordance with ASTM D-1004/DIN 53515. Example 1: Preparation of a Coextruded A/B Liner In the screw unit of a first extruder, 88.5 weight percent Polymer 1, 10 weight percent MB-81, and 1.5 weight percent White-MB are melt blended to form a first homogeneous mixture. In the screw unit of a second extruder, 8 9 weight percent Polymer 2, 10 weight percent MB-81, and 1 weight percent CB-MB are melt blended to form a second homogeneous mixture. The liner comprising the first (A) layer and the second (B) layer is formed by coextruding the first and second homogeneous mixtures, respectively. The thickness of the A layer, comprising the first homogeneous mixture, is 250 microns. The thickness of the second layer, comprising the second homogeneous mixture, is 1.75 mm. The liner is evaluated for certain performance attributes, which are set forth in Table Two, following Example Two. Example 2: Preparation of a Coextruded A/B/A Liner In the screw unit of first and third extruders, 89 weight percent Polymer 1, 10 weight percent FR-batch, and 1 weight percent White-MB are melt blended to form first and third homogeneous mixtures. In the screw unit of a second extruder, 89 weight percent Polymer 2, 10 weight percent FR-batch, and 1 weight percent White MB are melt blended to form a second homogeneous mixture. The liner comprising the first and third (A) layers and the second (B) layer is formed by coextruding the first, second, and third homogeneous mixtures, respectively. The thickness of the A layers, comprising the first and third homogeneous mixtures, is 200 microns. The thickness of the second layer, comprising the second homogeneous mixture, is 1.60 mm. The liner is evaluated for certain performance attributes, which are set forth in Table Two. As seen above, both liner 1 and liner 2 exhibit an average flexural modulus of no more than 150 MPa, with liner 2 having an average of 112 MPa and liner 1 having an average of 110 MPa ( (161 + 60) / 2) . In the case of the A/B structure of liner 1, the liner has an average flexural modulus of no more than 90 MPa, that is, an average flexural modulus of about 80 MPa, when measured from side of the more flexible B layer; the liner further has an average flexural modulus of no more than 70 MPa, when measured from the side of the less flexible A layer. In the case of the A/B/A structure of liner 2, the liner has an average flexural modulus in the cross direction of no more than 13 0 MPa; the liner further has an average flexural modulus in the machine direction of no more than 110 MPa. For the purpose of comparison, a 2 mm thick film comprising 88.5 weight percent Polymer 1, 10 weight percent MB-81, and 1.5 weight percent White-MB exhibits an Impact at -10°C of 23.1 J/mm and a flexural modulus of 185 MPa. Examples 3 and 4: Preparation of A/B/A Liners Utilizing a Substantially Linear Polymer in Each Layer In the case of the liner of Example 3, in the screw unit of first and third extruders, 83 weight percent Polymer 3, 16 weight percent of MB-81, and 1 weight percent White-MB are melt blended to form first and third homogeneous mixtures. In the screw unit of a second extruder, 83 weight percent Polymer 4, 16 weight percent FR-batch, and 1 weight percent CB-MB are melt blended to form a second homogeneous mixture. In the case of the liner of Example 4, in the screw unit of first and third extruders, 89 weight percent Polymer 3, 10 weight percent of MB-81, and 1 weight percent White-MB are melt blended to form first and third homogeneous mixtures. In the screw unit of a second extruder, 89 weight percent Polymer 4, 10 weight percent FR-batch, and 1 weight percent CB-MB are melt blended to form a second homogeneous mixture. The liners comprising the first and third (A) layers and the second (B) layer are formed by coextruding the first, second, and third homogeneous mixtures, respectively. In the case of the liners of each of Examples 3 and 4, the thickness of the A layers, comprising the first and third homogeneous mixtures, is 100 microns, and the thickness of the second layer, comprising the second homogeneous mixture, is 1.8 mm. The liners each have an overall thickness of 2 mm. The liners of Examples 3 and 4 are evaluated for certain performance attributes, which are set forth in Table Three. As snown above, liners 3 and 4, each of which utilize A and B layers which comprise a substantially linear ethylene polymer, exhibit an average flexural modulus of no more than 80 MPa (in the case of liner 4) , and of no more than 4 0 MPa (in the case of liner 3). In addition, in the case of the liner of Example 4, tear propagation measurements were made, the results of which are set forth in the following Table Four. Examples 5-7: Comparison of Ignition Resistance Additives In the case of Examples 5-7, 2 mm thick monolayer films are prepared, utilizing Polymer 2, carbon black, a selected ignition resistance additive, and, in the case of Example 5, Aerosil R972. The liners are evaluated for flame retardancy utilizing the LOI test described above. The composition of the liners, the oxygen consumption, and the burn time are set forth in the following Table Five. Each of the Examples set forth in Table Five is compliant with DIN 4102, having attained a rating of Bl. 1. A liner comprising: a, a first polymer component which comprises at least one first ethylene/a-olefin interpolymer which is a homogeneous linear or substantially linear ethylene/a- olefin interpolymer having a density of from 0.850 g/cm3 to 0.920 g/cm3 b. a second polymer component which comprises at least one second ethylene/a-olefin interpolymer having a density of from 0.905 g/cm3 to 0,935 g/cm3, provided that the density of the at least one second ethylene/a-olefin interpolymer is at least 0.002 g/cm3 greater than the density of the at least one first ethylene/a-olefin interpolymer, wherein the liner has a total thickness of 0.3 to 4 mm, and exhibits a flexural modulus, as determined in accordance with ISO 178, of no more than 150 MPa and an Impact Resistance at -10°C, as determined in accordance with ISO 6603, of at least 35 J/mm. 2. The liner of Claim 1, wherein the liner comprises an ignition resistant additive, whereupon the liner exhibits an ignition resistance of Bl, as determined in accordance with DIN 4102. 3. The liner of Claim 2, wherein the ignition resistant additive is provided in an amount of from 1 to 3 5 weight percent, based on the total weight of the liner. 4. The liner of Claim 2, wherein the ignition resistant additive is provided to each layer in an amount of from 3 to 15 weight percent, based on the total weight of layer. 5. The liner of Claim 2, wherein the ignition resistant additive is provided to each layer in an amount of from 7 to 13 weight percent, based on the total weight of the layer. 6. The liner of Claim 2, wherein the ignition resistant additive is selected from the group consisting of halogenated ignition resistant additives and intumescent ignition resistant additives. 7- The liner of Claim 1, wherein the at least one first ethylene/a-olefin interpolymer has a density of from 0.87 to 0-89 g/cm3 8. The liner of Claim 1, wherein the at least one first ethylene/a-olefin interpolymer is characterized as having an Mw/Mn of from 1,5 to 2.5, 9. The liner of Claim 1, wherein the at least one first ethylene/a-olefin interpolymer is prepared using a single site metallocene or constrained geometry catalyst. 10. The liner of Claim 1, wherein the at least one second ethylene/a-olefin interpolymer has a density of from 0.900 to 0.92 0 g/cm3 11. The liner of Claim 1, wherein the at least one second ethylene/a-olefin interpolymer is a heterogeneous linear polymer or a homogeneous linear or substantially linear polymer. 12. The liner of Claim 1, wherein at least one of the at least one first or second ethylene/a-olefin interpolymers is an interpolymer of ethylene and at least one C3-C20 a-olefin. 13. The liner of Claim 12, wherein the at least one C3-C20 a- olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, and 1-octene. 14. The liner of Claim 12, wherein at least one of first or second ethylene/a-olefin interpolymers is an interpolymer of ethylene, at least one C3-C20 a-olefin, and at least one diene. 15. The liner of Claim 1, comprising a first layer and at least one second abuse resistant layer, such that the thickness of the first layer and the thickness of each second abuse resistant layer is selected such that the thickness ratio is from 1:1 to 15:1, 16. The liner of Claim 15, wherein the thickness of the first layer and the thickness of each second layer is selected such that the thickness ratio is from 5:1 to 12:1. 17. The liner of Claim 16, wherein the thickness of the first layer and the thickness of each second layer is selected such that the thickness ratio is from 6:1 to 10:1. 18. The liner of Claim 1, wherein the liner comprises one first layer and two second abuse resistant layers, which are configured such that the first layer is between and adjacent to each of the second layers. 19. The liner of Claim 1, wherein the liner has a total thickness of from 1.5 to 2,5 mm. 20- The liner of Claim 1, characterized as having an average flexural modulus of no more than 130 MPa, as determined in accordance with ISO 178. 21. The liner of Claim 1, characterized as having an Impact resistance at -10°C of at least 35 J/mm, as determined in accordance with ISO 6603. 22. The liner of Claim 1, wherein the first layer comprises from 40 to 99 weight percent of the first polymer component. 23. The liner of Claim 1, wherein the first layer comprises from 60 to 97 weight percent of the first polymer component. 24. The liner of Claim 1, wherein the first layer comprises from 87 to 93 weight percent of the first polymer component. 25. The liner of Claim 1, wherein the at least one second layer comprises from 40 to 99 weight percent of the second polymer component. 26. The liner of Claim 1, wherein the at least one second layer comprises from 60 to 97 weight percent of the second polymer component. 27. The liner of Claim 1, wherein the at least one second layer comprises from 87 to 93 weight percent of the second polymer component, 28. The liner of Claim 1, wherein the first poly mer component comprises from 5 to 75 weight percent of an additional thermoplastic polymer. 29. The liner of Claim 1, wherein the second polymer component comprises from 5 to 60 weight percent of an additional thermoplastic polymer. 30. The liner of Claim 1, further comprising from 5 to 60 weight percent of a short fiber reinforcing material, based on the total weight of the liner. 31. The liner of Claim 28, wherein the short fiber reinforcing material is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, polyester fibers, polyamide fibers, or polyolefin fibers. 32. The liner of Claim 1, further comprising a reinforcing nonwoven or woven fibrous mat. 33. A liner substantially as herein described and exemplified.

Full Text

Liner Compositions
The subject invention pertains to liner compositions. In particular, the subject invention pertains to liner compositions which comprise a first layer and at least one second layer, wherein the first layer comprises at least one
homogeneous linear or substantially linear ethylene/a-olefin interpolymer.
Liner compositions have been historically utilized in a variety of application, such as pond liners, roofing membranes, tunnel liners, etc. Such applications typically require a balance of flexibility and impact resistance. In certain of these applications, it is necessary that the liner further comply with certain flame retardancy criteria.
Due to its flexibility and ability to incorporate flame retardants, flexible PVC has found utility in tunnel liner applications. However, PVC is disadvantageous in that it utilizes a plasticizer, which tends to migrate with time and cause a decrease in flexibility; and, in that it exhibits poor low temperature flexibility.
EP 508415-A2 discloses polymeric blends of a propylene homopolymer or copolymer, very low density polyethylene, a modified polymer, and a flame retardant filler. However, as characterized by EP 646623-A2, the compositions do not exhibit high weldability coupled with compliance with the flame retardance test set forth in DIN 4102 Bl, both of which are traditionally requirements for use in tunnel liner applications.
EP 646623-A2 discloses polymer compositions useful in tunnel liners, which comprise a blend of two very low density polyethylenes and a flame retardant composition. Exemplified is a blend of a very low density polyethylene having a density
of 0.900 g/cm3 and a melt index (I2) of 0.7 g/10 minutes with a very low density polyethylene having a density of 0.885 g/cm3

and a melt index (Ij) of 2.5 g/lO minutes. While very low density polyethylene does exhibit somewhat enhanced flexibility as compared to higher density linear low density polyethylene materials, it would be desirable to prepare structures exhibiting a further degree of flexibility, while not sacrificing the good impact resistance which is characteristic of very low density polyethylene.
Accordingly, the subject invention provides a flexible, protective, integral liner comprising:
a, a first polymer component which in turn comprises at least
one first ethylene/a-olefin interpolymer which is a
homogeneous linear or substantially linear ethylene/a-
olefin interpolymer having a density of from 0.850 g/cm3
to 0.920 g/cm3
b. a second polymer component which in turn comprises at
least one second ethylene/a-olefin interpolymer having a
density of from 0.905 g/cm3 to 0.935 g/cm3, provided that
the density of the at least one second ethylene/a-olefin
interpolymer is at least 0.002 g/cm3 greater than the
density of the at least one first ethylene/a-olefin
interpolymer,
wherein the liner has a total thickness of 0.3 to 4 mm, and exhibits a flexural modulus, as determined in accordance with ISO 178, of no more than 150 MPa and an Impact Resistance at -10°C, as determined in accordance with ISO 6603, of at least 35 J/mm.
In a preferred embodiment of the invention, the liner will further comprise an ignition resistance additive. In such embodiments, satisfactory flame retardancy (that is, ignition resistance of Bl, as determined in accordance with DIN 4102) will preferably be achieved without sacrificing the balance of properties described above. Even more preferably, the satisfactory flame retardancy will be achieved while employing low amount of the ignition resistance additive (that is, no

more than 20 weight percent, more preferably no more than 15 weight percent, and most preferably no more than 10 weight percent of a halogenated ingition resistance additive; no more than 35 weight percent, more preferably no more than 30 weight percent non-halogenated ignition resistance additive) .
The liners of the invention exhibit outstanding flexibility and mechanical properties, and can be processed on existing polyethylene manufacturing equipment. The liners of the invention which incorporate an ignition resistance additive will further exhibit excellent ignition resistance, will produce lower smoke emissions than flexible PVC liners, and will produce no burning drip while burning.
The liners of the invention will be useful in a variety of applications. In particular, the liners of the invention will be usefully employed to prevent the intrusion of water into buildings or other structures, and thus, to prevent water damage to such buildings or structures. Exemplary applications include, but are not limited to, tunnel liners, pond liners, water barriers, roof liners (particularly for tiled roofs) and geological membranes.
These and other embodiments are described in the following detailed description.
The liner of the invention will comprise at least first and second ethylene/a-olef in interpolymers. The term
"interpolymer" is used herein to indicate a copolymer, or a terpolymer, or a higher order polymer. That is, at least one other comonomer is polymerized with ethylene to make the interpolymer. The first and second ethylene/a-olefin interpolymers selected will achieve a balance of properties, for example, an average flexural modulus, as determined in accordance with ISO 178, of no more than 150 MPa, and an Impact Resistance at -10°C, as determined in accordance with ISO 6603, of at least 3 5 J/mm.

The liner of the invention may comprise a monolayer structure, with the first and second ethylene/a-olefin interpolymers being present as a homogeneous blend, or may comprise at least two layers, with the first and second ethylene/a-olefin interpolymers being present in disparate layers.
While the liner of the invention may be a monolayer, it will preferably comprise at least two layers (referred to herein as an A/B structure). Other structures having more than two layers are possible and will be desirable. One such multilayer structure will employ the same formulations in the layers of the faces of the liner and a different formulation in the interior layer (referred to herein as an A/B/A structure). Preferably, the first ethylene/a-olefin interpolymer will be
present in the B layer and the second ethylene/a-olefin interpolymer will be present in the A layer.
The first and second ethylene/a-olefin interpolymers will each be interpolymers of ethylene with at least one comonomer selected from the group consisting of C3-C20 a-olefins, non-conjugated dienes, and cycloalkenes. Exemplary C3-C20 α olefins include propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene. Preferred C3-C20 ^
-olefins include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene, more preferably 1-hexene and 1-octene. Exemplary cycloalkenes include cyclopentene, cyclohexene, and cyclooctene. The non-conjugated dienes suitable as comonomers, particularly in the making of ethylene/a-olefin/diene terpolymers, are typically non-conjugated dienes having from 6 to 15 carbon atoms. Representative examples of suitable non-conjugated dienes include:
(a) Straight chain acyclic dienes such as 1,4-hexadiene; l, 5-heptadiene; and 1,6-octadiene;

(b) Branched chain acyclic dienes such as 5-methyl-l,4-hexadiene; 3,7-dimethyl-1,6-octadiene; and 3,7-dimethyl-1,7-octadiene;
(c) Single ring alicyclic dienes such as 4-vinylcyclohexene; l-allyl-4-isopropylidene cyclohexane; 3-allylcyclopentene; 4-allylcyclohexene; and 1-isopropenyl-4-butenylcyclohexene;
(d) Multi-ring alicyclic fused and bridged ring dienes such as dicyclopentadiene; alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene; 5-methylene-6-methyl-2-norbornene; 5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-(3-cyclopentenyl)-2-norbornene; 5-ethylidene-2-norbornene; and 5-cyclohexylidene-2-norbornene,
One preferred conjugated diene is piperylene. The preferred dienes are selected from the group consisting of 1,4-hexadiene; dicyclopentadiene; 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; 7-methyl-1,6 octadiene; piperylene; and 4-vinylcyclohexene.
Preferably, the first ethylene/a-olefin interpolymer
(that employed in the B layer of an A/B or an A/B/A structure) will be selected to impact flexibility to the liner of the
invention. Preferably, the first ethylene/a-olefin interpolymer will have a density of at least 0.855 g/cm3, more preferably at least 0.860 g/cm3 even more preferably at least 0.865 g/cm3 and most preferably at least 0.870 g/cm3 Preferably, the first ethylene/a-olefin interpolymer will have
a density of no more than 0.920 g/cm3, more preferably no more than 0.910 g/cm3, even more preferably no more than 0.900 g/cm3 and most preferably no more than 0,890 g/cm3
Preferably, the second ethylene/a-olefin interpolymer
(that employed in the A layer of an A/B or an A/B/A structure) will be selected to impart abuse resistance to the liner of the

invention. Preferably, the second ethylene/a-olefin interpolymer will have a density of at least 0.895 g/cm3 more preferably at least 0.900 g/cm3 even more preferably at least 0.905-g/cm3 Preferably, the second ethylene/a-olefin
interpolymer will have a density of no more than 0.935 g/cm3 more preferably no more than 0.935 g/cm3, and most preferably no more than 0.920 g/cm3.
It is noted that the second ethylene/a-olefin
interpolymer will have a density which is at least 0.002 g/cm3 greater, more preferably at least 0.003 g/cm3 greater than that of the first ethylene/a-olefin interpolymer.
The molecular weight of the ethylene/a-olefin
interpolymers will be selected on the basis of attributes which are intended to be imparted to the liner by the presence of that interpolymer. It is well known that the molecular weight of the polymer will correlate with the melt index (Ij) of the
polymer. Typically, the ethylene/a-olef in interpolymers utilized as the first and second ethylene/a-olef in
interpolymers will have a melt index of at least 0.01, preferably at least 0.05, and more preferably at least 0.1 g/lO minutes. Typically, the ethylene/a-olef in interpolymers
utilized as the first and second ethylene/a-olef in interpolymers will have a melt index of no more than 30, preferably no more than 20, and most preferably no more than 10 g/10 minutes.
In the embodiment of the invention wherein the liner is a monolayer structure, the liner will comprise a blend of the first and second polymer components. In this embodiment, the blend of the first and second polymer components will in turn comprise the first ethylene/a-olef in interpolymer in an amount
of at least 20, more preferably at least 25, and most preferably at least 30 weight percent; preferably no more than 70, more preferably no more than 75, and most preferably no more than 80 weight percent. Further, in this embodiment, the

blend of the first and second polymer components will in turn comprise the second ethylene/a-olefin interpolymer an amount of at least 20, more preferably at least 25, and most preferably at least 30 weight percent; preferably no more than 80, more preferably no more than 75, and most preferably no more than 70 weight percent.
In the case of a multilayer structure, each first layer (the B layer in A/B or A/B/A structures) will comprise at least 40 weight percent, more preferably at least 60 weight percent, and most preferably at least 87 weight percent of the first polymer component (which may be the first polymer alone or as present in a homogeneous mixture with a second thermoplastic polymer) . Each first layer will comprise no more than 99 weight percent, more preferably no more than 97 weight percent, and most preferably no more than 93 weight percent of the first polymer component.
In the case of a multilayer structure, each second layer (the A layer of an A/B or an A/B/A structure) will comprise at least 40 weight percent, more preferably at least 60 weight percent, and most preferably at least 8 7 weight percent of the second polymer component. Each second layer will comprise no more than 99 weight percent, more preferably no more than 97 weight percent, and most preferably no more than 93 weight percent of the second polymer component.
In addition to the first and second ethylene/a-olefin
interpolymers utilized, either or both of the first and second polymer components may optionally comprise an additional thermoplastic polymer. When the additional thermoplastic polymer forms a part of the first polymer component, the additional thermoplastic polymer will preferably be an additional heterogeneous or homogeneous ethylene/a-olefin interpolymer having a density of from 0.855 to 0.920 g/cm3, more preferably from 0.870 to 0.890 g/cm3 and having a melt
index (I2) of from 0.01 to 30, preferably from 0.1 to 10 g/10 minutes. When the additional thermoplastic polymer forms a

part of the second polymer component, the additional thermoplastic polymer will preferably be an additional heterogeneous or homogeneous ethylene/a-olefin interpolymer having a density of from 0.855 to 0.92 0 g/cm3 more preferably from 0.860 to 0.880 g/cm3 and having a melt index (I2) of from
0.01 to 30, preferably from 0.1 to 10 g/10 minutes. While less preferred, the additional thermoplastic polymer may alternatively be a high pressure low density polyethylene or a polypropylene.
In the case of monolayer structures, the blend of the first and second polymer components may comprise, for instance from 0 to 4 0 weight percent, preferably from 0 to 25 weight percent, and more preferably from 0 to 15 weight percent of the additional thermoplastic polymer.
In the case of multilayer structures, the layer containing the first polymer component (the B layer in A/B and A/B/A structures), may utilize, as the first polymer component, either the first ethylene/a-olefin interpolymer alone or as a
blend of the first polymer with from 5 to 75 weight percent, and more preferably from 15 to 65 weight percent, and most preferably from 25 to 60 weight percent of the additional thermoplastic polymer. Likewise, the layer containing the second polymer (the A layer in A/B or A/B/A structures) , may utilize, as the second polymer component, either the second polymer alone or as a blend of the second polymer with from 5 to 60 weight percent, preferably from 10 to 50 weight percent, and more preferably from 40 to 50 weight percent of the additional thermoplastic polymer.
In the case of the multilayer structure, it is understood that the selection of the second polymer component of the second layer will be dependent on the selection of the first polymer .component of the first layer. That is, if the layer containing the first polymer component (the B layer in A/B or A/B/A structures) consists essentially of the first ethylene/a-olefin interpolymer, the second polymer component

may consist essentially of the second ethylene/α-olefin interpolyraer, without sacrificing flexibility. However, if the first polymer component comprises a blend of the first ethylene/a-olefin interpolymer with an additional thermoplastic polymer (for instance, when the first polymer component is a blend of a substantially linear ethylene/a-
olefin interpolymer (the first ethylene/a-olef in interpolymer) and a heterogeneously branched ethylene/a-olef in interpolymer
(the additional thermoplastic polymer)), then the second polymer component shall also be designed to contain an additional thermoplastic polymer (for instance, when the second polymer component is a blend of a heterogeneously branched ethylene/a-olefin interpolymer (the second ethylene/a-olefin
interpolymer) with a homogeneously branched ethylene/a-olef in interpolymer (the additional thermoplastic polymer)).
Although the present invention is intended to encompass the structures of the preceding paragraph, for instance, when it is desired to "cut back" the first ethylene/a-olefin
interpolymer with a less expensive additional thermoplastic polymer, from a performance standpoint, it is preferred that the first polymer component consist essentially of the first
ethylene/a-olefin interpolymer.
The liner of the invention will preferably comprise an ignition resistance additive, suitable to cause the liner to exhibit an ignition resistance of Bl, as determined in accordance with DIN 4102, incorporated herein by reference. Exemplary ignition resistance additives include halogenated ignition resistance additives and halogen-free intumescent systems. One preferred halogenated ignition resistance additive is as Luvogard MB81/PE, available from Lehmann & Voss, which is a brominated compound (83 percent bromine content), which utilizes antimony trioxide as a synergist. One preferred halogen-free intumescent system is ethylene-diamine-posphate (EDAP) or red phosphorus.

When a halogenated ingition resistance additive is employed, it will preferably be provided in an amount of at least 1 weight percent, more preferably at least 3 weight percent, and most preferably at least 5 weight percent; preferably no more than 20 weight percent, more preferably no more than 15 weight percent, and most preferably no more than 10 weight percent.
When a non-halogenated ignition resistance additive is employed, it will preferably be provided in an amount of at least 1 weight percent, more preferably at least 5 weight percent; preferably no more than 35 weight percent, more preferably no more than 3 0 weight percent.
Preferably, the ignition resistance additive will be present in each layer of the liner.
The liner of the invention will typically have a thickness of at least 0.3 mm, preferably at least 1.0 mm, and most preferably at least 1.5 mm; typically no more than 4 mm, preferably no more than 3 mm, and most preferably no more than 2.5 mm.
The liner of the invention will have a flexural modulus of no more than 150 MPa (which, unless otherwise indicated, is reported as an average between the average machine and cross direction measurements) , as determined in accordance with ISO 178.
Preferably, the liner of the invention will be characterized as having a flexural modulus in the machine direction which is within about 30 percent, more preferably within about 25 percent of that in the cross direction. Preferably, in the case of multilayer structures having three or more layers, such as, for example, A/B/A structures, the liner of the invention will have an average flexural modulus in the cross direction of no more than 150 MPa, preferably no more than 130 MPa. Preferably, in the case of multilayer structures having three or more layers, such as, for example, A/B/A structures, the liner of the invention will have an average

flexural modulus in the machine direction of no more than 125 MPa, preferably no more than 110 MPa.
Preferably, in the case of multilayer structures having two layers, for example, A/B structures, the liner of the invention will have an average flexural modulus of no more than 100 MPa, preferably no more than 90 MPa (when measured from side of the more flexible B layer). Preferably, in the case of multilayer structures having two layers, for example, A/B structures, the liner of the invention will have an average flexural modulus of no more than 100 MPa, preferably no more than 90 MPa (when measured from the side of the less flexible A layer) .
In the more preferred embodiment, wherein the A and B layers each comprise a substantially linear ethylene polymer, the liner of the invention will preferably have a flexural modulus of no more than 100 MPa, preferably no more than 80 MPa, more preferably no more than 60 MPa, and most preferably no more than 50 MPa.
When the liner is a multilayer structure, it may be characterized as having a thickness ratio, which is defined herein to mean the ratio of the thickness of the first layer (the B layer in an A/B or an A/B/A structure) to each second layer (the A layer(s) in an A/B or an A/B/A structure) of from 1:1 to 15:1, preferably from 5:1 to 12:1, and most preferably from 6:1 to 10:1.
Heterogenous polymers are ethylene/a-olefin interpolymers characterized as having a linear backbone and a DSC melting curve having a distinct melting peak greater than 115°C attributable to a high density fraction. Heterogeneous interpolymers will typically have an M„/M„ greater than 3 (when the density of the interpolymer is less than about 0.960 g/cm3) and will typically have a CDBI less than or equal to 50, indicating that such interpolymers are a mixture of molecules having differing comonomer contents and differing amounts of short chain branching.

The heterogeneous ethylene/a-olefin interpolymers that
can be used in the practice of this invention will be prepared with a coordination catalyst, such as a Ziegler or Phillips catalyst, at a high temperature and a relatively low pressure. Heterogeneous ethylene/a-olefin interpolymers are linear
polymers which are characterized as having an absence of long chain branches of polymerized monomer units pendant from the backbone. High density polyethylene (HDPE), generally having a
density of 0.941 to 0.965 g/cm-^, is typically a homopolymer of
ethylene, and it contains relatively few short chain branch chains relative to the various linear interpolymers of ethylene and an a-olefin. HDPE is well known, and is commercially available in various grades.
Linear interpolymers of ethylene and at least one a-
olefin of 3 to 12 carbon atoms, preferably of 4 to 8 carbon atoms, are also well known and commercially available. As is well known in the art, the density of a linear ethylene/a-olef in copolymer is a function of both the length of the a-olefin and the amount of such monomer in the copolymer relative to the amount of ethylene, the greater the length of the a-
olefin and the greater the amount of a-olefin present, the lower the density of the copolymer. Linear low density polyethylene (LLDPE) is typically a copolymer of ethylene and an a-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms (for example, 1-butene, 1-octene, etc.), that has sufficient a-olefin content to reduce the density of the
copolymer to. a density of from 0.915 to 0.935 g/cm3. When the copolymer contains even more a-olefin, the density will drop
below about 0,915 g/cm3 and these copolymers are known as ultra low density polyethylene (ULDPE) or very low density polyethylene (VLDPE) .

Heterogeneous ethylene/a-olefin interpolymers are available from The Dow Chemical Company as DOWLEXTM linear low density polyethylene and ATTANE™ ultralow density linear low density polyethylene. Heterogeneous linear ethylene/a-olefin interpolymers can be prepared via the solution, slurry or gas phase polymerization of ethylene and one or more optional a-
olefin comonomers in the presence of a Ziegler Natta catalyst, by processes such as are disclosed in U.S. Patent No. 4,076,698 to Anderson et al., which is incorporated herein by reference. Preferably, heterogeneous ethylene polymers are typically characterized as having molecular weight distributions, M^,/M„, in the range of from 3.5 to 4.1. Relevant discussions of both of these classes of materials, and their methods of preparation are found in U.S. Patent No. 4,950,541 and the patents to which it refers, all of which are incorporated herein by reference.
Homogeneous ethylene/a-olefin intezpolymers include both homogeneous linear and substantially linear ethylene/a-olef in interpolymers. By the term "homogenous", it is meant that any comonomer is randomly distributed within a given interpolymer molecule and substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer. The melting peak of homogeneous linear and substantially linear ethylene polymers, as obtained using differential scanning calorimetry, will broaden as the density decreases and/or as the number average molecular weight decreases.
The homogeneous ethylene/a-olefin interpolymers useful in the invention are characterized as having a narrow molecular weight distribution (Mw/Mn) . For the homogeneous ethylene/a-olef ins useful in the practice of the invention, the M^/M^ is
from 1.5 to 2.5, preferably from 1.8 to 2.2, most preferably about 2.0.
Substantially linear ethylene interpolymers are homogeneous interpolymers having long chain branching. Due to

the presence of such long chain branching, stibstantially linear ethylene interpolymers are further characterized as having a melt flow ratio (I10/I2) which may be varied independently of the polydispersity index, the molecular weight distribution Mw/Mn- This feature accords substantially linear ethylene
polymers with a high degree of processability despite a narrow molecular weight distribution.
It is noted that substantially linear interpolymers useful in the invention differ from low density polyethylene prepared in a high pressure process. In one regard, whereas low density polyethylene is an ethylene homopolymer having a density of
from 0.900 to 0.935 g/cm3, the homogeneous linear and substantially linear interpolymers useful in the invention require the presence of a comonomer to reduce the density to
the range of from 0.900 to 0.935 g/cm3.
The long chain branches of substantially linear ethylene interpolymers have the same comonomer distribution as the interpolymer backbone and can be as long as about the same length as the length of the interpolymer backbone. When a substantially linear ethylene/a-olefin interpolymer is
employed in the practice of the invention, such interpolymer will be characterized as substituted with from 0,01 to 3 long chain branches per 1000 carbons.
Methods for determining the amount of long chain branching present, both qualitatively and quantitatively, are known in the art.
For determining the presence of long chain branching, see, for example, U.S, Patent Nos. 5,272,236 and 5,278,272, each of which is incorporated herein by reference. As set forth therein, a gas extrusion rheometer (GER) may be used to determine the rheological processing index (PI), the critical shear rate at the onset of surface melt fracture, and the critical shear stress at the onset of gross melt fracture, as set forth below.

The gas extrusion rheometer useful in the determination of rheological processing index (PI), the critical shear rate at the onset of surface melt fracture, and the critical shear stress at the onset of gross melt fracture, is described by M. Shida, R. N. Shroff, and L. V. Cancio in Polymer Engineering Science, Vol. 17, No. 11, p. 770 (1977), and in "Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold co, (1982) on pp. 97-99, each of which is incorporated herein by reference. GER experiments are performed at a temperature of 190°C, at nitrogen pressures between 250 and 5500 psig (between 1.72 and 37.9 MPa) using a 0.0754 mm diameter, 20:1 L/D die with an entrance angle of 180°.
For substantially linear ethylene interpolymers, the PI is the apparent viscosity (in kpoise) of a material measured by
GER at an apparent shear stress of 2.15 x 106 dynes/cm3 (0,215 MPa). Substantially linear ethylene interpolymers useful in the invention will have a PI in the range of 0.01 kpoise to 50 kpoise, preferably 15 kpoise or less. Substantially linear ethylene interpolymers have a PI which is less than or equal to 70 percent of the PI of a linear ethylene interpolymer (either a Ziegler polymerized polymer or a homogeneous linear ethylene interpolymer) having an l2f Mw/Mn, each of which is within 10
percent of that of the substantially linear ethylene interpolymer.
An apparent shear stress versus apparent shear rate plot may be used to identify the melt fracture phenomena and to quantify the critical shear rate and critical shear stress of ethylene polymers. According to Ramamurthy, in the Journal of Rheology, 30(2), 1986, pp. 337-357, above a certain critical flow rate, the observed extrudate irregularities may be broadly classified into two main types: surface melt fracture and gross melt fracture.
Surface melt fracture occurs under apparently steady flow conditions and ranges in detail from loss of specular film gloss to the more severe form of "sharksin." Herein, as

determined using the above-described gas extrusion rheometer, the onset of surface melt fracture is characterized as the beginning of losing extrudate gloss at which the surface roughness of the extrudate can only be detected by magnification at 40 times. The critical shear rate at the onset of surface melt fracture for a substantially linear ethylene interpolymer is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture for a linear ethylene polymer having the same comonomer or comonomers and having an I2/ Mw/Mn and density within ten percent of that
of the substantially linear ethylene polymer.
Gross melt fracture occurs at unsteady extrusion flow conditions and ranges from regular (alternating rough and smooth, helical, etc.) to random distortions. The critical shear stress at the onset of gross melt fracture of substantially linear ethylene interpolymers, especially those
having a density greater than 0.910 g/cm3, is greater than 4 x
10^ dynes/cm2 (0.4 MPa).
The presence of long chain branching may further be qualitatively determined by the Dow Rheology Index (DRI), which expresses a polymer's "normalized relaxation time as the result of long chain branching." (See, S. Lai and G. W. Knight, ANTEC '93 Proceedings, INSITE™ Technology Polyolefins (SLEP)- New Rules in the Structure/Rheology Relationship of Ethylene a-Olefin Copolymers, New Orleans, La., May 1993. DRI values range from 0 for polymers which do not have any measurable long chain branching, such as TafmerTM products available from Mitsui Petrochemical Industries and Exact"^ products available from Exxon Chemical company) to about 15, and are independent of melt index. In general, for low to medium pressure 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. Substantially linear ethylene interpolymers

will have a DRI of preferably at least 0.1, more preferably at least 0.5, and most preferably at least 0.8.
DRI may be calculated from the equation;
DRI = (3.652879 * TQI • 00649/ŋ0-1)/10
where TQ is the characteristic relaxation time of the interpolymer and TIQ is the zero shear viscosity of the interpolymer. Both TQ and r]^ are the "best fit" values to the Cross equation
n/rio - 1/(1 + (y * Xo)l-n)
in which n is the power law index of the material, and r\ 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 to 100 radians/second at 160° C and a gas extrusion rheometer (GER) at extrusion pressures from 1,000 to 5,000 psi (6.89 to 34.5 MPa), which corresponds a shear stress of from 0.086 to 0,43 MPa, using a 0.0754 mm diameter, 20:1 L/D die at 190°C. Specific material determinations may be performed from 140 to 190°C as required to accommodate melt index variations.
For quantitative methods for determining the presence of long chain branching, see, for example, U.S. Patent Nos. 5,2 72,23 6 and 5,278,272; Randall (Rev. Macromol. Chem. Phys., C29 (2Sc3) , p. 285-297) , which discusses the measurement of long chain branching using °C nuclear magnetic resonance spectroscopy, Zimm, G.H. and Stockmayer, W.H., J. Chem. Phys., 17, 1301 (1949); and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112, which discuss the use of 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).

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 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 polymers. In particular, deGroot and Chum found that the presence of long chain branches in substantially linear ethylene polymers correlated well with the level of long chain
branches measured using °C NMR.
Further, deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, as such, one can account for the molecular weight increase attributable to octene short chain branches by knowing the mole percent octene in the sample. By deconvoluting the contribution to molecular weight increase attributable to 1-octene short chain branches, deGroot and Chum showed that GPC-DV may be used to quantify the level of long chain branches in substantially linear ethylene/octene copolymers.
deGroot and Chum also showed that a plot of log(I2, melt
index) as a function of log(GPC weight average molecular weight), as determined by GPC-DV, illustrates that the long chain branching aspects (but not the extent of long chain branching) of substantially linear ethylene polymers are comparable to those of high pressure, highly branched low density polyethylene (LDPE) and are clearly distinct from heterogeneously branched ethylene polymers produced using Ziegler-type catalysts (such as linear low density polyethylene and ultra low density polyethylene) as well as from homogeneous linear ethylene polymers (such as Tafmer""^ products available from Mitsui Petrochemical Industries and Exact*"^ products available from Exxon Chemical Company).
Homogeneously branched linear ethylene/a-olefin interpolymers may be prepared using polymerization processes

(for example, as described by Elston in USP 3,645,992, incorporated herein by reference) which provide a homogeneous short chain branching distribution. In his polymerization process, Elston uses soluble vanadium catalyst systems to make such polymers. However, others such as Mitsui Petrochemical Company and Exxon Chemical Company have used so-called single site catalyst systems to make polymers having a homogeneous linear structure. U.S. Patent No. 4,93 7,299 to Ewen et al. and U.S. Patent No. 5,218,071, to Tsutsui et al., each of which is incorporated herein by reference, disclose the use of catalyst systems based on hafnium for the preparation of homogeneous linear ethylene polymers. Homogeneous linear ethylene/a-olefin interpolymers are currently available from Mitsui Petrochemical Company under the trade name "Tafmer" and from Exxon Chemical Company under the trade name "Exact".
Substantially linear ethylene/a-olefin interpolymers are available from The Dow Chemical Company as Affinity™ polyolefin plastomers. Substantially linear ethylene/a-olefin interpolymers may be prepared in accordance with the techniques described in U.S. Patent No. 5,272,236 and in U.S. Patent No. 5,278,272, each of which is incorporated herein by reference.
The homogeneous linear and substantially linear
ethylene/a-olefin interpolymers may be suitably prepared using
a single site metallocene or a constrained geometry metal complex. Constrained geometry catalysts are disclosed in U.S. Application Serial No. 545,403, filed July 3, 1990 (EP-A-416,815); U.S. Application Serial No. 702,475, filed May 20, 1991 (EP-A-514,828) ; as well as US-A-5,470,993 , 5,374,696, 5,231,106, 5,055,43 8, 5,057,475, 5,096,867, 5,064,802, and 5,132,380. In U.S. Serial Number 720,041, filed June 24, 1991, (EP-A-514,828) certain borane derivatives of the foregoing constrained geometry catalysts are disclosed and a method for their preparation taught and claimed. In US-A 5,453,410 combinations of cationic constrained geometry catalysts with an alumoxane were disclosed as suitable olefin polymerization catalysts.

Suitable activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to U. S. Serial No. 07/547,718), EP-A-520,732 (equivalent to U. S. Serial No. 07/876,268), WO 95/00683 (equivalent to U.S. Serial No. 08/82,201), and EP-A-520,732 (equivalent to U. S. Serial No. 07/884,966 filed May 1, 1992.
Catalysts found to be particularly suitable in the preparation of substantially linear ethylene/a-olefin interpolymers include, for instance, the catalysts described in the Examples set forth below, as activated by trispentafluorophenylborane and triisobutylaluminum modified methylalumoxane cocatalysts.
The molar ratio of metal complex: activating cocatalyst employed preferably ranges from 1:1000 to 2:1, more preferably from 1:5 to 1.5:1, most preferably from 1:2 to 1:1. In the preferred case in which a metal complex is activated by trispentafluorophenylborane and triisobutylaluminum modified methylalumoxane, the titanium:boron:aluminum molar ratio is typically frotn 1:10:50 to 1:0.5:0,1, most typically from about 1:3:5.
A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1:100,000 to 1:10, more preferably from 1:50,00 0 to 1:20, and most preferably from 1:10,000 to 1:30. In most polymerization reactions the molar
ratio of catalyst :polymerizable compounds employed is from 10-
12:1 to 10-1:1, more preferably from 10-91 to 10-5:1.
At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts

must be prepared and recovered in an oxygen and moisture free atmosphere • Preferably/ therefore, the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen.
The polymerization may be carried out as a batchwise or a continuous polymerization process, with continuous polymerization processes being required for the preparation of substantially linear polymers. In a continuous process, ethylene, comonomer, and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom.
In general, the first polymer may be polymerized at conditions for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, reactor pressures ranging from atmospheric to 3500 atmospheres. The reactor temperature should be greater than 80°C, typically from 100°C to 250°C, and preferably from 100°C to 150°C, with temperatures at the higher end of the range, and the temperatures greater than 100°C favoring the formation of lower molecular weight polymers.
In conjunction with the reactor temperature, the hydrogen:ethylene molar ratio influences the molecular weight of the polymer, with greater hydrogen levels leading to lower molecular weight polymers. When the desired polymer has an I2
of 1 g/10 min, the hydrogen:ethylene molar ratio will typically be 0:1. When the desired polymer has an I2 of 1000 g/10 min.,
the hydrogen:ethylene molar ratio will typically be from 0.45:1 to 0.7:1. The upper limit of the hydrogen:ethylene molar ratio is from 2,2 to 2.5:1.
Generally the polymerization process is carried out with a differential pressure of ethylene of from 10 to 1000 psi (70 to 7000 kPa) , most preferably from 40 to 60 psi (30 to 300 kPa) . The polymerization is generally conducted at a temperature of from 80 to 250°C, preferably from 90 to 170°C, and most preferably from greater than 95°C to 140°C.

In most polymerization reactions the molar ratio of
catalyst rpolymerizable compounds employed is from 10-1 :l to
lO-1:1 more preferably from 10-9 :1 to 10-5 :1, Solution polymerization conditions utilize a solvent for the respective components of the reaction. Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures. Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene
and Isopar-ETM, available from Exxon Chemicals Inc. ;
cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene.
The solvent will be present in an amount sufficient to prevent phase separation in the reactor. As the solvent functions to absorb heat, less solvent leads to a less adiabatic reactor. The solvent-.ethylene ratio (weight basis) will typically be from 2.5:1 to 12:1, beyond which point catalyst efficiency suffers. The most typical solvent:ethylene ratio (weight basis) is in the range of from 5:1 to 10:1.
The ethylene/a-olefin interpolymer may alternatively be prepared in a gas phase polymerization process, using the catalysts as described above as supported in an inert support, such as silica. The ethylene/a-olefin interpolymer may further be made in a slurry polymerization process, using the catalysts as described above as supported in an inert support, such as silica. As a practical limitation, slurry polymerizations take place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent. Likewise the a-olefin monomer or a mixture of different a-olefin monomers may be used in whole or part as the diluent. Most preferably the diluent comprises

in at least major part the a-olefin monomer or monomers to be polymerized.
A typical liner, with a total thickness of 2 mm, of the invention will be characterized as having a flexural modulus, as determined in accordance with ISO 178, of no more than 118 MPa as a mean value, preferably of no more than 8 0 MPa. The liners of the invention will be characterized as having an Impact Resistance at -lO^C, as determined in accordance with ISO 6603, of at least 35 J/mm, more preferably at least 50 J/mm.
The following examples are provided to illustrate typical embodiments of the invention, and are not intended to serve as limits as to its scope,
The following materials are employed in the preparation of the liners of the examples:

Density is measured in accordance with ASTM D792 in which the samples are annealed at ambient temperature for 24 hours before the measurement is taken.
Melt index (I2) is measured in accordance with ASTM D-123 8, at a temperature of 190°C, and using a weight of 2.16 kg (in the case of I2) and 5 kg (in the case of I5) .
Ignition resistance is measured in accordance with DIN 4102.
Modulus is determined in accordance with ISO 5272961.
Yield and ultimate tensile strength, yield and ultimate elongation, and toughness are determined in accordance with ISO 5272961.
Hardness Shore A and Hardness Shore D are determined in accordance with ISO 868.
ISO Impact E is determined in accordance with ISO 18093. Impact at -10°C is determined in accordance with ISO 6603.
Flexural modulus is determined in accordance with ISO 178.
Modulus (man Young) is determined in accordance with ISO 178.
Displacement, strain, stress, and load at yield are determined in accordance with ISO 178.
Tear Propagation is measured in accordance with the following procedures. Load thickness at maximum load is measured in accordance with ASTM D-1004/DIN 53515. Energy at break point is measured in accordance with ASTM D-1004/ DIN 53515. Peak absolute is measured in accordance with ASTM D-1004/DIN 53515.
Example 1: Preparation of a Coextruded A/B Liner
In the screw unit of a first extruder, 88.5 weight percent Polymer 1, 10 weight percent MB-81, and 1.5 weight percent White-MB are melt blended to form a first homogeneous mixture.

In the screw unit of a second extruder, 8 9 weight percent Polymer 2, 10 weight percent MB-81, and 1 weight percent CB-MB are melt blended to form a second homogeneous mixture.
The liner comprising the first (A) layer and the second (B) layer is formed by coextruding the first and second homogeneous mixtures, respectively. The thickness of the A layer, comprising the first homogeneous mixture, is 250 microns. The thickness of the second layer, comprising the second homogeneous mixture, is 1.75 mm.
The liner is evaluated for certain performance attributes, which are set forth in Table Two, following Example Two.
Example 2: Preparation of a Coextruded A/B/A Liner
In the screw unit of first and third extruders, 89 weight percent Polymer 1, 10 weight percent FR-batch, and 1 weight percent White-MB are melt blended to form first and third homogeneous mixtures.
In the screw unit of a second extruder, 89 weight percent Polymer 2, 10 weight percent FR-batch, and 1 weight percent White MB are melt blended to form a second homogeneous mixture.
The liner comprising the first and third (A) layers and the second (B) layer is formed by coextruding the first, second, and third homogeneous mixtures, respectively. The thickness of the A layers, comprising the first and third homogeneous mixtures, is 200 microns. The thickness of the second layer, comprising the second homogeneous mixture, is 1.60 mm.
The liner is evaluated for certain performance attributes, which are set forth in Table Two.

As seen above, both liner 1 and liner 2 exhibit an average flexural modulus of no more than 150 MPa, with liner 2 having an average of 112 MPa and liner 1 having an average of 110 MPa ( (161 + 60) / 2) .
In the case of the A/B structure of liner 1, the liner has an average flexural modulus of no more than 90 MPa, that is, an average flexural modulus of about 80 MPa, when measured from side of the more flexible B layer; the liner further has an average flexural modulus of no more than 70 MPa, when measured from the side of the less flexible A layer.
In the case of the A/B/A structure of liner 2, the liner has an average flexural modulus in the cross direction of no more than 13 0 MPa; the liner further has an average flexural modulus in the machine direction of no more than 110 MPa.
For the purpose of comparison, a 2 mm thick film comprising 88.5 weight percent Polymer 1, 10 weight percent MB-81, and 1.5 weight percent White-MB exhibits an Impact at -10°C of 23.1 J/mm and a flexural modulus of 185 MPa.
Examples 3 and 4: Preparation of A/B/A Liners Utilizing a Substantially Linear Polymer in Each Layer
In the case of the liner of Example 3, in the screw unit of first and third extruders, 83 weight percent Polymer 3, 16 weight percent of MB-81, and 1 weight percent White-MB are melt blended to form first and third homogeneous mixtures. In the screw unit of a second extruder, 83 weight percent Polymer 4, 16 weight percent FR-batch, and 1 weight percent CB-MB are melt blended to form a second homogeneous mixture.
In the case of the liner of Example 4, in the screw unit of first and third extruders, 89 weight percent Polymer 3, 10 weight percent of MB-81, and 1 weight percent White-MB are melt blended to form first and third homogeneous mixtures. In the screw unit of a second extruder, 89 weight percent Polymer 4,

10 weight percent FR-batch, and 1 weight percent CB-MB are melt blended to form a second homogeneous mixture.
The liners comprising the first and third (A) layers and the second (B) layer are formed by coextruding the first, second, and third homogeneous mixtures, respectively. In the case of the liners of each of Examples 3 and 4, the thickness of the A layers, comprising the first and third homogeneous mixtures, is 100 microns, and the thickness of the second layer, comprising the second homogeneous mixture, is 1.8 mm. The liners each have an overall thickness of 2 mm.
The liners of Examples 3 and 4 are evaluated for certain performance attributes, which are set forth in Table Three.

As snown above, liners 3 and 4, each of which utilize A and B layers which comprise a substantially linear ethylene polymer, exhibit an average flexural modulus of no more than 80 MPa (in the case of liner 4) , and of no more than 4 0 MPa (in the case of liner 3).
In addition, in the case of the liner of Example 4, tear propagation measurements were made, the results of which are set forth in the following Table Four.

Examples 5-7: Comparison of Ignition Resistance Additives
In the case of Examples 5-7, 2 mm thick monolayer films are prepared, utilizing Polymer 2, carbon black, a selected ignition resistance additive, and, in the case of Example 5, Aerosil R972. The liners are evaluated for flame retardancy utilizing the LOI test described above. The composition of the liners, the oxygen consumption, and the burn time are set forth in the following Table Five.

Each of the Examples set forth in Table Five is compliant with DIN 4102, having attained a rating of Bl.

1. A liner comprising:
a, a first polymer component which comprises at least one
first ethylene/a-olefin interpolymer which is a
homogeneous linear or substantially linear ethylene/a-
olefin interpolymer having a density of from 0.850 g/cm3 to 0.920 g/cm3
b. a second polymer component which comprises at least one
second ethylene/a-olefin interpolymer having a density of
from 0.905 g/cm3 to 0,935 g/cm3, provided that the density
of the at least one second ethylene/a-olefin interpolymer
is at least 0.002 g/cm3 greater than the density of the at
least one first ethylene/a-olefin interpolymer,
wherein the liner has a total thickness of 0.3 to 4 mm, and exhibits a flexural modulus, as determined in accordance with ISO 178, of no more than 150 MPa and an Impact Resistance at -10°C, as determined in accordance with ISO 6603, of at least 35 J/mm.
2. The liner of Claim 1, wherein the liner comprises an ignition resistant additive, whereupon the liner exhibits an ignition resistance of Bl, as determined in accordance with DIN 4102.
3. The liner of Claim 2, wherein the ignition resistant additive is provided in an amount of from 1 to 3 5 weight percent, based on the total weight of the liner.
4. The liner of Claim 2, wherein the ignition resistant additive is provided to each layer in an amount of from 3 to 15 weight percent, based on the total weight of layer.
5. The liner of Claim 2, wherein the ignition resistant additive is provided to each layer in an amount of from 7 to 13 weight percent, based on the total weight of the layer.

6. The liner of Claim 2, wherein the ignition resistant additive is selected from the group consisting of halogenated ignition resistant additives and intumescent ignition resistant additives.
7- The liner of Claim 1, wherein the at least one first ethylene/a-olefin interpolymer has a density of from 0.87 to 0-89 g/cm3
8. The liner of Claim 1, wherein the at least one first ethylene/a-olefin interpolymer is characterized as having an Mw/Mn of from 1,5 to 2.5,
9. The liner of Claim 1, wherein the at least one first ethylene/a-olefin interpolymer is prepared using a single site metallocene or constrained geometry catalyst.
10. The liner of Claim 1, wherein the at least one second ethylene/a-olefin interpolymer has a density of from 0.900 to 0.92 0 g/cm3
11. The liner of Claim 1, wherein the at least one second ethylene/a-olefin interpolymer is a heterogeneous linear
polymer or a homogeneous linear or substantially linear polymer.
12. The liner of Claim 1, wherein at least one of the at least
one first or second ethylene/a-olefin interpolymers is an
interpolymer of ethylene and at least one C3-C20 a-olefin.
13. The liner of Claim 12, wherein the at least one C3-C20 a-
olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, and 1-octene.
14. The liner of Claim 12, wherein at least one of first or
second ethylene/a-olefin interpolymers is an interpolymer of
ethylene, at least one C3-C20 a-olefin, and at least one diene.

15. The liner of Claim 1, comprising a first layer and at least one second abuse resistant layer, such that the thickness of the first layer and the thickness of each second abuse resistant layer is selected such that the thickness ratio is from 1:1 to 15:1,
16. The liner of Claim 15, wherein the thickness of the first layer and the thickness of each second layer is selected such that the thickness ratio is from 5:1 to 12:1.
17. The liner of Claim 16, wherein the thickness of the first layer and the thickness of each second layer is selected such that the thickness ratio is from 6:1 to 10:1.
18. The liner of Claim 1, wherein the liner comprises one first layer and two second abuse resistant layers, which are configured such that the first layer is between and adjacent to each of the second layers.
19. The liner of Claim 1, wherein the liner has a total thickness of from 1.5 to 2,5 mm.
20- The liner of Claim 1, characterized as having an average flexural modulus of no more than 130 MPa, as determined in accordance with ISO 178.
21. The liner of Claim 1, characterized as having an Impact resistance at -10°C of at least 35 J/mm, as determined in accordance with ISO 6603.
22. The liner of Claim 1, wherein the first layer comprises from 40 to 99 weight percent of the first polymer component.
23. The liner of Claim 1, wherein the first layer comprises from 60 to 97 weight percent of the first polymer component.
24. The liner of Claim 1, wherein the first layer comprises from 87 to 93 weight percent of the first polymer component.
25. The liner of Claim 1, wherein the at least one second layer comprises from 40 to 99 weight percent of the second polymer component.

26. The liner of Claim 1, wherein the at least one second layer comprises from 60 to 97 weight percent of the second polymer component.
27. The liner of Claim 1, wherein the at least one second layer comprises from 87 to 93 weight percent of the second polymer component,
28. The liner of Claim 1, wherein the first poly mer component comprises from 5 to 75 weight percent of an additional thermoplastic polymer.
29. The liner of Claim 1, wherein the second polymer component comprises from 5 to 60 weight percent of an additional thermoplastic polymer.
30. The liner of Claim 1, further comprising from 5 to 60 weight percent of a short fiber reinforcing material, based on the total weight of the liner.
31. The liner of Claim 28, wherein the short fiber reinforcing material is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, polyester fibers, polyamide fibers, or polyolefin fibers.
32. The liner of Claim 1, further comprising a reinforcing nonwoven or woven fibrous mat.

33. A liner substantially as herein described and exemplified.

Documents:

in-pct-2000-381-che-abstract.pdf

in-pct-2000-381-che-assignment.pdf

in-pct-2000-381-che-claims filed.pdf

in-pct-2000-381-che-claims grand.pdf

in-pct-2000-381-che-correspondence others.pdf

in-pct-2000-381-che-correspondence po.pdf

in-pct-2000-381-che-description complete filed.pdf

in-pct-2000-381-che-description complete grand.pdf

in-pct-2000-381-che-form 1.pdf

in-pct-2000-381-che-form 19.pdf

in-pct-2000-381-che-form 26.pdf

in-pct-2000-381-che-form 3.pdf

in-pct-2000-381-che-form 5.pdf

in-pct-2000-381-che-other documents.pdf

in-pct-2000-381-che-pct.pdf

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Patent Number

202327

Indian Patent Application Number

IN/PCT/2000/381/CHE

PG Journal Number

05/2007

Publication Date

02-Feb-2007

Grant Date

12-Oct-2006

Date of Filing

13-Sep-2000

Name of Patentee

M/S. DOW GLOBAL TECHNOLOGIES INC

Applicant Address

WASHINGTON STREET, 1790 BUILDING, MICHIGAN 48674

Inventors:

#	Inventor's Name	Inventor's Address
1	KATZER, Karin	Seestrasse 187 CH-8810 Horgen
2	QUACK, Wolfgang	Mozartstrasse 15 D-40822 Mettmann

PCT International Classification Number

C08L 23/04

PCT International Application Number

PCT/US1999/003911

PCT International Filing date

1999-02-23

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/078,215	1998-03-16	U.S.A.