AU8936598A - Blends of graft-modified substantially linear ethylene polymers and other thermoplastic polymers - Google Patents

Description

S F Ref: 316420D1

AUSTRALIA

PATENTS ACT 1990 FOR A STANDARD

PATENT

ORIGINAL

Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: The Dow Chemical Company 2030 Dow Center Abbott Park Midland Michigan 48640 UNITED STATES OF AMERICA Morgan M. Hughes, Kyle G_ Kummer, Stephen R. Betso, Michael E. Rowland and Morris S. Edmnondsonl Spruson Ferguson, Pe cc-nt Attorneys Level 33 St Martin-: ower, 31 Market Street Sydney, New South Wales, 2000, Australia Blends of Graft-Modified Substantially Linear Ethylene Polymers and Other Thermoplastic Polymers The following statement is a full description of this invention, including the best method of performing it known to me/us- BLENDS OF GRAFT-MODIFIED SUBSTANTIALLY

LINEAR

ETHYLENE POLYMERS AND OTHER THERMOPLASTIC

POLYMERS

This invention relates to elastic, substantially linear ethylene polymers. In one aspect, tiiis invention relates to such polymers grafted with an unsaturated organic compound, for example, maleic anhydride, while in another aspect, the invention relates to blends of this grafted polymer with one or more other thermoplastic polymers, for example, a polyester or a polyamide. In still another aspect, this invention relates to such blends in comination with a filler.

1C In yet another aspect, this invention relates to such blends further comprising one or more other olefin polymers, either grafted or ungrafted.

The art is replete with concern for improving the toughness (also known as ductility) of various thermoplastic resins, for -c example, polyesters, polyamides. The toughness or ductility of a thermoplastic resin is typically measured by use of the notched IZOD impact test (ASTM D-256)- However, the art typically discusses thermoplastic toughness in the context of ambient temperature with little, if any, recognition of the desirability of thermoplastic *1 toughness in many applications at low temperature (less than 0 C).

Moreover, not only do most commercially available thermoplastic resins have less than desirable impact resistance at low temperatures, but most also have less than desirable optical and other physical •properties.

The graft modification of polyolefins, such as polyethylene and polypropylene, with various unsaturated monomers is also well known in the art. Such a modification renders an essentially nonpolar material cempatible, at least to some limited extent, with a polar material.

This, in turn, impacts on certain of the properties of the polyolefin, for example, its ability to adhere or laminate to a solid. For example, USP 4,19a,327 teaches a modified crystalline polyolefin composition having improved adhesion to polar solid materials.

USP

4,397,916 and 5,055,526 also teach adhesive resin compositions of modified polyolefins and laminates made from such polyolefins.

As these references suggest, much of the existing art is primarily concerned with the modification of these polyolefins to develop compositions having specific adhesive properties or improvements in adhesive properties. However, not only do these references discuss lightly or not at all the possible advantageous influence that these graft-modified resin can have on these compositions, but some note that these resins can actually have a detrimental influence on one or more properties of the polvolefin and/or the composition. For example, USP 4,134,927; 3,884,882 and 5,140,074 all report undesirable changes in the rheological properties due to crosslinking of the modified material. These changes tc ultimately impact the processibility of the material and thus, its utility in commercial applications.

The subject invention is directed to, thermoplastic compositions characterized as a substantially homogeneous blend of at least one thermoplastic polymer and at least one substantially linear ethylene polymer grafted with at least 0.01 wt based on the weight of the grafted ethylene polymer, of an unsaturated organic compound containing at least one site of ethylenic unsaturation and at least one carboxyl group, the ethylene polymer characterized as having: a melt flow ratio, 110/12 z 5.63; (ii) a molecular weight distribution, Mw/Mn, defined by the equation: RalMn r (110/12) 4.63; (iii a density greater than 0.850 g/cm 3 and (iv) a critical shear rate at onset of surface melt Fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having the same 12 and Mw/Mn.

The inventive compositions demonstrate desirable impact resistance at both ambient and low temperatures as well as desirable optical properties and small particle sizes relative to known polymers. The thermoplastic compositions of this invention can be either filled or unfilled. In one embodiment of the invention, these compositions can further comprise one or more other polyolefins, either grafted or ungrafted.

Figure 1 reports comparative notched IZOD impact energy data at ambient temperature for PBT and various blends of PBT with MAH-g-ITP, maleic anhydride grafted ethylene-propylene rubber (MAH-g-EPR), and maleic anhydride grafted ethylene-propylene-diene monomer (MAH-g-EPDM), respectively.

Figure 2 reports comparative Dynatup impact energy data at -20 F (-28.8 C) for PBT and the same blends as identified in Figure 3.

Figure 3 reports comparative notched IZOD impact energy data at ambient temperature for poly(butylene terephthalate) (PBT) and various blends of PBT with a maleic anhydride grafted substantially linear ethylene polymer (MAH-g-ITP) and a maleic anhydride grated Tafmer" resin (MAH-g-TaEmer).

iC DESCRIPTION OF THE PREFERRED EMBODIMENTS The substantially linear ethylene polymers used in the.practice of this invention are known, and they and their method of preparation are fully described in USP 5,272,236 and USP 5,278,272. As here used, *substantially linear" means that the polymer backbone is substituted with from 0.01 long-chain branches/1000 carbons to 3 long-chain branches/1000 carbons,'preferably from 0.01 long-chain branches/1000 carbons to 1 long-chain branch/1000 carbons, more preferably from 0.05 long-chain branches/1000 carbons to 1 long-chain branch/1000 carbons.

Long-chain branching is here defined as a chain length of at least 1, about 6 carbon atoms, above which the length cannot be distinguished using 13 C nuclear magnetic resonance spectroscopy. However, the longchain branch can be about the same length as the length of the polymer backbone.

These unique polymers (subsequently referred to as "CGC -g polymers") are prepared by using constrained geometry catalysts (CGC); and are characterized by a narrow molecular weight distribution and if an interpolymer, by a narrow comonomer distribution. As here used, interpolymer" means a polymer of two or more comonomers, for example, a copolymer, terpolymer, etc., or in other words, a polymer made by polymerizing ethylene with at least one other comonomer. Other basic characteristics of these CGC polymers include a low residuals content (that is, low concentrations in the CGC polymer of the catalyst used to prepare the polymer, unreacted comonomers, and low molecular weight oligomers made during the course of the polymerization), and a S1j controlled molecular architecture which provides good processability even though the molecular weight distribution is narrow relative to 6-3j conventional olefin polymers.

While the CGC polymers used in the practice of this invention include elastic, substantially linear ethylene homopolymers, preferably the CGC polymers used in the practice of this invention Scomprise from 95 to 50 weight percent (wt ethylene, and from 5 to wt of at least one a-olefin comonomer, more preferably 10 to wt of at least one a-olefin comonomer. Typically, the CGC polymers are copolymers of ethylene and an a-olefin of from 3 to 20 carbon atoms (for example, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, IC 1-heptene, 1-octene, styrene, etc.), preferably of from 3 to 10 carbon atoms. More preferably these polymers are a copolymer of ethylene and 1-octene. The density of these CGC polymers is typically from 0.850 to 0.935 grams per cubic centimeter (g/cm 3 preferably from 0.870 to 0.910 g/cm 3 The melt flow ratio, measured as 110/12 (ASTM D-1238), is greater than or equal to 5.63, and is preferably from 6.5 to more preferably from 7 to 10. The molecular weight distribution (Mw/Mn), measured by gel permeation chromatography (GPC), is defined by the equation: Mw/Mn S (110/12) 4.63, JO and is preferably from 1.8 to 2.5. For substantially linear ethylene polymers, the 110/12 ratio indicates the degree of long-chain branching, that is the larger the 110/12 ratio, the more long-chain branching in the polymer.

According to Ramamurthy in Journal of Rheoloov, 30(2), 337-357, 5 1986, above a certain critical flow rate, surface melt fracture may occur, which may result in irregularities ranging from loss of specular gloss to the more severe form of "sharkskin". As used herein, the onset of surface melt fracture is characterized as the beginning of losing extrudate gloss at which the surface roughness of O extrudate can only be detected by 40x magnification The substantially linear ethylene polymers will further be characterized by a critical shear rate at the onset of surface melt fracture which is at least percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having about the same 12 and -b Mw/Mn- The unique characteristic of the homogeneously branched, -4substantially linear ethylene polymers is a highly unexpected flow property where the 110/12 value of the polymer is essentially independent of the polydispersity index (that is, Mw/M n of the polymer. This is contrasted with conventional linear homogeneously C branched and linear heterogeneously branched polyethylene resins having rheological properties such that to increase the 110/12 value the polydispersity index must also be increased.

The preferred melt index, measured as 12 (ASTM D-1238, condition 190/2.16 (formerly condition is from 0.5 g/10 min to 200 io min, more preferably from 1 to 20 g/10 min. Typically, the preferred CGC polymers used in the practice of this invention are homogeneously branched and do not have any measurable high density fraction, that is, short chain branching distribution as measured by Temperature Rising Elution Fractionation which is described in USP 5,089,321.

t) Stated in another manner, these polymers preferably do not contain any polymer fraction that has a degree of branching less than or equal to 2 methyls/1000 carbons. These preferred CGC polymers also usually exhibit a single differential scanning calorimetry (DSC) melting peak.

Any unsaturated organic compound containing at least one site of _2C ethylenic unsaturation (for example, at least one double bond), at least one carboxyl group (-COOH), and that will graft to a CGC polymer as described above can be used in the practice of this invention. As here used, "carboxyl group* includes carboxyl groups cer s and derivatives of carboxyl groups such as anhydrides, esters and salts -S (both metallic and nonmetallic). Preferably, the organic compound contains a site of ethylenic unsaturation conjugated with a carboxyl group. Representative compounds include maleic, acrylic, methacrylic, itaconic, crotonic, a-methyl crotonic, and cinnamic acid and their anhydride, ester and salt derivatives, and fumaric acid and its ester o and salt derivatives. Maleic anhydride is the preferred unsaturated organic compound containing at least one ethylenic unsaturation and at least one carboxyl group.

The unsaturated organic compound content of the grafted CGC polymer is preferably at least 0.01 wt and more preferably at least 0.05 wt based on the combined weight of the polymer and the organic compound. The maximum amount of unsaturated organic compound content can vary to convenience, but typically it does not exceed 10 wt preferably it does not exceed 5 wt and more preferably it does not exceed 2 wt of the grafted CGC polymer.

The unsaturated organic compound can be grafted to the CGC polymer by any known technique, such as those taught in USP 3,236,917 and USP 5,194,509. For example, in the '917 patent the polymer is introduced into a two-roll mixer and mixed at a temperature of 60 C.

The unsaturated organic compound is then added along with a free radical initiator, such as, for example, benzoyl peroxide, and the O components are mixed at 30 C until the grafting is completed. In the '509 patent, the procedure is similar except that the reaction temperature is higher, for example, 210 to 300 C, and a free radical initiator is not used or is used at a reduced concentration.

An alternative and preferred method of grafting is taught in USP iS 4,950,541, by using a twin-screw devolatilizing extruder as the mixing apparatus. The CGC polymer and unsaturated organic compound are mixed and reacted within the extruder at temperatures at which the reactants are molten and in the presence of a free radical initiator.

Preferably, the unsaturated organic compound is injected into a zone maintained under pressure within the extruder.

In one embodiment, the graft-modified CGC polymers act as compatibilizers for the filled compositions of this invention. Many molded and extruded products contain fillers, for example, silica, talc, glass, clay, carbon black, and the like, for strength and/or 6 some other desirable property. Often these fillers are only marginally compatible with the resinous matrix within which they are incorporated a' nd as such, the amount of filler that can be incorporated into the matrix, that is, the loading level, is limited. Compatibilizers are used to coat or otherwise treat the filler to render it more S3 compatible with the matrix, and thus allow a higher loading than "otherwise possible to be achieved. The graft-modified substantially linear ethylene polymers used in this invention are particularly desirable compatibilizers because higher loading levels can be achieved, that is either more filler can be incorporated into a given resin matrix based on the amount of compatibilizer, or less compatibilizer is required to incorporate the same amount of filler.

S-6- In addition, the compatibilizers of this invention impart desirable properties to the composition in both fabricated and prefabricte form. In fabricated form, the strength and impact properties (both at ambient and low temperature) are enhanced relative to fabricated compositions$ devoid of grafted substantially linear ethylene polymer.

in prefabricated form. the processability of the compositions are enhanced relative to compositions devoid of grafted substantially linear ethylene polymer.

The amount of graft-modif led substantially linear ethylene polymer required to effectively serve as a conpatibilizer will, of course, vary with the nature of the resinous matrix, the nature and amount of filler, and the chemical and physical characteristics of the substantially linear ethylene polymer and unsaturated organic compound containing a carboxyl group (and the extent of grafting). Typically, 6the weight ratio of graft-modified substantially linear ethylene polymer to filler is from 1:50 to about 50:1. preferably from 1:40 to 20.1.

The graft-modifiled substantially linear ethylene polymer is dry blended or melt blended with other thermoplastic polymers to make the homogeneous compositions of this invention, and then these compositions are molded or extruded into a shaped article. As here used, 'substanltially homogeneous' means that the components of the composition are sufficiently mixed with one another such that the make-up of one portion of the composition is substantially the same as ;SS2 that of any other portion of the composition, such other thermoplastic polymers include any polymer with which the grafted substantially linear ethylene polymer is compatible, and include both olef in and non-clef in polymers. grafted and ungraf ted. The grafted substantially linear ethylene polymer can also be blended with another 3~0 substantially linear ethylene polymer, a conventional heterogeneously branched or homogeneously branched linear ethylene polymer, a nonolefin polymer, any of which can be grafted or ungraf ted. or any combination of these polymers. Examples of -such polymers include high density polyethylene (HDPE), low density polyethylene (LDPE), linear density polyethylene (LLDPE), ultra low density polyethylene (uLDpE), polypropylene. ethylene-propylele copolymer, ethylene-styrenle copolymer, polyisobutylene, ethylene-propylene-diene monomer (EPDM).

polystyrene. acrylonitrile-butadiene-styrene copolymer ethylene-acrylic acid (EAA), ethylene/vinyl acetace (EVA).

ethylene/Vinyl alcohol (EVOH), polymers of ethylene and carbon monoxide (ECO, including those described in USP 4,916.208). or ethylene, propylene and carbon monoxide (EPCO) polymers, or o[ ethylene, carbon monoxide and acrylic acid (ECOAA) polymers, and the like. Representative of the non-olefin polymers are the polyesters.

polyvinyl chloride (PVC), epoxies, polyurethanes, polycarbonates.

,O polyamides, and the like. These blending polymers are characterized by a compatibility with the grafted substantially linear ethylene polymer such that the melt blend does not exhibit gross phase separation, that is a separation in which the individual components of the blend are visible to the unaided eye, after thorough blending and during subsequent processing of the blend. If more than one of these polymers is blended with one or more grafted substantially linear ethylene polymers, then all usually exhibit sufficient compatibility with each other, one-to-one or at least in combination with one or more other polymers, such that the polymeric components do not exhibit :Ic gross phase separation which could lead to extrusion processing difficulties, such as extrudate surging, and film band-effects.

The amount of graft-modified substantially linear ethylene polymer that is blended with one or more other polymers is dependent upon many factors, including the nature of the other polymer or polymers, the intended end use of the blend, and the presence or absence and the nature of additives. For molded articles, S "particularly engineered materials (for example, hoses, shrouds, etc.) the grafted substantially linear ethylene polymer is blended with an Sengineering plastic, for example, polyamide or polyester, such that .t the blended composition typically comprises from 2 to 70 wt preferably from 5 to 30 wt of the graft modified substantially linear ethylene polymer(s) on a total weight basis. In those applications in which the grafted substantially linear ethylene polymer is blended with other polyolefin polymers, for example, a nongrafted substantially linear ethylene polymer or a conventional polyolefin polymer (LLDPE, HDPE, PP, etc.), the blend typically -8- 1 r comprises from 2 to 70 wt preferably from 5 to 30 wt of the graft-modified substantially linear ethylene polymer- Wire and cable are end use applications for such polymer blends. The presence of the graft-modified substantially linear ethylene polymer in these blends, both for engineered materials and wire and cable, provides improved impact and/or strength properties to the compositions.

In other embodiments, the graft-modified substantially linear ethylene polymer comprises from a relatively minor amount (for example, 10 wt up to a substantial majority, for example, 90 wt rC of the finished article. In those applications in which the paintability of the finished article is of importance, incorporation from 30 to 70 wt of a graft-modified substantially linear ethylene polymer will impart desirable paintability properties to an otherwise unpaintable molded article, for example, an article prepared from a polyolefin such as polyethylene and polypropylene.

In another application, the grafted substantially linear ethylene polymer is made into a film comprising up to 100 wt of the graft-modified substantially linear ethylene polymer. Such films exhibit desirable adhesive properties, and are useful as tie layers in 0 various packaging applications, for example, tying another polyolefin to polypropylene, polyester, polyamide, EVOH, paperboard. foil, etc.

These laminated or coextruded structures have utility as lidding stock, pouches for liquid foods, bag and box packaging structures.and barrier packaging films.

x5 As noted above, the polymer blends in which the graft-modified substantially linear ethylene polymer is incorporated can include other additives, such as fillers, colorants, antioxidants. antistats, slip agents, tackifiers, and fragrances. These additives are incorporated by known methods in known amounts.

In another embodiment of this invention, the grafted substantially linear ethylene polymer is -let-down" or diluted with virgin substantially linear ethylene polyolefin or another grafted substantially linear ethylene polymer prior to mixing it with a blending polymer. For example, after the grafted substantially linear 53) ethylene polymer has been prepared as described in USP 4,950.541, it is then back-blended in an extruder with virgin substantially linear -9- ~c~-6 ethylene polymer t~o a predetermined dilution. Let-down or dilution ratios 'will vary with the ultimate application of the grafted substantially linear ethylene polymer, but weight ratios from 1:10 tO 10:1 are typical.

The grafted substantially linear ethylene polymers used in the practice of this invention, and the compositions comprising these polymers, are more ftilly described in the following examples. Unless indicated to the contrary, the substantially linear ethylenes used in the examples are prepared in accordance with the techniques set forth go in USP 5,272,236 via a solution polymerization process utilizing a

(CH

3 4

C

5

)-(CH

3 2 Si-t-(t"C4

H

9 )J i(CH 3 2 organometallic catalyst activated with tris(perfluorophenyl)borane. Unless indicated to the contrary, all parts and percentages are by weight, total weight basis.

Unless indicated to the contrary, the following test procedures are .~utilized: 1. Notched MZOD Impact ASTM D-256 (at 23 (ft-lb/in) C, 0 C, -18 C, -29 C and

C)

2) 2. Tensile (psi) ASTM D-638 3. Yield (psi) ASTM D-638 4. Elongation M% ASTM D-638 Whiteness Index (WI ASTME-313 micicrophsso micotoedmolded S. DyatupASTMD-3763 -86 Samp1 Prenration j All samples were prepared by feeding polymer as described in r~..Table 1 into a Werner-Pfleiderer ZSK-53/5L~ co-rotating twin screw C)extruder operated at the conditions described in Table 2. After the polymer was fed into the extruder, a mixture of maleic anhydride (MAH)/znethyl ethyl ketone (NEK)/LUPERSOL 130 (initiator) at a weight ratio of 1:1:0.032, respectively, was fed into the end of Zone 1 of the extruder through an injection nozzle by a metering pump. LUPERSOL L O 130 is 2,5-di(t-butyl peroxy)hexyle- 3 manufactured and sold by Atochemf. The extruder was maintained at a vacuum level of greater than or equal to 26 inches of mercury (88 kPa) to facilitate devolatization of solvent, unreacted MAl and other contaminates. The percent of incorporation of MKkH into each polymer is also reported in Table 1. Example Cl is an ultralow density ethylene/l-octele resin Smanufactured and sold by The Dow Chemical Company under the tradenamle AlTT?.NE. Example C2 is DowlexeB 2517 resin, a L.LDPE ethylelefl-octele resin manufactured and sold by The Dow Chemical Company. Example C3 is Taftnere P-0180 resin, an ethylenelproPylene copolymer resin manufactured and sold by Mitsui Petrochemical. Examples Cl, C2 and C3 to are comparative examples. The resin used in Examples 1-4 was a substantially linear ethylene polymer of ethylene and 1-octene.

TABLE I Incorporation of Maleic Anhydride into Conventional and Substantially Linear Ethylene Polymers Example Melt Density* Melt Flow Incorporation index* (g/CM 3 R~atio* (ln1) :Cl 3.4 0.906 7.65 40.2 C2 25.0 0.917 25.3 C3 5.0 0.870 5.91 48.9 1 7.0 .0.903 7.57 68.9 2 5.-0 0.871 7.66 57.3 O4 .75 0.870 7.58 62.3 250 0.870 30.6 .j *Ungraf ted polymer -11-- TABLE 2 F~~xtruder iprt~ C on s 7 1 27 IC3 1 __F2 Barrel Tem11P

-I-

Zone I Zone 2 t Zone 3 Zo ne 164 191 _156_ 193 177 202 _142 1 _176 195 140 186 206 3 4 150 162 19S 154 198 203 221 201_ 198 236 S 2010 8 192 polymer Melt Tern (C) screw speed Cnm polymer Feed Rate 177 162 173 1621 163 NA 300 300 320 320 1255 1300 1320 h (lb per hr/ 150/ 150/ 135f 5 0 150 35 f 8 2 2 61 kg per hrL_ 66.2 68.2 61.4 4 5 5 .9 MAHIM"I 6.45/ 5.92/ 5,96/ Initiator 2.93 2.69 2 r .71 Feed Rate I kq pe

IL

(lb per hr/ r 1jr N/A Not Available 150/ 68.2 5.57/ 130/ 59.1 S.90/ 2.68 135/ 61.4 5.84

I

2.65 135/ 61.4 5.46 2.48 Lb The data of Table 1 show that the grafting of a substantially Slinear ethylene polymer is more efficient than the grafting of a nonsubstantially linear ethylene polymer having similar physical properties of melt index, density, and melt flow ratio. The polymer of Example 1 is a substantially linear ethylene polymer with a melt index of 7.0 g/ 10 min and a density of 0.903 g/crl 3 with 68.9% of the tO mM being incorporated into it. In comparison, the polymier of Comparative Example I is a non-substantially linear ethylene polymer (uLDpE) with a melt Index of 3.4 g/10 min and a density of 0.906 -12g/cm 3 which incorporated only 40.2% of the MAH under similar conditions. The substantially linear ethylene polymer incorporated more MAH under similar conditions than did the comparative nonsubstantially linear ethylene polymer. These results mean that the Sgraft-modified substantially linear ethylene polymers of this invention can be prepared with lower loss of materials (that is lower levels of MAH required to obtain the same level of grafting as for non-substantially linear ethylene polymers), and lower emissions due to the use of less volatiles.

SAdhesive Properties The adhesive properties of the grafted polymer samples of Comparative Example 1 and Example 1 were determined by heat seal lamination. The graft-modified polymers were fabricated into blown film having a thickness of 0.003 inches (0.008 cm). Film test samples, one inch (2.5 cm) in width, were cut from the blown film and heat sealed to polypropylene (PF-101, available from Pacur, Inc.), polyamide (Nylon 6, available from Capron-Allied ethylene/vinyl alcohol (Soranol" D, available from Nippon Chemical Co.), polycarbonate (Lexanh, available from General Electric Plastics) and polyetherimide (Altem™, available from General Electric Plastics) films at selected temperatures. The heat seal conditions were Ib/in 2 (280 kPa) of pressure applied for 0.5 seconds by means of heated seal bars set at the desired temperature. The strength of the heat seals was determined on an Instron tensionmeter apparatus using a 15 180 degree pull at a crosshead speed of 2 in/min (5 cm/min).

The data from these tests are reported in Table 3.

S-13- _o 'r

SUBSTRATE

Polypropylene Polyamide TABLE 3 Heat Seal C mparisons Cl FILM HEAT SEAL TEMPERATURE

STRENGTH

(lb. per in/kg per cm) 130 0 140 0 150 0.1/0.1 160 0.3/0.3 170 1.8/1.6 180 2.0/1.7 130 0.6/0.S 140 0.610.5 150 1.0/0-87 160 1.5/1.3 17 2.0/4.3 Ex. 1 FILM HEAT SEAL STRENGTH (lb per in/kg per cmr) 0 0 0-4/0.3 1.1/0.95 2.6/2.3 2.82/4 1.0/0.87 1.0/0.87 1.5/1.3 1.5/1.3 2.14-5 film failure I Ethylene/Vinyl 130 1.3/2.8 1.0/0.87 alcohol 140 1.3/2.8 -1.010.87 150 1.3/2.8 1.2/2.6 160 1.6/3.5 1.5/2.6 170 2.0/4.3 2.0/4.3 180 2.5/4.8 2.3/5.0 -Polycarboflate 230 0.2/0.4 1.5/2.6 Polyetherimide 230 1.0/0.87 0.8/1.7 IThe film test samples of Example 1 gave improved adhesion to polypropylenle, polyaniide and polycarbonate substrates, as well as Ssimilar adhesionl to EVOH and polyetheriDide, as compared to the film test samples of Comparative Example 1. Additional improvements in the adhesive properties of the graft-modified substantially linear ethylene polymers can be realized with respect to changes in resin density and fabrication techniques, for example, extrusion lamination -14or multilayer extrusion. Im provement can also be obtained in the adhesive properties of such blends by using a grafted substantially linear ethylene polymer that has been bacX-blended or let-downl with an ungraf ted substantially linear ethylene polymer- The use of graft-mfodif led substantially linear ethylene polymers to improve the impact'properties of various polymer blends was evaluated by incorporating the polymer into a polyainide resin

(CAPRON

8207, manufactured and sold by Allied-Signlal). Melt blends of the o~afid it .10ad25 t of the graft-modified subtafltially linear ethylene polymer were prepared on an extruder prior to molding on an injection molding machine. The injection molded test samples (IZOD specimens) were evaluated for room temperature notched

IZOD

impact performance. The formulations and results are reported in \S Table 4.

TABLE 4 TZOD ImpaQLCDM2Apnorafl Pol amide 100% None 1306 Pol amide 90%) Cl -2.711.4 Pol amide 75% Cl 15.418.2 2 Pol amide 90% Ex. 1 (10% 4.0/2.1 Pol amide 7 5 Ex. 1 16.1/8.59 As is evident from the data in this Table, polyamlide blends containing the graft-mlodified substantially linear ethylene polymer .ohave higher IZOD impact performance as compared to blends containing a similar graftmodified ULDPE, that is, comparative Example 1.

Additional improvements can be re :alized by lowering in the polymer density.

ccrnn~ibiI zati n Proec These properties were evaluated by blending the graftmodified substanltially linear ethylene polymer of Example One with a base composition containing an unmodified substantially linear ethylene polymer (1 g/10 min MI, 0.902 g/cm 3 density), an inorganic filler (240 parts per hundred resin (phr) vinyl silane treated aluminum trihydrate), peroxide (5 phr Vulcup 40 KE available from Hercules Inc.). coagent (0.8 phr TAC triallyl cyanurate, available from Union Carbide), and a hydrocarbon oil (80 phr Sunpar 2280 available from Sun Oil Company). Melt blends containing 0. 5 and 10 parts of the graftmodified substantially linear ethylene polymer phr and 100. 95, and parts ungrafted base resin were prepared on a small Banbury internal kO mixer. The blended samples were compression molded and evaluated for tensile strength properties before and after curing. The curing conditions were 1 minute at 400 F (204 The tensile strength properties for these blends are reported in Table TABLE iL Tensile Strenoth Properties Sample Ungrafted Ex 1 Tensile Strength Base Level Resin (phr) (phr) Uncured cured _(psi/kPa) (psi/kPa) A 100 0 709/4890 1243/8570 B 95 5 109777564 1486/10,250 C 90 10 1223/8432 1421/9797 As shown by the data in this Table, the incorporation of graftmodified substantially linear ethylene polymer into these compositions allows for compatibilization of an inorganic filler with a resin matrix resulting in higher tensile strength properties. In addition, C) higher tensile strength properties are obtained both before and after curing.

S "The processibility of the graft-modified substantially linear ethylene polymers as compared to graft-modified non-substantially linear ethylene polymers was determined from the reduced melt -16- E i n crmlslmie *m a e.I =elr *ruw m viscosity vs. shear rate data obtained from capillary rheology evaluations at 190 C. In order to obtain these data, the apparent melt viscosity (poise) vs. apparent shear rate (1/seconds) data was generated according to the ASTM D-3835 method. The reduced melt viscosity data were calculated by dividing the melt viscosity (n) obtained at each shear rate by the melt viscosity measured at the lowest possible shear rate. For the condition used in these determinations, the lowest shear rate corresponds to 2.96 seconds- 1 An example of these reduced melt viscosity calculations are \Q illustrated below.

Caoillarv Rheoloav Data Apparent Melt Viscosity at 2.96 seconds- 1 74,800 poise (7480 Pa-s) Apparent Melt Viscosity at 7.40 seconds-1 46,400 (4640 Pa-s) poise (n) Reduced Melt Viscosity at 2.96 seconds I 1.000 Reduced Melt Viscosity at 7.40 seconds-1 0.620 These reduced melt viscosity data are calculated from the lowest (2.96 seconds to the highest shear rate (2960 seconds- 1 obtained

L

.0 from the capillary rheology evaluations. These reduced melt viscosity data are reported in Table 6 for Comparative Examples 1 and 3 and i. Examples 1 and 2.

a e *e 'e -17- M1904 C I ON MOM~r~~-I~ -4 TABLE 6 Reduced Melt Viscosity Data Reduced Melt Viscosity (x 10 3 Apparent Shear Rate Cl C3 1 2 (second -1) 2.96 1000 1000 1000 1000 7.40 620 610 600 600 14.80 450 450 430 420 29.60 330 330 300 295 74.00 220 220 190 185 148.00 150 150 130 125 296.00 110 90 90 740.00 60 58 51 48 1480.00 37 N/A 31 29 2960.00 22 N/A 19 18 N/A Not Available

I

r The data in Table 6 illustrates the effect of shear rate on melt viscosity (that is, reduced) for Comparative Example 1 vs. Example 1, and Comparative Example 3 vs. Example 2. These data shows that the compositions of this invention have significantly lower melt viscosities as compared to the noninventive compositions at a variety of shear rates.

'0 The percent difference between the reduced melt viscosity values for Example 1 and Comparative Example 1 were calculated at each corresponding shear rate. This data is reported in Table 7.

e -18- D~PP" B"~B~OBID~BQ~srara~irc~bPloa~~ TABLE 7 Calculated Percenlt Difference in Reduced M'elt Viscoit E ves C Apparent Shear Rate Percent Differenlce* in (seconds- 1 Reduced Melt ViscositY 29.60 10.0 74.00 15.8 296.0022.0 74017.6 1480.00 19.4 *P rc n 2960.00C lc la io (at 7.40 seconds 1 600 The percent difference data in Table 7 show that the graftmodified substantially linear ethylene polymers of this invention V. afford processabilitY advantages over the graft-modified non- X C" substantially linear ethylene polymers (the lower the melt viscosity at a given shear rate, generally the better the processibility of the polymer). Moreover, the magnitude of these differences increases with I:.:;shear rate. The benefit of lower melt viscosities is improved extrusion processability, that is, lower excrudate energy consumption, i nonsurging, and smoother extrudate.

Tmat Poere f Cran Bed otinina Graft-modified suibst-antiaflLY Liar L EthYlene -Polymer The following materials were used in this test: ADME OF 500A. a polyprc~pylefle grafted With 1.5 wt MAH and manufactured and sold by Mitsui Petrochemical; the grafted polymer had a melt index of 3.0 g/10 min at 230 C and a density of 0.900 gicm3_ -19- I~r~ Primnacor® 3460. a copolymer of ethylene and acrylic acid manufactured and sold by The Dow Chemical Company; this material contained 9.7 wt acrylic acid monomer and had a melt index of g/l0 min- Graft-.modified substantially linear ethylene polymer:

ENGAGETM

EG8200 polyoletin elastomer made by The Dow Chemical Company, as grafted with 1.3 weight percent maleic anhydride. The graft modified material had a melt index of 0.25 g/10 min and a density of 0.870 g/cm 3 kO ProfaXcO 6524, a polypropylene manufactured and sold by Himonit; it had a melt index of 4 g/10 min at 230 C and a density of 0.9 g/cm 3 The graft-modified substantially linear ethylene polymer (referred to below as Insited" Technology Polymer or ITE') was prepared Saccording to the procedure described in US? 4,950,541. The polymer components were dry mixed at a certain weight ratio (as reported in Table and were then fed into a Werner-Pfleiderer ZSK-30 twin-screw extruder operated at about 210 C. The blends were made in one extrusion pass.

TABLE 8 Copoition of T'esting gamlga sample Graft- Polypropylenq Graft-

EAA

*modified (Prof ax®D Modified (Primacor®) *Polypropylene 6524) Substantially (AdmerO QF Linear 500A) Ethylene- Polymer (ITP) C4 100 50 s 5 so 6 50 7 so 20 50 20 injection molded samples were prepared using a .50 ton (45 tonne) Negri-Bossi Injection Molder operateid with a barrel temperature between 200 and 250 C, a barrel pressure of 40 bars (4 ME'a), cooling ~Smold temperature of 85 F (29 and a residence time in the cooling mold of about 12 seconds. The samples were formed into 2.5" x 6.5" x 0.075" (5 cm x 17 cm x 0.19 cm) plaques.

The flex modulus and IZOD impact properties (at room temperature and -30 C) were measured for each of the samples in Table 8. These c" properties are important in many applications, for example, automobile parts. The properties were measured according to ASTM D-790 and D- 256, respectively, and the results are reported in Table 9. Samples 6 and 7 exhibit very good low temperature impact properties, the result of the presence of the graft-modified substantially linear ethylene O0 polymer.

TABLE 9 Tmnact Properties and Flex Modulus Sample Flex Modulus IZOD at Room IZOD at -30 C (kpsi/Pa) Temp (ft-lb per (ft-lb per in in/J per cm) J per cm) C4 135/9.31 x 105 8.3/4.4 0.55/0.29 2.76/1/47 0.52/0.28 8/5.5 x 104 3.51/1.87 1.07/0.57 6 39/2.7 x 105 6.2/3.3 12.1/6.46 7 56/3.9 x 105 6.55/3.49 5.82/3.11 8 70/4.8 x 105 9.09/4.85 0.84/0.45 Comparison of TTnpact and Other Properties of Snecimans Made by Tniection Moldino of Blends of Polyester and Graft-Modified S 5 Substantiallv Tinear Ethv]ene Polvmer A blend containing 20% by wt substantially linear ethylene/1octene polymer (ITP) grafted with about 1% maleic anhydride and 80% by wt polybutylene terephthlate (PBT) was compounded on a Welding Engineers counter-rotating twin screw extruder operated at 200 rpm 3 0 using the temperature profile reported in Table -21- Iw TABLE Zone Barrel Temp 1 (feed) _240 2 250 3 ;250 4 260 260 6 260 7 260 die 250 The ITP was prepared according to the methods taught in USP S.272,236 and USP 5,278,272, and it was grafted with maleic anhydride as described in the Sample Preparation section above. Certain Sphysical properties of these polymers are reported in Table 11 below.

The PET was Ce~eleex( 2002 manufactured and sold by Hoechst Celenese Corporation. This polyester had a density of 1.31 glcm 3 and a melt flow of 10 g/1 0 min (250 C. 2160 The Tafmer resin was the same as that used in Example C3 above, and it was grafted with maleic jOC anhydride in the same manner as was the ITP.

TABLE 11 )lscitiofl f T'P ~nd MI--'P Rs Melst Flo 1.0 (g/14 min 1.8 Melt Flw74252

I

-22- I Mop 1 5 m

A

The resulting blend scrand was. c o.led by means-of a-water bath and pelletized using a~choppery The.,pelfeLS were d8ryed. unfder vacuum.

and test, specimens were -i nj ecto mode na 30tn--(27 toniie) injection molder under_ the'&oditi~ft§S reported- in Table 1.2." TABLE 12".

Boy Injection'Molder Operatini Condition Zonel I Zone~ 2 6 Zone 3 .260-C: nozzle 263 in-ection pressure'-: 35-50 bar (3.5-5 MPa) mold temperature 70 C 1' L soseswh w The molder produced tensile and impac spCimen hich ere tested using 1.5TH procedures. For purposes- of comparis 'on, sp ecimens were also prepared from PBT,' and an un -grafted 11 P/VBT 2 0/ 80 blend.

The results of various X'Table 13.

physical 'property,- evaluations are rejportedl-in TABLE 13 PrpetyPET PBT/ITP PBT/MAB-a-ITP Weight %ITP 0 20. Yield Tensile 8100/ 4800/ 5200/ (psi/kPa) 55850 .3309 0350 Break Tensile 5800/ 3306/ -1800/ (si/kPa) 39990 22750 -12410 Eloncation 123 15 2 Notched 12od (ft-lb per iri/J per cm) C Dynatup (ft-.lb/J) 1.2/0.64 1.5/0.80 12.1/6.416 I i i 29-1/39.5 1.0/1.4 62.2/84.3 -23- Won is

I

I

II

I

As can be seen in the reported impact. data, the blends containing MAH-g-ITP demonstrate improved impacL properties at amfbient temperature and at -30 C.

The notched IZOD impact energy was measured according to ASTM Dcb, 256 for the PBT, a 20/80 wt blend of ITPIPBT, a 20/g0 wt blend of MAH-g-EPR/PBT, a 20/80 wt blend of MAH-g-EPDM/PBT, a 20/80 wt blend of MAH-I--ITFIPBT, a 10/10/80 wt blend of ITP/MAH-g-ITP/PBT, and a 20/80 wt blend of MAH-g-Tafmer/PBT. The measurements were made under ambient conditions, and the results are reported in Figure ~O1. The description of the MJAH-g-EPDM, MAE-g-EPR. and MAii-g-Taffmer, as well as their notched IZOD impact energy, are reported in Table 14.

TABLE 14 nescrintion o ooriieRsn

I

I

Property MAI4-g-EDM 1 MAH-0j-EPR 2 MAH--Tafmer melt Flow 0-04 j0.08 0.34 min) (11, @190 C) melt Flow 0.71 1.64 4.71 min) !in 190 C) IIn/II Ratio 17.7 120.5 13.8 Density 0.87 0.87 0.87 (q/cm 3 Maleic 0.50 0.70 1.1 Anhydride (Wt II INotched IZOD 0.7511 s (J/cn) lEthylene-propylele diene elastomer functionalized with maleic VS anhydride and sold by Uniroyal Chemical (Product designated ROYALTUF 465A).- 2 Ethylene-propylene elastomer f unctionalized with maleic anhydride and sold by Exxon Chemical (Product designated -Exxelor VA 1801).

)c 3 jui ethylene-propylene elastoner (Tafmer P-0180 from Mitsui) graft modified with maleic anhydride as described above.

As can be seen from the results reported in Tables 13 and 14, the notched IZOD impact energy of the PBT blends of this invention incorporating 20 weight of the MAH-grafted ITP are markedly greater -24than the comparative resins.

Figure 1 reports the notched IZOD impact energy under ambient conditions of several compositions in which the amount of elastomer in the PBT was varied. As reported, compositions containing MAII-g-ITP display a greater impact energy over a wide array or concentrations, and a decidedly greater impact energy when the concentration of the elastomer is in excess of 15 wt of the composition.

Figure 2 reports status similar to Figure 1 except the impact energy is measured on a Dynatup at -20 F (-29 C) using ASTM D-3763-86.

f O At this low temperature, the composition containing MAH-g-ITP has marketedly improved impact resistence over the entire range of reported concentrations.

Figure 3 reports the effect of varying amounts of MAH-g-ITP and SMAH-g-Tafmer in PBT and as evidenced by this report, concentrations of either in excess of 15 wt increase notched IZOD impact energy of the blend, with the blend containing MAH-g-ITP exhibiting superior impact energy as between the two blends.

Polvamide-Polvolefin Compositions Substantially homogeneous polyamide-polyolefin compositions were O prepared using the polyolefins reported in Table 15 and the polyamides reported in Table 16. The polyamides were predried in an oven at 70 C S" for 24 hours.

TABLE Decito/Grade Melt Flow Density M4AH DsrpinI 190 C 1cm 3 (wt) 1. KkM-g-EpDm is an 0.04 0.87 etbylene/proplene/diene elastomfer functionalized with maleic anhydride and sold by Uniroyal chemical

(ROYPLTUF

465A 08 MAHi-g-EPR is an 0.08 08 ethylene/Propylene elastotuer modified with maleic anhydride and sold by Exon~f chemical Exxelor VA 1801li a 04508709 MAH-g-ITP(I)isa 04087.9 substantially linear, homogeneous ethylefl/ octefle polymer graftmodified with maleic anh dride.'D9 4. MAH-a-ITP( 2 is a 0.46 09 substantially linear, homogeneous ethylene! 1octefle polymer graftmodified with maleic T()i 5.0 0.87

N/A

substantily linear, homogeneo0us ethylene/ioctene po mer.

MAB maleic anhydride N/A not applicable -26- TABLE 16 ypical (dry as molded) e Re (dry as molded) RT room temperature r r r The blend compositions reported in Table 17 were prepared by weighing the dried polyamide and polyolefin resins at the indicated proportions. Each of these dry blends were then melt blended on a mm Werner-Pfleiderer twin screw extruder. The extruder melt temperatures were between 260 and 270 C. Each melt blended sample was i0 pelletized and subsequently dried in a vacuum oven at 70 C for 24 hours before injection molding.

The dried melt blended samples were injection molded on a 55 ton tonne) Neggi Bossi injection molder. An ASTM mold was used to obtain the injection molded test samples (that is tensile and IZOD t5 bars). The injection molding temperatures were between 240 and 260 C.

The ASTM mold temperature was set at 70 C. The molded test samples were equilibrated at 50% relative humidity, and then were tested.

-27- TABLE 17 Bl ended Compo'I t ipfl Blend comparative 1 comparative 2 comparative 3 comparative 4 Example 1 ExaMRle 2 Example 3 Exampie %Nylon E6&Grade (bY wt.) 80% of 1000-1(10w MW) 80% of 1000-1 (10w.141,) 80% of 1200-l(high Mw) 80% of 1200-1(hich 80% of 1000-1(0oW MW.) 80% of 1000-1 (low M,) 80% of 1200-l(high M of 1200-1(high Mw,) 80% of 1000-1(10W MW) 80% of 1000-1 (low M,) polyolef in Grade (by wt.) 20% of MAI--g-EPR 20% of MAH-q-EPDM 20% of MAH-g-EPR 20% of MAH-q-EPDM 20% of MAHl-g-ITP(l) 20% of MAH-a-ITP(2) 20% of MAH-g-ITP(l) 20% of 1HAM-c-ITP(2) 10% of MAH-G-ITP(1) plus 10%- ITP(A) 10% of MAH-g-ITP(l) plus I0% ITP(B) 35% of MAH-g-ITP(l) 35% of MAI--ITP(2) Example 6 Example 7 65% of 1000-1(10W M 'J I Example 8 65% of 1000-1(10W The test data obtained on the injection molded blend samples prepared from low molecular weight polyamide (that is Nylon 1000-1) and high molecular weight polyaride (that is Nylon 1200-1) resins are shown in Tables 18 and 19, respectively.

-28- TABLE 18 Test Data for Low Mw Blend compositions Notched IZOD ft-lb er in J 3 r cm Blend II 23 C 0 C -18 C -9C 40CTnie ield Elong WI

YI

(psi/ Comp 1 17.7/ 5,6/ 3.4/ 2.3/ 2.6/ 63/ 62/ 6. 461.

9.44 ~29 1. 25 46 Comp 2 14.1/ 5.2/ 26 67/ 68/ 5. 102.

7.3 2.8 1.7 1.4 13 41850 4S370P Ex. 6 20.1/ 16.5/ 4.31 4.6/ 3.0 1640/ C90 64:11 1.0 34.6, 2.

9.7 10.1 1.3 3.5 2.5 4450 460 Ex. 8 22.1/ 7.1/ 2.7/ 2.4/ 6500/ 67/4 4. 11.5/ 10.7 4.51 2.4/ 2.0 480 63 Nln 10.4/ 0.9/ 1.0/ 0.9/ 1320/ 10/4-04.2 1001 0.78.9 0.4 0.5 0.5 4870 4820 Ex co/n1 6. 4 7/ 67ro75 534l 10-0/ 31 3.5 .S 4750 656 V.p -r TABLE 19 Test Data--for Hiah M tPolvrn1lie Blend CornDSftIfl.

Blend 4 1 Notche d IZOD (ft-lb per in/J per cm)-- 23 C IO f-18 C [-29 C] j4 C Tensile (psi/ 1.1 I IkPa) (psi/ kPa) ie Elong.

YD.

I

I I r 5.2/ 3 1/ 2.8/ 7070/ Comp. 3 21 117.8 11.A 9.50 2.8 1:7 1.5 48750 6560/ 49370 7030/ 59 .6 I r 1 3.3/ 2.7/ comp. 4 Ex. 3 EX. 4 18.9/ 16.5/ 4.9/ e I a 1 A 3. 45230 124.1 4 .6/ 22.2/ 11.8 20.9/ 11 13 20,1 10.9 15.3/ 15.4/ 8.22 4.3/ 2.5 2.8/ 1.5 1.7 2.5/ 1.3 53230 257 0/ 59090 50190 7670/ 5280 174 .2 75.0U yon 11. 1/ 1.2/ 1 13/ 0.9/ 112400/ 1 1o0-1 0.69 0.58 64 10.69 0.48 83490 12,,ntrl I -<4 These IZOD impact data may be plotted as a functionl of temperature. From these plots, the ductile-brittlc transition temperature (DBTT) value for each composition,. for example, the temperature which marks the transition from ductile to brittle -3failure, can be calculated. A comparison of these DBTT values are reported in Tables 20 and 21.

TABLE Ductile-Brittle Transition Temperature values Blend I DBTT Dispersed Particle C) Size (microns) Min Max. Avg Conparative 1 8 0.10 2.5 Conparative 2 5 0.17 10.0 Exam le 1 -12 0.05 1.3 0.3 Exam le 2 3 Examle 5 9 Exam le 6 9 Exa ple 7 -27 Example 8 -13 TABLE 21 Ductile-Brittle Transition Temperature Values Blend 4 DBTT Dispersed Particle Size (microns) __innM Max. Avg.

Comparative 3 -11- Comparative 4- 10 Exmle3 26 0.05 1.0 0.1 Example 4 -1 The ductile-brittle transition temperatures clearly show that the compositions which contain the maleic anhydride graft-modified 6substantially linear, ethyleneloctene polymers have superior low temperature toughness as compared to the other compositions evaluated.

These unexpected results are especially evident for the compositions which containl the maleic anhydride graft-modified substantially linear ethyleloctele polymer having a low specific gravity (that is 0.870 %3 a/cm 3 CompoSitions which exhibit low temperature toughness have commercial advantages over other compositions, especially those used in outdoor applications.

In addition, the comparative polyolefins must have a specific value of modulus and are not effective when used in small amounts for example, less than about 25 wt The IZOD impact data clearly show that maleic and hydride graft-modified substantially linear, ethylene/octene polymer can effectively impact modify polyamidepolyolefin resin compositions at reduced or low concentrations. At these reduced concentrations, these novel polyamide-polyolefin resin 0C compositions exhibit the superior low temperature toughness that was previously not available. These improved properties are indicative of compositions having superior heat aging and weatherability performance.

Although this invention has been described in considerable detail through the preceding examples, such detail is for the purpose of illustration only and is not to be construed as a limitation upon the invention. Many variations can be made upon the preceding examples without departing from the spirit and scope of the invention as described in the following claims.

*3 e -32-

Claims (14)

1. A composition comprising a substantially homogeneous blend of at least one thermoplastic polymer and at least one substantially linear ethylene polymer grafted with at least 0.01 wt based on the weight of the grafted ethylene polymer, of an unsaturated organic compound containing at least one site of ethylenic unsaturation and at least one carboxyl group, the ethylene polymer characterized as having: a melt flow ratio, 110/12 2 5.63; (ii) a molecular weight distribution. M/Mn. defined by the i O equation: Mw/Mn I (110/12) 4.63; (iii) a density greater than 0.850 g/cm 3 and (iv) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin [s polymer having about the same 12 and Mw/Mn.

2. The composition of Claim 1 in which the substantially linear ethylene polymer comprises between about 95 and 50 wt polymerized ethylene monomer and between about 5 and 50 wt of at least one polymerized alpha-olefin comonomer of 3 to about 20 carbon atoms.

3. The composition of Claim 2 in which the substantially linear ethylene polymer has a density between about 0.860 and about 0.935 g/cm 3

4. The composition of Claim 3 in which the substantially linear ethylene polymer has a melt flow ratio from about 6.5.to 2 5. The composition of Claim 4 in which the substantially linear ethylene polymer has a melt index from about 0.5 to 200 g/10 min.

6. The composition of Claim 5 in which the substantially linear i ethylene polymer has a molecular weight distribution measured by gel S i permeation chromatography of between about 1.8 and -33- The composition of Claim 6 in which the substantially linear ethylene polymer is an interpolymfer of ethylene and at least one comololer selected fromn the group consisting of propylene. 1-butene. 1-hexene, 4 -methyl-lpeltene, and 1-octele.

8. The composition of Claim 7 in which the substanltially linear ethylene polymer is a. copolymfer of ethylene and I-butene, 1-hexene. 4- methyl-l-petene or 1-octele.

9. The compositionl of claim 6 in which the substantially linear ethylene polymer is a. copolymfer of ethylene and I-octele. The compositioni of claim 6 in which the unsaturated organic compound is seleCted from the group consisting of nialeic, acrylic, methacrylic. itaconic, crotonic, alpha-methyl crotoflic and cinnamnic acids. anhydrides, esters and their metal salts, and fuinaric acid and its ester and metal salts.

11. The compositioni of Claim 7 in which the unsaturated organic compound is maleic anhydride.

12. The comnposition of Claim I in which the grafted unsaturated organic compound is between about 0.05 and about 10 of the weight of the grafted polymer.

13. The composition of Claim 1 in which the thermoplastic polymer comprises at least one of a polyurethane. polycarbonate, polystyrene, polyester, epoxy, polyalnide and a polyolet in containing polar groups.

14. The com-position of Claim 13 further comprising a nongraf ted Ssubstantially linear ethylene polymer- The composition of Claim 1 in which the thermoplastic polymer is a polyester. -34-

16. The composition of claim 1 in which the thermoplastic polymer is a polyamide.

17. The composition of claim I in which the thermoplastic polymer is at least one of EAA, EVA, ECO, EPCO and ECOAA. S 18. The composition of claim 1 further comprising filler.

19. The composition of claim 18 in which the filler is at least one of silica, talc, glass, clay, and carbon black. A composition comprising a substantially homogeneous blend of at least one thermoplastic polymer and at least one substantially linear ethylene polymer grafted with to at least 0.1 wt%, based on the weight of the grafted ethylene polymer, of an unsaturated organic compound containing at least one site of ethylenic unsaturation and at least one carboxyl group, substantially as hereinbefore described with reference to any one of the examples but excluding the Comparative Examples. Dated 16 October, 1998 The Dow Chemical Company Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON .9* i' t*