MXPA99009420A - Polymer compositions having improved elongation - Google Patents

Abstract

The subject invention is directed to polymer compositions which comprise a homogeneous ethylene/&agr;-olefin interpolymer, a wax and a nucleating agent, wherein the nucleating agent is provided in an effective amount such that the percent elongation at break of the polymer composition is at least fifty percent greater than the percent elongation at break of a comparative composition which lacks the nucleating agent. The polymer compositions of the invention will find utility in applications requiring high elongation at break, while maintaining a high onset of crystallization temperature, such as in the high-speed coating of fabrics, carpet backing, floor tile and sheeting, and adhesives.

Description

POLYMERIC COMPOSITIONS THAT HAVE IMPROVED ELONGATION The present invention is directed to polymer compositions having improved elongation. In particular, the present invention is directed to polymeric compositions comprising a linear or substantially linear homogeneous ethylene polymer, a wax having a low molecular weight and which has a higher crystalline melting point than the linear or substantially homogeneous ethylene polymer. linear and a nucleation agent. Homogeneous ethylene polymers having a density less than 0.910 g / cm3, particularly less than 0.900 g / cm3, preferably less than 0.800 g / cm3, and even more preferably less than 0.880 g / cm3, have good elongation properties, ie , such as a high elongation to rupture and the capacity to resist high degrees of tension before rupture, with the degree of elongation properties, thus increasing the density of the polymeric decreases. However, homogeneous ethylene polymers having such elongation properties lack a highly crystalline fraction that imparts the use of increased upper temperature and the favorably high crystallization temperature principle. To compensate for the use of the poor upper temperature and the low principle of the crystallization temperature characteristic of the homogeneous ethylene polymer having a density of less than O 910 g / cm 3, it may be convenient to mix a material of superior quality, such as homogeneous ethylene polymer of a higher density or a traditional wax However, while the addition of such superior quality material can increase the use of the higher temperature and provide a higher temperature crystallization principle, it causes a highly deteriorated loss of properties of Elongation Industrialists could find great advantage in polymeric compositions that have favorable upper use temperatures and high crystallization principle temperatures, but retain the elongation favorable to breakage and the ability to withstand high degrees of stress before breakage that is characteristic of poli homogeneous ethylene esters having a density less than 0910 g / cm3 Hot melt adhesives comprising homogeneous linear or substantially linear ethylene polymers are known. See, for example, WO 97/33921, WO / 12212 and WO 94/10256. Each of the hot melt adhesive formulations exhibit many commercially attractive attributes, it would be convenient for certain formulations to improve the elongation at break of these compositions. The industrialists could also find great advantage in hot melt adhesive formulations for use in formulations that they require high elongation at break without incurring a detrimental effect on the yield or strain at break, such as, for example, in binding adhesives. Accordingly, the present invention provides a polymer composition comprising (a) an ethylene / interpolymer. homogeneous α-olefin, (b) a wax, and (c) a nuc agent Lection, wherein the nucleating agent is provided in an effective amount such that the percentage elongation at break of the polymer composition is at least fifty percent greater than the percentage elongation at break of a comparative composition lacking the agent In the preferred embodiments, the homogeneous ethylene / α-olefin interpolymer could be a linear or substantially linear homogeneous ethylene / α-olefin interpolymer, which preferably has a density less than 0 910 g / cm 3, more preferably less than 0900 g / cm3, still more preferably less than 0890 g / cm3 and still more preferably less than 0880 g / cm3 In the preferred embodiments, the wax may be a paraffin wax, microcrystalline wax, Fischer-Tropsch wax or polyethylene by-product wax, or homogeneous wax, which is preferably characterized as having an Mp not greater than 3000, and having a density greater than that of the homogeneous ethylene polymer of the component (a) preferred embodiments, the nucleating agent could be provided in an amount of at least 001 weight percent, more preferably at least 0-5 weight percent, even more preferably at least 0-1 weight percent and even more preferably of at least 0 2 weight percent, preferably not more than 10 weight percent, more preferably not more than 5 weight percent, even more preferably not more than 1 weight percent, and even more preferably less than 5 weight percent. Preferred polymer compositions of the invention exhibit a percent elongation at break of at least four times greater than the percent elongation at break of a a comparative composition lacking nucleating agent The present invention further provides a hot melt adhesive composition comprising (a) an olefin polymer, (b) a nucleating agent, and (c) optionally, one or more of the thickener , plasticizer or wax These and other embodiments are described more fully in the following detailed description FIGURE 1, is a bar graph representation of the elongation properties of the polymer compositions of the invention and comparative compositions lacking a nucleating agent. Polymer compositions of the invention comprise at least one homogeneous ethylene / α-olefin interpolymer which is an interpolymer of ethylene and at least one C3-C20 α-olefin. The term "interpolymer" is used herein to mean a copolymer, or a terpolymer, or a higher order polymer. That is, at least one different comonomer polymerized with ethylene to form an interpolymer. The homogeneous ethylene / α-olefin interpolymer is a homogeneous linear or substantially linear ethylene / α-olefin interpolymer. By the term "homogeneous", it is understood that any comonomer is randomly distributed within a given interpolymer molecule and substantially all interpolymer molecules have the same ethylene / comonomer ratio within the interpolymer. The melting peak of homogeneous linear and substantially linear ethylene polymers, were obtained using differential scanning calorimetry, will be expanded as heterogeneous polymers, when a homogeneous polymer has a melting peak greater than 115 ° C (as is the case of polymers having a density greater than 0.940 g / cm 3), additionally they will not have a different lower temperature melting peak. In addition or as an alternative, the homogeneity of the polymer is described by IDRCC (Short Chain Branching Distribution Index) or IEDC (Composition Distribution Extension Index), which is defined as the weight percentage of the polymer molecules that have a comonomer content within 50 percent of the average total molar comonomer content. The IDRCC of a polymer is easily calculated from data obtained from techniques known in the art, such as, for example, fractionation of increasing temperature elution (abbreviated hereinafter as "FEAT"), which is described, for example , in Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol., 20, p. 441 (1982), in the U.S. Patent. 4,798,081 (Hazlitt et al.), Or in the U.S. Patent. 5,089,321 (Chum et al.). The IDRCC and IEDC for the homogeneous ethylene / α-olefin interpolymers useful in the invention preferably greater than 50 percent, more preferably greater than 70 percent, IDRCC and IEDC greater than 90 percent being easily achieved. The homogeneous ethylene / α-olefin interpolymers useful in the invention are characterized by having a narrow molecular weight distribution (Mp / Mn). For homogeneous ethylene / α-olefins useful in the polymer compositions of the invention, Mp / Mn is 1. 5 to 2.5, preferably from 1.8 to 2.2, even more preferably 2.0.

The substantially linear ethylene interpolymers are homogeneous interpolymers having long chain branching. Due to the presence of said long chain branching, the substantially linear ethylene interpolymers are further characterized by having a melt flow ratio (o / l) that can vary independently of the polydispersity index, i.e., the molecular weight distribution Mp / Mn. According to this aspect, the substantially linear ethylene polymers with a high degree of processability despite a narrow molecular weight distribution. It is noted that the substantially linear interpolymers useful in the invention differ from low density polyethylene in a high pressure process. one aspect, while the low density polyethylene is an ethylene homopolymer having a density of 0900 to 0935 g / cm3, the linear and substantially linear homogeneous interpolymers useful in the invention require the presence of a comonomer to reduce the density on the scale from 0900 to 0935 g / cm3 The long chain branches of the substantially linear ethylene interpolymers have the same comonomer distribution as the interpolymer base structure and can be as long as the same length of the interpolymer base structure When the interpolymer of ethylene / α-olefma substantially and linear is used in the practice of the invention the polymeric material could be characterized by having a base structure of the interpolymer substituted with 001 to 3 long chain branches per 1000 carbons. Methods for determining the amount of long chain branching, both qualitative as quantitatively known in the art are qualitative methods for determining the presence of the long chain branching, see, for example, U.S. Patent Nos. 5,272,236 and 5,278,277 As a fourth group, a reometer of the same comonomer or comonomers, and having a l2, Mp / Mn, and density, each being within 10 percent of the substantially linear ethylene interpolymer. An evident short stress against the apparent shear rate can be used to identify the melting fracture phenomenon and to quantify the rate of melting. Critical shear stress and critical short stress of ethylene polymers According to Ram a urthy, in Journal of Rheology, 30 (2), 1986, pp. 337-357, above a certain regime of critical shear stress, the observed irregularities of strudates are broadly classified into two main types fracture of superficial fusion and fracture of coarse melt The surface melting fracture occurs under flow conditions evidently at rest and scales in detail from loss of specular gloss to the more severe form of "shark skin". In the present, the use of the gas extrusion rheometer is determined. described above, the principle of the surface melting fracture is characterized as the principle of extrudate gloss loss in which the rigidity of the extrudate surface is only detected by a 40-fold increase. The rate of critical shear stress at the beginning of Surface melt fracture for a linear ethylene interpolymer is at least 50 percent greater than the shear rate c Ritic at the beginning of the melt fracture for the linear ethylene polymer having the same comonomer or comonomers having a l2, Mp / Mn and gas extrusion (REG) can be used to determine the rheological processing index (IP), the regime of critical shear stress at the beginning of the surface melt fracture, and the critical short stress at the beginning of the thick melt fracture, which in turn indicates the presence or absence of long chain branches as the next fourth group. The gas extrusion rheometer useful in determining the rheological processing index (IP), the regime of critical shear stress at the beginning of the surface melt fracture and the critical shear stress at the beginning of the coarse melt fracture, was described by M Shida, RN Shoroff and LV Cancio in Polymer Engmeepng Science, Vol 17, No. 11, page 770 (1977), and in "Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold co. (1982) on pages 250 and 5500 psig (between 1 72 and 379 MPa) using a diameter of 00754, given 20 1 L / D with an entry angle of 180 degrees For substantially linear ethylene interpolymers, the IP is the apparent viscosity (in kpoises) of a material measured by REG at an apparent short voltage of 0215 MPa. The substantially linear ethylene interpolymers useful in the invention have an IP on the scale of 001 kpoises to 50 kpoises, preferably 15 kpoises or less Substantially linear ethylene interpolymers have an IP that is less than or equal to 70% of the IP of a linear ethylene interpolymer (either a Ziegler polymer polyepper or a homogeneous linear ethylene interpolymer) having the density within 10% percent of the substantially linear ethylene polymer The coarse melt fracture occurs under non-stable extrusion flow conditions and varies from regular to random distortions (alternating rough and uniform). me, helical, etc.) The critical shear stress at the beginning of the coarse melt fracture of the substantially linear ethylene interpolymers, especially those having a density greater than 0 910 g / cm3, is greater than 4 x 106 d? nas / cm2 (04 MPa) The presence of long chain branching is also determined qualitatively by Dow's Rheology Index (DRI), which expresses a "normalized relaxation time as the result of chain branching. long "(See, S Lai and GW Knight, ANTEC '93 Proceedmgs, INSITE ™ Technology Poiyolefins (SLEP) -New Rules of the Structure / Rheology Relationship of Ethylene a-Olefin Copolymers, New Orleans La, May 1993 DRI values vary of 0 for polymers that have no measurable long chain branching such as the Tafmer ™ products available from Mitsui Petrochemical Industries and the Exact ™ products available from Exxon Chemical Company) , up to 15 and are independent of the melt index. In general, for low to medium pressure ethylene polymers, in particular at lower densities, DRI provides improved melt elasticity and high shear fluidity correlations in relation to the correlations attempted with the merge flow relationships. The substantially linear ethylene interpolymers could have a DRI preferably of at least 0.1, more preferably of at least 0.5 and even more preferably of at least 0.8. You can calculate DRI from the equation: -r.,, -? XX- * 1.00649, ".... DRI = (3.652879 *. O /? O-1) / 10 where t0 is the characteristic relaxation time of the interpolymer and 0 0 is the shear viscosity of zero of the interpolymer. Both t0 and? 0 are the values of "best adapted" for the crossed equation, that is, ? /? o = K1 + (Y * tD) 1"n) in which n is the index of the energy law of the material and? Y ? they are the measured viscosity and the shear rate, respectively. The determination of the base line of the viscosity and the data of the shear rate obtained using a Rheometric Mechanical Spectrometer (RMS-800) under a dynamic sweep mode of 0.1 to 100 radians / second at 160 ° C and a reometer of Extrusion of gases (REG) at extrusion pressures of 6.89 to 34.5 MPa, which corresponds to the shear stress of 0.086 to 0.43 MPa, using a diameter of 0.0754 mm. a die of 20: 1 L / D at 190 ° C. Determinations of specific material can be carried out from 140 to 190 ° as required for adapted melt index variations.

For quantitative methods for the purpose of determining the presence of long chain branching, see, for example, Patents of E.U.A. Nos. 5,272,236 and 5,278,272; Randall (Rev. Macromol. Chem. Phys., C29 (2 &3), pp. 285-297), which describes the measurement of long chain branching using 13C 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) p. 103-112, which describes the use of gel permeation chromatography coupled with a low angle laser light scanning detector (CPG-DBLLAB) and gel permeation chromatography with a differential viscometer detector (CPG-DV). A. Willem deGroot and P. Steve Chum, both of The Dow Chemical Company, on October 4, 1994 Conference of the Federation of Analytical Chemistry and Spectroscopy Society (FACSS) in St. Louis, Missouri, presents data demonstrating that CPG-DV is a useful technique for quantifying the presence of substantially linear long chain branching in ethylene polymer. In particular, deGroot and Chum found that the presence of long chain branches are substantially linear ethylene polymers well correlated with the level of long chain branches using 13 C NMR. In addition, deGroot and Chum found that the presence of content does not change the hydrodynamic volume of the samples in solution and, so, one can take into account the increased atpbuible molecular weight of short chain octene branches by the known molar percent octene. in the sample By deconvolution of the contribution of the increase of the atpbuible molecular weight to the short chain branches of 1-octene, deGroot and Chum show that GPC-DV can be used to quantify the level of long chain branches in ethylene copolymers / substantially linear octane The homogeneous ethylene polymer can be suitably prepared using a single site metallocene or a constructed geometric metal complex Constructed geometry metal complexes are described in US Application No. 545,403, filed July 3, 1990 ( EP-A-416-815), Application of EUA Series No. 702,475, filed on June 20, 1991 (EP -A-514,828), as well as US-A-5,470,993, 5,374,696, 5,231,106 5,055,438, 5,057,475, 5,096,867, 5,064,802 and 5,132 380 In the US Series Number 720,041, filed on June 24, 1991, (EP-A-514,828) describes certain borane derivatives of the above-constructed geometry catalysts and a method for their preparation taught and claimed In US-A-5,453,410 combinations of geometric catalysts constructed with an alumoxane are described as suitable olefin polymerization catalysts Metal complexes Illustrative constructed geometries in which titanium is present in the oxidation state +4 including but not limited to the following: (n-butylidene) di methyl (5- tetramethylmethylcyclopentadienyl) silanetitanium (IV) di methyl; (n-buty lamido) di meti lo (? s-tetra methylcyclopentadienyl) silanetitanium (IV) dibenzyl; (t-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl (t-butylamido) d -methyl (? 5-tetramethylcyclopentadienyl) silane-titanium (IV) dibenzyl; (cyclododecylamido) dimethyl (? 5-tetramethylcyclo-pentadienyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl: (1-adamantyl-amido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (t-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (l-adamantylamido) dimethyl (? 5-tetramethylcyclo-pentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) diisopropoxy (? 5-tetramethyl-cyclopentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) diisopropoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) -diisopropoxy (5-tetramethylcyclopentadienyl) -silanetitanium (IV) dimethyl; (cyclododecylamido) diisopropoxy (5-tetramethylcyclopentadienyl) -silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido) diisopropoxy (5-tetramethylcyclopentadienyl) -silanetitanium (IV) dimethyl; (2,4,6-trimethylaniiido) diisopropoxy (? 5-tetramethyl-cyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) dimethoxy (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl (cyclododecylamido) -dimethoxy (? 5- tetra methylcyclopentadienyl) - silanetitanium (IV) dibenzyl; (l-adamantylamido) diisopropoxy (β-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (1-adamantylamido) diisopropoxy (5-tetramethylcyclopentadienyl) -silanetitanium (IV) dibenzyl; (n-butylamido) dimethoxy (? s-tetramethylcyclo-pentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) dimethoxy - (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido) dimethoxy (? 5- tetra methylcyclopentadienyl) silanetitanium (IV) dimethyl; (2,4,6-trimethylanilido) dimethoxy (? 5-tetramethyl-cyclopentadienyl) silane-titanium (IV) dibenzyl; (1-adamantylamido) dimethoxy (? 5-tetramethylcyclo-pentadienyl) silanetitanium (IV) dimethyl; (1-adamanti I amido) di methoxy (? 5-tetramethylcyclopentadie nyl) silanetitanium (IV) dibenzyl; (n-butylamido) -ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) ethoxymethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) -silanetitanium (IV) dimethyl; (cyclododecylamido) ethoxymethyl (5-tetramethyl-cyclopentadienyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylan and I id o) ethoxymethyl o- (? 5-te tra methi I cyclopentadienyl) silanetitanium (IV) di methyl; (2,4,6-trimethylanilido) ethoxymethyl (? 5-tetramethyl-cyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) dimethyl (? 5 -tetramethylcyclopentadienyl) silane-titanium (IV) dimethyl; (l-adamantylamido) -ethoxymethyl (? 5-tetramethylcyclo-pentadienyl) silanetitanium (IV) dimethyl; and (1- adaman ti lamido) etox? ethereal (? -tetramet? lc? clo-pentad? in?) silanetitanium (IV) dibenzyl Illustrative constructed metal complexes in which titanium is present in the oxidation state +3 including but not limited to following (n-but? lam? do) d? met? lo (? 5-tetramet? lc? clopentad? in?) silanetitanio (lll) 2- (N, Nd? met? lam? no) benc? lo, (t-butylamido) d? met? lo (? 5-tetramet? lc? clopentad? in? lo) s? lanet? tan? or (III) 2- (N, Nd? met? lam? no) benzyl, (c? clododec? lam? do) d? met? lo (? -tetramet? lc? pentadienil) silanetitanio (lll) 2 - (N, Nd? Met? Lam? No) benc? Lo, (2,4,6-tr? Met? Lan? Do?) D? Met? Lo (? 5- te trametilcicl open tad? En? Lo? ) s? lanet? tamo (lll) 2- (N, Nd? met? lam? no) benc? lo, (l-adamant? lam? do) d? met? lo (? 5-tetramet? lc? clopentad? in? lo) s ? lanet? tan? o (lll) 2- (N, Nd? met? lam? no) benc? lo, (n-but? lam? do) d? sopropox? (? 5-tetramet? lc? clopentad? in? lo? s? lanet? tan? o (lll) 2- (N, Nd? met? lam? no) benc? lo, (c? clododec? lam? do) d? sopropox? (? 5-tetramet ? lc? clopentad? in? lo?)? s? lanet? tan? o (lll) 2- (N, Nd? met? lam? no) benc? lo, (2,4,6-tr? met? lan? l? do) d? sopropox? (? -2-met? l? nden? lo) s? lanet? tan? o (lll) 2- (N, Nd? met? lam? no) benc? lo, ( 1-4 adamant? Lam? Do) d? Sopropox? (? 5-tetramet? Lc? Clopentad? In?) Silanetitanium (III) 2- (N, Nd? Met? Lane) benzyl, ( n-butylamido) d? methox? (? 5-tetramet? lc? clopentad? in?) s? lanet? tan? o (lll) 2- (N, Nd? met? lam? no) benc? lo, ( c? clododec? lam? do) d? methox? (? -tetramet? lc? clopentad? in?) s? lanet? tan? o (lll) 2- (N, N-dimethylamino) benzyl; (l-adamantylamino) dimethoxy (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (n-butylamido) ethoxymethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (cyclododecylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (2,4,6-trimethylanilido) ethoxymethyl (? S-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; and (1-adamantylamino) ethoxymethyl (? 5-tetramethyl-cyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl. Illustrative built-metal geometric complexes in which titanium is present in the oxidation state +2 including but not limited to the following: (n-butylamido) -dimethyl- (5-tetramethylcyclopentadienyl) silanetitanium (II) 1, 4 -diphenyl- 1,3-buta-diene, (n-butylamido) -dimethyl- (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (t-butylamido) dimethyl (? 5- tetra methylcyclopentadienyl) silane-titanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethyl (? 5-tetramethyl-cyclopentadienyl) silanetitanium (II 1, 3-pentadiene (cyclododecylamido) dimethyl - (? 5- tetra methyl-cyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene (c? clododec? lam? do) d? met? lo (? 5 -tetramet? lc "clopentad" in?) silanetitanium (II) 1, 3-pentadiene, (2,4,6-tmetmet? l-an? l? do) d? met?! o (? 5-tetramethylcyclopentadieni lo) - s? lanet? tan? o (II) 1, 4-dfen? lo-1, 3-butadiene, (2,4,6-tr? met? lan? l? do) d? met? lo (? 5- tetramet? lc? clopentadienyl) silanetitanium (II) 1,3-pentadiene, (2,4,6-tr? met? lan? l? do) d? et? lo (? 5-tetramet? l c? clopentad? in? it) s? lanet? tan? o (IV) dimethyl, (1-adamant? Lam? Lam? Do) d? Met? Lo (? 5-tetramet? Lc? Clopenta-dienyl) silane-titanium (II) 1,4-d? Phenol-1 , 3-butadiene, (1-adamant? Lam? Lam? Do) d? Met? Lo (? 5-tetramet? Lc? Clopentad? In? Lo) s? Lanet? Tan? O (II) 1, 3 -pentad? ene, (t-but? lam? do) -d? met? lo? (? 5-tetramet? lc? clopentad? in? lo? s? lanet? tan? or? (II) 1,4-d? phen-1,3-butadiene, (t-but? l-am? do) -d? met? lo (? 5-tetramet? lc? clopentad? in? it) s? lanet? tan? (II) 1, 3-pentadiene, (n-but? Lam? Do) d? Sopropox? (? 5-tetramet? Lc? Clopentad? In?) -s? Lanet? Tan? O (II) 1, 4-d? F in? L-1, 3-butadiene, (n-but? Lam? Do) d? Sopropox? (? 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentad? Ene (c? clododec? lam? do) -d ?? sopropox? (? 5-tetramet? lc? clopentad? in?) silanetitanio (II) 1,4-d? f en? it-1, 3-butad? eno, (cyclododecylamido) -d? sopropox? (? 5- tetra me ti lc? clopentad? in? lo) -s? lanet? tamo (II) 1,3-pentadiene, (2,4,6-tr? met? lan? l? do) d? sopropox? (? 5-2-met? l? nden? lo) s? lanet so? o (II) 1, 4-d? f in? -1-3, butadiene, (2,4,6-tr? met? lan? l? do) -d? sopropox? (? 5 - tetramethylcyclopentadienyl) silanetitam (II) 1,3-pentadiene, (1-adamant? lam? lam? do) d? sopropox? (? 5-tetramet? lc? clopentad? in?) silanetitanium (II) 1 , 4-diphenyl-1,3-butadiene; (1-adamantylammido) diisopropoxy (? 5-tetramethyl-cyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (cyclododecylamido) dimethoxy (? 5- tetra methylcycline opentadienyl) -silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido) dimethoxy (5-tetra methylmethylpentadienyl) silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-buta-diene; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (1-adamantyl-amylamido) dimethoxy (? -tetra methyl methylcyclopentadienyl) silanetitanium (II) 1,4-difyl enyl-1,3-butadiene; (1-adamantyl-amylamido) dimethoxy (5-tetramethylcyclopentadienyl) -silanetitanium (II) 1,3-pentadiene; (n-butylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-buta-diene; (n-butylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (cyclododecylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) -silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido) ethoxymethyl (5- methyl tetracyclopentadienyl) silanetitanium (II) 1,3-pen.ladiene; (2,4,6-trimethylanilido) ethoxymethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (1-adamantylammido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; and (1-adamantylammido) ethoxymethyl (β-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene. The complexes can be prepared by the use of well-known synthetic techniques. The reaction is carried out in a suitable solvent that does not interfere with the temperature of -100 to 300 ° C, preferably -78 to 100 ° C, more preferably 0 to 50 ° C. A reducing agent is used to cause the metal to be reduced from a higher to a lower oxidation state. Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alkali metal or alkaline earth metal clays such as sodium / mercury amalgam and sodium / potassium clay., sodium naphthalenide, potassium graphite, lithium alkyls, lithium alkadienyls or potassium and Gringnard reagents. Suitable reaction media for the formation of the compounds include aliphatic and aromatic hydrocarbons, ethers and cyclic ethers, particularly branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane. octane and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; aromatic compounds and hydrocarbyl substituted aromatics such as benzene, toluene and xylene, dialkyl ethers of C -4, dialkyl ether derivatives of C? _ of (poly) alkylene glycols and tetrahydrofuran. Mixtures of the above are also suitable. Suitable activating cocatalysts and activation techniques can be previously observed with respect to the 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 US Series No. 07 / 547,718). EP-A-520,732 (equivalent to Series No. 07 / 876,268), WO 95/00683 (equivalent to US Series No. 08 / 82,201) and EP-A-520,732 (equivalent to US Series No. 07 / 884,966 filed May 1, 1992). Activation cocatalysts suitable for use herein include perfluorinated tri (aryl) boron compounds and more spatially tris (pentafluorophenyl) borane; non-polymeric, compatible, non-coordinating, ion-forming compounds (including the use of such compounds under oxidation conditions), especially the use of ammonium, phosphate, oxonium, carbonium, silylium, sulphonic salts of non-coordinating anions and ferrocenium salts of compatible non-coordinating anions. Suitable activation techniques include the use of volume electrolysis. A combination of the activation cocatalysts mentioned above and the techniques can be used as a well.

Illustrative, but not limiting, examples of boron compounds that can be used as activation catalysts are: tri-substituted ammonium salts such as: trimethylammonium tetrakis (pentafluoro-phenyl) borate; triethylammonium tetrakis (pentafluorophenyl) borate; tripropylammonium tetrakis (pentafluorophenyl) borate; tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate; tri (sec-butyl) ammonium tetrakis (pentafluoro-phenyl) borate; N, N-dimethylanilinium tetrakis (pentaflouorophenyl) borate; N, Nd-methylanylyl n-butyltris (pentaflourophenyl borate; N, N-dimethynyl yl benzyltris (pentafluorophenyl) borate; N, Ndimethylanyl, benzyltris (pentafluorophenyl) borate; N, N-methyalkynyl tetrakis (4- (t-butyldimethylsilyl); -2,3,5,6-tetrafluorophenyl) borate; NN-dimethylarynyl tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate; NN-di methyla nyl or pentafluorofenoxitris (pentafluorophenyl) ) borate; NN-diethylanilinium tetrakis (pentafluorophenyl) borate; N, N-dimethyl-, 2,4,6-trimetyl I to nil in io tetrakis (pentafluorophenyl) borate; trmethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; tripropylammonium tetrakis (2, 3,4,6-tetrafluorophenyl) borate; tri (n-butyl) ammonium tetrakis (2, 3,4,6-tetrafluorophenyl) borate dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyiol) borate; N, N-dimethylammonium tetrakis (2, 3,4,6-tetrafluorophenyl) borate; NN-diethylanilyl tetrakis (2, 3, 4,6-tetrafluorophene nile) borate; and N, N-dimethyl-2,4,6-trimethylanilyl tetrakis (2,3,4,6-tetrafluorophenyl) borate; disubstituted ammonium salts such as: di (ip ropi I ammonium tetrakis (pentafluorophenyl) borate; and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis (pentafluoro-phenyl) borate; tri (o-tolyl) phosphonium) tetrakis (pentafluorophenyl) borate; and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentaf luorofenyl) borate; disubstituted oxonium salts such as: diphenyloxonium tetrakis (pentafluoro-phenyl) borate; di (o-tolyl) oxonium tetrakis (pentafluorophenyl) ) borate; and di (2,6-dimethylphenyl) oxonium te t raq uis (pentaf luorof eni I) borate; and disubstituted sulfonium salts such as: diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis ( pentafluo rofenyl) borate; bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate A preferred activating cocatalyst is tripentafluorophenylborane Alumoxanes, especially methylalumoxane or methylalumoxane modified with triisobutylaluminum or they are also suitable activators and can be used for the activation of the metal complexes present. The molar ratio of the metal complex: activation cocatalyst preferably employed ranges from 1: 1000 to 2: 1, more preferably from 1: 5 to 1.5.1, more preferably from 1: 2 to 1: 1. In the preferred case in which a metal complex is activated by methylalumoxane modified with trispentafluorophenylborane and tributylaluminum, the molar ratio of titanium: boron: aluminum is usually 1:50:50 to 1: 0.5: 0.1, more usually 1: 3: 5 A support, especially silica, alumina or a polymer (especially poly (tetrafluoroethylene) or a polyolefin) can be used and conveniently used when the catalyst is used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of the catalyst (based on metal): support from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20, and even more preferably from 1: 10,000 to 1:30, in the reaction with higher polymerization the molar ratio of the catalyst: polymerizable compounds used is 10'1: 1 to 10"1: 1, more preferably 10" 9: 1 to 10"s: 1 In All the times, the individual ingredients as well as the recovered catalyst components can be protected from oxygen and moisture.Therefore, the catalyst components and catalysts can be prepared and recovered in an atmosphere free of oxygen and moisture. Thus, the reaction was carried out in the presence of a dry inert gas such as, for example, nitrogen.The polymerization was carried out as a batch mode or a continuous polymerization process, with continuous polymerization process which is required for the preparation of substantially linear polymers. In a continuous process, ethylene. comonomer and optionally solvent and diene are continuously supplied in the reaction zone and polymer product continuously removed therein. In general, the homogeneous linear or substantially linear polymer can be polymerized at Ziegler-Natta or Kaminsky-Sinn type polymerization reaction conditions, that is, the reactor pressures raise the atmospheric pressure to 3,500 atmospheres (350 MPa). The temperature of the reactor could be higher than 80 ° C, normally from 100 ° C to 250 ° C and preferably from 100 ° C to 150 ° C, than the lower end temperatures of the scale, i.e. temperatures above 100 ° C C that favor the formation of polymers of lower molecular weight. In conjunction with the reactor temperature, the molar ratio of hydrogen: ethylene influences the molecular weight of the polymer, with higher levels of hydrogen leading to the lower molecular weight polymers. When the desired polymer has a l2 of 1 g / 10 min., The molar ratio of hydrogen: ethylene is usually 0: 1. When the desired polymer has a l2 of 1000 g / min., The molar ratio of hydrogen: ethylene is usually from 0.45: 1 to 07: 1. the upper limit of the molar ratio of hydrogen. Ethylene is normally 2.2-2.5: 1. In general, the polymerization process is carried out with an ethylene differential pressure of 70 to 7000 kPa, more preferably 30 to 300 kPa. The polymerization is generally carried out at a temperature of 80 to 250 ° C, preferably 90 to 170 ° C and more preferably greater than 95 to 140 ° C. In most polymerization reactions the molar ratio of the polymerizable polymerizable catalyst employed is 1012 1 to 10"1 1, more preferably 10" 9 1 to 10"51 Solution polymerization conditions utilize a solvent for the respective components of the reaction Preferred solvents include mineral oils and various hydrocarbons which are liquid to 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-E ™, 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 a quantity suf To avoid phase separation in the reactor As the solvent works to absorb heat, less solvent leads to a less adiabatic reactor. The ratio of ethylene solvent. { bases in weight) is usually from 2 5 1 to 12 1, beyond which the efficiency of the catalyst point suffers. The most normal ratio of ethylene solvent (base in weight) is in the range of 5 1 to 10 1 Polymerization further it can be carried out in a slurry polymerization process, using the catalyst as described above supported on 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 the slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethylene, propane or butane may be useful in all or part of the diluent. Similarly, the α-olefin monomer or a mixture of different α-olefin monomers can be used in all or part of the diluent. More preferably, the diluent comprises at least a part of the monomer or α-olefin monomers can be polymerized. The homogeneous ethylene polymer is normally present in the composition of the invention in an amount of at least 5 percent by weight, preferably at least 10 percent by weight, more preferably at least 20 percent by weight, more preferably at least 50 weight percent and still more preferably at least 70 weight percent: usually less than 99 weight percent, preferably less than 95 weight percent, more preferably less than 90 weight percent weight and still more preferably less than 80 weight percent. The homogeneous ethylene polymer normally has a density of at least 0.855 g / cm3, preferably at least 0.860 g / cm3, more preferably at least 0.865 g / cm3 and even more preferably at least 0.865 g / cm3; normally not greater than 9,910 g / cm3, preferably not greater than 0.900 g / cm3, more preferably not greater than 0.80 g / cm3 and even more preferably not greater than 0.880 g / cm3. The homogeneous ethylene polymer will usually have a melt index (12) of at least 50 g / 10 min, preferably around 60 g / 10 min; preferably not greater than 10,000 g / min., even more preferably not greater than 1500 g / 10 min. While the polymeric compositions of the invention usefully comprise a homogeneous ethylene polymer alone, in combination with a wax and a nucleating agent, in an exemplary preferred embodiment two or more homogeneous ethylene polymers can be employed, which differs from one another in terms of of its density and / or melt index. In a preferred embodiment, the polymer composition comprising a first homogeneous ethylene polymer and a second homogeneous ethylene polymer differs from at least 20 g / 10 min, in terms of the melt index. In such embodiments, the first homogeneous ethylene polymer could have a melt index of at least 1 g / 10 min, preferably at least 10 g / 10 min, more preferably at least 30 g / 10 min. ., and even more preferably at least 50 g / 10 min .; preferably not greater than 200 g / 10 min., more preferably not more than 150 g / 10 min., even more preferably not more than 100 g / 10 min., and even more preferably not more than 80 g / 10 min. The second homogeneous ethylene polymer could have a melt index of at least 100 g / 10 min. preferably at least 120 g / 10 min., more preferably at least 170 g / 10 min., more preferably at least 220 g / 10 min .; preferably not greater than 10,000 g / 10 min., more preferably not greater than 5000 g / 10 min., more preferably not greater than 3000 g / 10 min., and even more preferably not greater than 1500 g / 10 min. The polymeric compositions of the invention may further comprise a wax or other higher melting ethylene polymer (collectively hereafter "waxes"). Said waxes will increase the use of higher temperature, and the principle of crystallization temperature of the polymeric compositions. Accordingly, the wax will normally have a crystalline melting point, as determined by differential scanning calorimetry (CBD) which is at least 10 ° C, preferably at least 20 ° C and even more preferably at least 30 ° C greater than that of the homogeneous ethylene polymer. Waxes useful in the polymeric compositions of the present invention include paraffin waxes, microcrystalline waxes, Fischer-Tropsch, polyethylene and polyethylene byproducts wherein the Mp is less than 3000. Ethylene / α-olefin interpolymers are also suitable. ultra low molecular weight prepared using a catalyst of restricted geometry and may be referred to as homogeneous waxes. Said homogeneous waxes as well as the processes for preparing said homogeneous waxes are described more fully above together with the description of ultra low molecular weight ethylene polymers. Homogeneous waxes lead to a polymer viscosity and low formulation, but are characterized by peak crystallization temperatures that are greater than the peak crystallization temperatures of the corresponding higher molecular weight materials of the same density. Shomogene waxes will be homopolymers or interpolymers of ethylene and a C3-C2 α-olefin. The homogenous wax will have a number average molecular weight of less than 6000, preferably less than 5000. Such homogeneous waxes will normally have an average molecular weight in number of at least 800, preferably of at least 1300. The homogeneous waxes, in contrast with the paraffin waxes and crystalline ethylene homopolymer or interpolymeric waxes, will have an Mp / Mn of 1.5 to 2.5, preferably 1.8 to 2.2. In the case of waxes based on polyethylene and homogeneous waxes, the wax will have a density greater than that of the homogeneous ethylene polymer of the component (a) of the polymer compositions of the invention, and will normally have a density of at least 0.910 g / cm3, preferably at least 0.915 g / cm3 , more preferably 0.920 g / cm3 and even more preferably 0.925 g / cm3. The wax will normally be provided in the polymer composition of the invention in an amount of at least 1 percent, preferably at least 5 percent by weight. more preferably of at least 10 percent weight and still more preferably of at least 20 weight percent Normally wax will be provided in the polymer composition of the invention in an amount greater than 40 weight percent, preferably not greater than 35 percent by weight, more preferably not greater than 30 percent by weight The polymer compositions of the invention will furthermore comprise a nucleating agent. The term "nonation agent" is defined to mean unmatepal useful for controlling particle size and process by which crystals of liquids, supersaturated solutions or saturated vapors are formed. Two classes of nucleating agents include (1) preformed particles that are dispersed in the polymeca composition under high shear stress, and (2) particles that are formed in situ in the fusion of the other components of the polymer composition, said particles crystallize at a super-temperature ior than the other atmospheres of the polymer composition, forming a network of fibers that serves as a nucleation site for the homogeneous polymer and wax Illustrative preformed particles that are dispersed in a polymer system under high shear stress include organophilic multilayer particles. particles can be prepared from hydrophilic phyllosilicates by well-known methods in the art. Illustrative of said materials are smectite clay minerals such as montmoplonite, nontronite, beidelite, volconscoite, hectopta, saponite, sauconite, magadite, kemaite and vermiculite. Other useful multilayer particles include illite minerals such as lediquita and illite mixtures with the clay minarets named above. Other useful multilayer particles, particularly useful with anionic polymers, are double-layer hydroxides such as Mg6AI34 (OH)? 8β (CO3)? H2O (see WT Reichle, J. Catal., Vol. 94, page 547 (1985), which have positively charged layers and exchange anions in the spaces between the layers.) Other multilayer particles have little or no charge in the layers may be useful in this invention, said materials include chlorides such as ReCI3 and FeOCI, chalcogenides such as TiS2, MoS3; cyanides such as Ni (CN) 2; and oxides such as H2Si2O5, V5O13, HTiNbO5, Cro 5 or 5S2. W02V2 8O7, Cr3O8, MoO3 (OH) 2, VOPO4-2H2O, CaPO4CH3-H2O, nHAs0.-H2O and Ag6M? 0O33. The hydrophilic multilayer particles may be rendered organophilic by the exchange of sodium, potassium or calcium cations with a suitable material such as a water-soluble polymer, a quaternary ammonium salt, an amphoteric surface-active agent, and a chloride or calcium compound. Similar Representative examples of water soluble interchangeable polymers include water soluble polymers of vinyl alcohol (for example polyvinyl alcohol), polyalkylene glycols such as polyethylene glycol, water soluble cellulosic polymers such as methyl cellulose and carboxymethyl cellulose, polymers of ethylenically unsaturated carboxylic acids such as poly (acrylic acid) and its salts and polyvinyl pyrrolidone. Representative examples of the quaternary ammonium salts (cationic surface active agents) that may be employed in this invention include quaternary ammonium salts having octadecyl, hexadecyl, tetradecyl or dodecyl groups; with preferred quaternary ammonium salts including dihydrogenated bait ammonium salt, octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt and Ammonium salt of ditetradecyl dimethyl. The organophilic multi-layer particles are those prepared by ion exchange of quaternary ammonium cations. A more preferred organophilic multilayer material is a montmorillonite clay treated with a quaternary ammonium salt, more preferably dimethyl dihydrogen bait ammonium salt commercially sold as Claytone ™ HY (a trademark of Southern Clay Products). The organophilic multi-layer particles are also prepared by the exchange of sodium, potassium or calcium cations with an inorganic material, a polymeric substance obtained by hydrolyzing a polymerizable metal alcoholate such as Si (OR) 4, AI (OR) 3, Si ( OC2H5) 4, Si (OCH3) 4, Ge (OC3H7), or Ge (OC2H5), either alone or in any combination. Alternatively, the inorganic material could be a colloidal inorganic compound. Representative colloidal inorganic compounds that can be used include S? O2, Sb2O3, Fe2O3, T? O2, ZrO2 and SnO2, alone or in any combination The organophilic multilayer material can also be prepared through the exchange of functionalized organosilane compounds , as described in WO 93/11190, pages 9-21 Illustrative nucleating agents that are in particles that are melt-formed from other components of the polymeric composition include acetals, such as t-napthylidene sorbitol, tritium sorbitol. (4-met? L-1-naft? L? Deno), tr? - (4-methox? Ox? -1-naft? L? Deno) sorbitol and dibenzylidene zilitol. An example of these materials is sorbitol 3. , 4-d? Meth? Dibenzylidene, which is available from Milliken Chemical, Inc., as Mili ad ™ 3988, which is also available as a mixture of 10 weight percent in 90 percent low density polyethylene as M i liad ™ 5L71-10, as well as dibenzylidene sorbitol Millad 3905P The concentration of the nucleating agent in the polymeca composition of the invention can be an effective amount to produce an improved density in elongation at break and dependent application, but preferably is not less than 0.1% by weight, more preferably not less than 005 weight percent, even more preferably not less than 0 1 weight percent and even more preferably not less than 2 weight percent based on the total weight of the polymeca composition, and preferably not greater than 10 percent by weight, more preferably not greater than 5 percent by weight, even more preferably not greater than 1 percent by weight and even more preferably not greater than 5 percent by weight of the total polymer composition of the polymer composition The polymer composition of the invention is characterized by having an elongation at break that is at least 50 percent higher, preferably at least 100 percent larger, more preferably 200 percent larger, even more preferably at least 400 percent larger than the comparative polymer compositions lacking the nucleating agent As illustrated below in the examples, the highly preferred polymer compositions are possible, when they exhibit a percent elongation at break that is at least 600 percent, yet at least 700 percent greater than comparative compositions that lack the nucleating agent While the melt adhesives in The invention preferably comprises at least one homogeneous ethylene polymer, instead of or in addition to, comprising any of a variety of traditional define polymers. The term "define polymer" is a part used herein that refers to homopolymers. of C2-C8 α-olefin or ethylene / α-olefin interpolymers prepared, for example, with a Ziegler Natta low density polyethylene catalyst, for example, in a high pressure reaction process Olefin polymers prepared in a high pressure process are generally known as low density polyethylene (LDPE) and are characterized by branched chain units polymerized monomer of the polymer base structure. LDPE polymers generally have a density between 0.910 and 0.935 g / cm3. Ethylene polymers and copolymers prepared by the use of a coordination catalyst, such as a Ziegler or Phillips catalyst, generally known as linear polymers due to the substantial absence of branched chains of polymerized monomer units pending the base structure. High density polyethylene (HDPE), generally has a density of 0.941 to 0.965 g / cm3, is usually an ethylene homopolymer and if it contains relatively few branching chains in relation to several linear copolymers of ethylene and an α-olefin. HDPE is well known, commercially available in various grades and can be used in this invention. Olefin polymers which are linear copolymers of ethylene and at least one α-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms, are also well known and commercially available. The density of an ethylene / α-olefin copolymer is well known in the art as a function of length of the α-olefin and the amount of said monomer in the copolymer in relation to the amount of ethylene. the larger α-olefin length and the larger α-olefin amount present, the lower density of the copolymer. Linear low density polyethylene (LDPE) is usually a copolymer of ethylene and an α-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms (eg, 1-butane, 1-octene, etc.). ), which has sufficient a-olefin content to reduce the density of the PEDB copolymer. When the copolymer contains one or more α-olefins, the dropping density is above 0.91 g / cm 3 and these copolymers are known as ultra low density polyethylene (PEDUB) or variable low density polyethylene (LDPE). The densities of these linear polymers vary from 0.87 to 0.91 g / cm3. Both the materials made by the free radical catalysts and the coordination catalysts are well known in the art, as are their methods of preparation. The heterogeneous linear ethylene polymers are available from The Dow Chemical Company as Dowlex ™ LLDPE and as Attane ™ PEDUB resins. The linear ethylene polymers can be prepared via the solution, slurry or gas phase polymerization of ethylene of one or more optional α-olefin comonomers in the presence of a Ziegler Natta catalyst, by the processes such as are described in the U.S.A. No. 4,076,698 of Anderson et al. Preferably, heterogeneous ethylene polymers are typically characterized by having molecular weight distributions, Mp / Mn, on the scale of 3.5 to 4.1. the relevant discussions of these kinds of materials and their methods of preparation are found in the U.S. Patent. No. 4,950,541 and the patents to which it refers.

Similarly, since the olefin polymers are ethylene polymers having at least one comonomer selected from the group consisting of vimlo esters of a saturated carboxylic acid wherein the acid portion has up to 4 carbon atoms, mono acids or unsaturated dicarboxylic acids of 3 to 5 carbon atoms, an unsaturated acid salt, ethers of unsaturated acid derived from an alcohol having from 1 to 8 carbon atoms and mixtures thereof. The terpolymers of ethylene and these comonomers are also suitable. Lonomers, which are completely or partially neutralized copolymers of ethylene and the acids described above, are described in more detail in US Patent 3,264,272. In addition, the terpolymers of ethylene / vinyl acetate / carbon monoxide or ethylene / methyl acrylate / monoxide of coal containing up to 15 percent by weight of carbon monoxide can also be used. The weight ratio of ethylene to comono unsaturated carboxylic moiety is preferably 95 to 4060 more preferably 90 to 4550, and even more preferably 85 to 6040. The melt index (12 to 190 ° C) of these ethylene modification interpolymers may vary from 0 to 1. at 150, preferably from 03 to 50, and more preferably from 07 to 10 g / 10 min The physical properties, mainly the elongation, are known to decline to lower levels when the melt index of the ethylene copolymer is above 30 g / 10 min Suitable ethylene / unsaturated carboxylic acid, salt and ester interpolymers include ethylene / vinyl acetate (EAV) including, but not limited to, stabilized EAV is described in US Patent 5,096,955; ethylene / acrylic acid (EAA) and its ionomers; ethylene / methacrylic acid and its ionomers; ethylene / methyl acrylate, ethylene / ethyl acrylate; ethylene / isobutyl acrylate; ethylene / n-butyl acrylate; ethylene / isobutyl acrylate / methacrylic acid and its ionomers; ethylene / n-butyl acrylate / methacrylic acid and its ionomers; ethylene / isobutyl acrylate / acrylic acid and its ionomers; ethylene / n-butyl acrylate / acrylic acid and its ionomers; ethylene / methyl methacrylate; ethylene / vinyl acetate / methacrylic acid and its ionomers, ethylene / vinyl acetate / acrylic acid and its ionomers; ethylene / vinyl acetate / carbon monoxide; ethylene / methacrylate / carbon monoxide; ethylene / n-butyl acrylate / carbon monoxide, ethylene / isobutyl acrylate / carbon monoxide; ethylene / vinyl acetate / monoethyl maleate; and ethylene / methyl acrylate / monoethyl maleate. Particularly suitable copolymers are EAV, EAA copolymers; ethylene / methyl acrylate; ethylene / isobutyl acrylate; and ethylene / methyl methacrylate and mixtures thereof. Certain properties, such as strain elongation, can be improved though certain combinations of these ethylene interpolymers, as described in the U.S. Patent. 4,379,190. The processes for forming these ethylene interpolymers are well known in the art and may be commercially available.

When an ethylene interpolymer is used in addition to a homogeneous ethylene polymer, the ethylene interpolymer is usually added in an amount of up to 25 weight percent to increase the cohesive strength, improve the spray capacity, modify the open time , increase flexibility, etc. This modified polymer may be any compatible elastomer, such as a thermoplastic blocking copolymer, a polyamide, an amorphous or crystalline polyolefin such as polypropylene, polybutylene or polyethylene wherein the Mp is greater than 3000, an ethylenic copolymer such as ethylene-acetate vinyl (EAV), ethylene-methyl acrylate or a mixture thereof. Surprisingly, the homogeneous ethylene / α-olefin interpolymers are also compatible with the polyamides, resulting in pressure-sensitive adhesives resistant to the plasticizer. Modifying polymer can be used morally in a relatively low concentration, without diminishing the improved properties of the homogeneous ethylene / α-olefin interpolymer. A preferred modification polymer for increasing open time and heat resistance is a polybutene-1 copolymer such as Duraflex ™ 890 (Shell). In another embodiment of the invention providing a hot melt adhesive formulation, such as hot melt adhesive formulation will preferably comprise a homogeneous ethylene polymer, a wax, a nucleating agent and a thickener.

The hot melt adhesive formulations in the invention, the homogeneous ethylene polymer, as described above, could preferably be improved in an amount of at least 5 weight percent, preferably at least 10 weight percent, more preferably at least 20 weight percent, more preferably at least 50 weight percent and even more preferably at least 70 weight percent; usually less than 99 weight percent, preferably less than 95 weight percent, more preferably less than 90 weight percent and even more preferably less than 80 weight percent. In the hot melt adhesive formulations in the invention, the wax could normally be provided in an amount of at least 1 weight percent, preferably at least 5 weight percent, more preferably at least 10 weight percent. one hundred weight, and more preferably at least 20 weight percent. The wax will normally be provided in a hot melt adhesive formulation in an amount of not more than 40 weight percent, preferably not more than 35 weight percent, more preferably not more than 30 weight percent. In the hot melt adhesive formulations of the invention, the nucleating agent could normally be provided in an amount of not less than 0.01 weight percent, more preferably not less than 0.05 weight percent, still more preferably not less than 0.1 percent by weight and most preferably not less than 0.2 percent by weight based on the total weight of the hot melt adhesive formulation; and preferably not greater than 10 weight percent, more preferably not greater than 5 weight percent, even more preferably not greater than 1 weight percent and even more preferably not greater than 0.5 weight percent of the formulation of hot melt adhesive. In the hot melt adhesive formulations of the invention, the thickener could normally be provided in an amount of at least 1 percent by weight, more preferably at least 5 percent by weight and more preferably at least 10 percent by weight. cent in weight; and usually not more than 80 weight percent, preferably not more than 60 weight percent, more preferably not more than 45 weight percent of the hot melt adhesive formulation. In general terms, the plasticizers useful in the hot melt adhesives of the invention comprise resins derived from renewable resources such as resin derivatives including resin wood, tallow oil, resin gum; Resin esters and natural and synthetic terpenes and derivatives thereof. The aliphatic, aromatic or aliphatic-aromatic petroleum-based oil mixture is also useful in adhesives of this invention. Representative examples of useful hydrocarbon resins include alpha-methyl styrene resins, C5 resins, Cg resins, branched and unbranched C res 0 resins, as well as styrenic and hydrogenated modifications thereof. The scale of plasticizers being in liquid form at 37 ° C that have a ring and a ball softening point of 135 ° C. Solid thickener resins with a softening point greater than 100 ° C, more preferably with a softening point of 130 ° C particularly are useful in providing the cohesion strength of the adhesives of the present invention. For the adhesives of the invention, the preferred thickener resin is predominantly aliphatic. However, thickener resins that increase the aromatic character are also useful, particularly when a second thickener or compatible mutant plasticizer is employed. Illustrative plasticizers include Eastotac® H-100, H-115 and H-130 from Eastman Chemical Co. in Kingsport, TN which are partially hydrogenated cycloaliphatic petroleum hydrocarbon resins with softening points of 100 ° C., 115 ° C and 130 ° C, respectively. These are available in grade E, grade R and grade L and grade W indicating the different levels of hydrogenation with E being less hydrogenated and W feeling the most hydrogenated. The E grade has a bromine number of 15, the R grade a bromine number of 5, the grade a bromine number of 3 and the W grade has a bromine number of 1. There is also an Eastotac® H-142R Eastman Chemical Co. which has a smoothing point of 140 ° C Other thickener resins include Escorez® 5300 and 5400 partially hydrogenated cycloaliphatic petroleum hydrocarbon resins and Escorez® 5600, a hydrogenated aromatic modified petroleum hydrocarbon resin all available from Exxon Chemical Co. in Houston, TX; Wingtack® Extra which is a petroleum aliphatic aromatic hydrocarbon resin, available from Goodyear Chemical Co. in Akron, OH; Hercolite® 2100, a partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from Hercules, Inc. in Wilmington, DE; and Zonatac® 105 and 501 Lite, which are styrenated terpene resins made from d-limonene and available from Arizona Chemical Co. in Panama City, FL. There are numerous types of resins and modified resins available with different levels of hydrogenation including resin gums, resin woods, tallow oil resins, distilled resins, dimerized resins and polymerized resins. Some specific modified resins include glycerol and pentaerythritol esters of wood resins and tallow oil resins. Commercially available grades include, but are not limited to, Sylvatac® 1103, a pentaerythritol resin ester available from Arizona Chemical Co., Unitac® R-100 Lite, a pentaerythritol resin ester from Union Camp in Wayne, NJ, Permalyn® 305, a wood-modified erythritol available from HERCULES and Foral 105 which is a hydrogenated pentaerythritol resin ester also available from Hercules, Sylvatac® R-85 and 295 are resin acids with a melting point of 85 ° C. and 95 ° C available from Arizona Chemical Co. and Foral AX is a hydrogenated resin acid with a melting point of 70 ° C available from Hercules, Inc. Nirez V-2040 is a phenolic modified terpene resin available from Arizona Chemical Co. The hot melt adhesive of the invention optionally may comprise a plasticizer. When a plasticizer is employed, it can usually provide a hot melt adhesive formulation in an amount of at least 1 weight percent, preferably at least 5 weight percent, and more preferably at least 10 percent in weigh; and usually in an amount of not more than 30 percent by weight, preferably not more than 25 percent by weight and more preferably not more than 20 percent by weight of the hot melt adhesive formulation. A plasticizer is broadly defined as a normally organic composition that can be added to thermoplastics, rubbers and other resins to improve extrusion capacity, flexibility, maneuverability, stretching. The plasticizer can be a liquid or solid at room temperature. Illustrative liquid plasticizers include hydrocarbon oils, polybutene, liquid thickener resins, and liquid elastomers. The plasticizing oils are mainly hydrocarbon oils which have a low aromatic content and which are paraffinic or naphthenic in nature. The plasticizer oils preferably have low volatility, are transparent and, as far as possible, have little color and odor. The use of the plasticizers of this invention also contemplates the use of olefin oligomers, low molecular weight polymers, vegetable oils and their derivatives and similar plasticizing liquids. When the solid plasticizing agent is employed, preferably they have a softening point above 60 ° C, it can be supplied by combining the ethylene / α-olefin interpolymer with a thickening resin and a solid plasticizer such as a plasticizer of dimethanol dibenzoate cyclohexane , the resulting adhesive composition can be applied at temperatures below 120 ° C, preferably below 100 ° C. Although a cyclohexane dimethanol benzoate compound commercially available from Velsicol is exemplified under the tradename Benzoflex ™ 352, any solid plasticizer which would subsequently recrystallize from the thermoplastic composition is suitable. Other plasticizers that could be suitable for this purpose are described in EP 0422 108 B1 and EP 0 410 412 B1, both assigned to H.B. Fuller Company. In embodiments of the invention which also comprise a plasticizer, preferably a solid plasticizer will be employed. The hot melt adhesives of the invention will be characterized as having a percent elongation at break that is at least 25 percent higher, preferably at least 50 percent higher and more preferably at least 100 percent higher than a comparative hot melt adhesive which lacks the nucleating agent. Additives such as antioxidants (eg, hidden phenolics (eg, Irganox ™ 2020, Irganox ™ 1010), phosphites (eg, Irgafos ™ 168)), accumulation additives (eg, polyisobutylene), antiblocking additives, colorants , pigments, extender oils, fillers and thickeners are also included in the present compositions, to the extent that they do not detrimentally affect the elongation properties that are characteristic of the polymeric compositions of the invention. In the case of antioxidants, accumulation additives, antiblocking additives, colorants, etc., said optional components could normally be present in the polymer compositions of the invention in an amount of less than 5 weight percent, preferably less than 3 weight percent. percent by weight, more preferably less than 1 percent by weight. In the case of extender and thickener oils, such as the substantially improved components in larger amounts. Except as provided above in another way, in the case of the hot melt adhesive formulations of the invention which are discussed in greater detail above, when it is convenient to include said components, they will normally be provided in an amount greater than 5 percent. by weight, preferably at least 10 percent by weight, more preferably at least 20 percent by weight, preferably not more than 70 percent by weight, more preferably not more than 60 percent by weight. Also, the compositions of the invention optionally further comprise other polymeric components, including but not limited to, polypropylene, styrene-butadiene block copolymers and conventional polyolefins (such as, for example, linear low density polyethylene, low density polyethylene. and ethylene-vinyl acetate copolymers). The compositions of the present invention are formed by any convenient method, including the dry blending of the individual components and subsequently the melt blending, either directly in the extruder used to form the finished article or by the melt pre-mix in a separate extruder or a mixer such as, for example, a Haake unit or a Banbury mixer. The polymeric compositions of the invention find utility in applications requiring high elongation at break, while maintaining a principle of high crystallization temperature, such as the high-speed coating of fabrics, under-carpets, tiles, laminates and adhesives. Examples Preparation of Polymer Compositions. The ingredients used in the polymeric compositions of the invention and of the comparative examples are shown in the following Table One. The homogeneous ethylene polymers were prepared according to the procedures of the U.S. Patents. Nos. 5,272,236 and 5,278,272 and in accordance with the processes for preparing ultra low molecular weight ethylene polymers and homogeneous waxes exhibited in WO / 97/26287. The compositions of the examples and comparative examples were prepared according to the following procedure. The homogeneous polymer was added in the amount indicated in the following Table Two in a Haake mixer which was preheated to 130 ° C and operated at 20 revolutions per minute. After melting the polymer, the mixing speed was increased to 200 revolutions per minute and the polymer was mixed for 2 minutes. The nucleating agent was then added in the amount indicated in Table Two and the resulting material was mixed for two minutes. The wax was added in the amount indicated in Table Two, and the resulting materials were mixed for two minutes. After cooling to 95 ° C, the sample was removed from the mixture. Preparation of the plate. Samples formed in plates were made by compression formation using the following procedure. Fifteen (15) grams of the sample indicated in Table Two were placed between two glass fiber cloths coated with polytetrafluoroethylene, and pressed at 1.38 MPa for 2 to 3 minutes at a temperature of 130 ° C. The pressure was increased to 38 MPa, and the sample was maintained at this pressure for 2 to 3 minutes. The sample was cooled to 25 ° C and allowed to equilibrate for at least 12 hours. In accordance with ASTM D-1708, a punch press equipped with a micro-tension die was used to cut specimens by bell-shaped micro-tension from the plates that were evaluated for elongation at break, tension at the Rupture and peak voltage. The nominal stress-strain diagram for each sample was determined using an Instron ™ 4507 Material Test System (available from Instron Corporation). The cross speed was 10 cm / minute.

Table One: Ingredients n r cn O OÍ tn Table Two: Polymer Compositions Hear The percentage of stress to rupture, peak tension and tensile strength of the compositions of Examples and Comparative Examples 1-10 are shown in Figure 1. As illustrated herein, the object of the invention provides compositions that exhibit at least four times greater than the percentage of stress at rupture (in the cases of Examples 1, 3, 6, 7 and 9), at least six times greater than the percentage of effort at rupture (in the case of Examples 1, 7 and 9) and at least fifteen times greater than the percentage of stress at break (in the case of example 9) than comparative compositions lacking the nucleating agent. As further illustrated in Figure 1, the object of the invention provides compositions exhibiting a percentage of stress at break that is at least 120 percent (in the case of examples 1, 3, 5, 7 and 9). ), preferably at least 200 percent (in the case of examples 1, 7 and 9) and more preferably at least 400 percent (in the case of the example 9). As further illustrated in Figure 1, the object of the present invention provides compositions exhibiting tensile stress which is at least 7 times greater (in the case of Examples 1, 3, 5, 7 and 9) than that of Comparative compositions lacking nucleating agents. As further illustrated, the present invention provides compositions exhibiting a tensile stress of at least 3.4 MPa (in the case of Examples 1, 3, 5, 7 and 9), with Example 7 exhibiting a tensile stress at nearly 4 1 MPa As further illustrated in Figure 1, the compositions of the invention exhibit a peak voltage that is at least 10 percent higher (in the cases of Examples 1, 3, 5, 7 and 9), preferably at least 20 percent higher (in the cases of examples 1, 3, 5 and 9) and more preferably at least 30 percent higher (in the cases of examples 3 and 9) than In addition, as illustrated, the present invention provides compositions exhibiting a peak voltage that is at least 45 MPa (in the case of Examples 1, 3, 5, 7 and 9). Contain a Single Homogeneous Ethylene Polymer Example 11 was prepared according to the procedure described with respect to Examples and Comparative Examples 1-10 Example 11 contains 6885 weight percent of Polymer C, 29 85 weight percent of Wax A and 03 weight percent of Nucleation Agent A Comparative Example 12 contains 70 weight percent of Polymer C and 30 weight percent of Wax A. Example 11 exhibits a percentage of elongation at breakdown, peak voltage and tensile strength improved with respect to those of Comparative Example 12 Formulation Preparation of Hot Melt Adhesives The hot melt adhesive formulations are mixed with a Haake mixer using the following procedure. First, the mixer is heated to 130 ° C. The mixer is normalized and when a speed of 20 revolutions per minute is achieved, the polymer formulation of the formulation is added. After the polymer had melted, the speed was raised to 200 revolutions per minute and the molten polymer was mixed for two minutes. The nucleating agent was added (when used) and the combination was mixed for two minutes. The wax and thickener were then added and the formulation mixed for two minutes. The formulation was cooled to 95 ° C and removed from the mixer. The prepared formulations are shown in the following Table Three.

HMA-A is characterized by having a percentage of stress at break that is at least 800 percent, compared to HMA-B Comparative that has a percentage of effort at break of 420 percent. HMA-A has a voltage performance that is within 10 percent of the voltage performance of the Comparative HMA-B. HMA-A also have a voltage break that is within 10 percent of the breakdown voltage of HMA-B Comparative. Preparation of Homogeneous Ethylene Polymers, Ultra Low Molecular Weight Ethylene Polymers and Homogeneous Waxes for Use in the Polymer Compositions of the Invention The following provides useful methods and conditions for forming homogeneous ethylene polymers, ultra low molecular weight ethylene polymers and waxes for use in the compositions polymers of the invention. Preparation of Catalyst One Part 1: Preparation of TiCla (DDS.? S The apparatus (referred to as R-1) was graduated in the hopper and purged with nitrogen; It consisted of a 10 L glass container with a bottom mounted surface valve, 5-neck head, polytetrafluoroethylene packing, clamp and agitation components (bearing, arrow and vane). The collars were equipped in the following manner: the agitation components were placed in the central neck, and the outer collars had a reflux condenser covered with gas inlet / outlet, an inlet for solvents, a thermocouple and a stopper. Dry deoxygenated dimethoxyethane (DME) was added to the flask (about 5 L). In the drying box, 700 g of TiCl 3 were weighed in an equalizing powder addition funnel; the funnel was capped, removed from the sedative box and placed in the reaction vessel in place of the stopper. TiCl 3 was added for 10 minutes with stirring. After the addition was completed, additional DME was used to wash the remaining TiCl3 in the flask. The addition funnel was replaced with a stopper and the mixture was heated to reflux. The color changed from purple to pale blue. The mixture was heated for 5 hours, cooled to room temperature, the solid allowed to settle and the supernatant was decanted from the solid. The TiCl3 (DDS) was left in R-1 as a pale blue solid. Part 2: Preparation of [(Me4CR) SiMe7N-t-BulfMqCn7 The apparatus (designated as R-2) was graded as described for R-1, except that the flask size was 30 I. The head was equipped with seven collars; agitator in the central neck and the external necks containing conditioned condenser in the upper part with nitrogen inlet / outlet, vacuum adapter, reagent addition tube, thermocouple and plugs. The flask was charged with 4.5 I of toluene, 1.14 kg of (Me4CsH) SiMe2NH-t-Bu, and 3.46 kg of i-PrMgCI 2M in Et2O. The mixture was heated and the ether was allowed to boil in a trap cooled to -78 ° C. After four hours, the temperature of the mixture reached 75 ° C. At the end of this time, the heater was turned off and DME was added to the hot stirring solution, resulting in the formation of a white solid. The solution was allowed to cool to room temperature, the material was allowed to settle and the supernatant was decanted from the solid. The [(Me4C5) SiMe2N-t-Bu] [MgCl] 2 was left in R-2 as an off-white solid.

Part 3: Preparation of f (r? 5-Me4Cs) SiMe, N-t-Bu1TiMe, The materials in R-1 and R-2 were labeled in DME (3L of DME in R-1 and 5L in R-2). The content of R-1 was transferred to R-2 using a transfer tube connected to the bottom valve of the 10 I flask and one of the upper openings in the 30 I flask. The remaining material in R-1 was washed using Additional DME. The mixture darkened rapidly to a dark red / brown color and the temperature in R-2 was brought from 21 ° C to 32 ° C. After 20 minutes, 160 ml of CH2Cl2 was added through a dropping funnel, resulting in a green / brown color change. This was followed by the addition of 3.46 kg of MeMgCI in 3 M THF, which caused an increase in temperature from 22 ° C to 52 ° C. The mixture was stirred for 30 minutes, then 6 I of the solvent was removed under vacuum. Isopar E (6 I) was added to the flask. This cycle of vacuum / solvent addition was repeated, removing 4 I of solvent and adding 5 I of Isopar E. In the final vacuum step, 1.21 additional solvent was removed. The material was allowed to settle overnight, then the liquid layer was decanted into another 30 I glass container (R-3). The solvent in R-3 was removed under vacuum to leave a brown solid, which was re-extracted with Isopar E; This material was transferred in a storage cylinder. The analysis indicated that the solution (17.23 I) was 0.1534 M in titanium, this is equal to 2.644 moles of [(? 5-Me4C5) SiMe2N-t-Bu] TiMe2. This gives an overall yield of 3.2469 moles of [(? 5-Me4C) SiMe2N-t-Bu] TiMe2 or 1063 g. This is a global yield of 72 percent based on the titanium added as TiCl3. Catalyst Preparation Two Part 1: Preparation of TiCl3 (DME)? S The apparatus (referred to as R-1) was graduated in the hopper and purged with nitrogen; It consisted of a 10 L glass container with a bottom mounted surface valve, 5-neck head, polytetrafluoroethylene packing, clamp and agitation components (bearing, arrow and vane). The collars were equipped in the following manner: the agitation components were placed in the central neck, and the outer collars had a reflux condenser covered with gas inlet / outlet, an inlet for solvents, a thermocouple and a stopper. Dry deoxygenated dimethoxyethane (DME) was added to the flask (about 5.2 L). In the drying box, 300 g of TiCl 3 were weighed into an equalizing powder addition funnel; the funnel was capped, removed from the sedative box and placed in the reaction vessel in place of the stopper. TiCl 3 was added for 10 minutes with stirring. After the addition was completed, additional DME was used to wash the remainder of Ti Cl3 in the flask. This process was repeated with 325 g of additional TiCl3, giving a total of 625 g. The addition funnel was replaced with a stopper and the mixture was heated to reflux. The color changed from purple to pale blue. The mixture was heated for 5 hours, cooled to room temperature, the solid was allowed to settle and the supernatant was decanted from the solid. The T? CI3 (DDS) was left in R-1 as a pale blue solid Part 2 Preparation of I ( Me4Cs) S? Me7N-t-BuUMgCH7 The apparatus (designated as R-2) was graded as described for R-1, except that the flask size was 30 I The head was equipped with seven necks, shaker in the neck central and external necks containing condenser conditioned on top with nitrogen inlet / outlet, vacuum adapter, reagent addition tube, thermocouple and plugs The flask was charged with 7 I of toluene, 309 kg of i-PrMgCI 2 17M in Et2O and 1 03 kg of (Me4C5H) S? Me2NH-t-Bu The mixture was heated and the ether was allowed to boil in a trap cooled to -78 ° C After three hours, the temperature of the mixture reached 80 ° C , at that time a white precipitate formed The temperature was then increased to 90 ° C for 30 minutes and kept at this temperature for 2 hours At the end of this time, the heater was turned off and 2 I of DME was added to the hot stirring solution, resulting in the formation of an additional precipitate. The solution was allowed to cool to room temperature, the material was allowed to settle and the supernatant was decanted from the solid. An additional wash was carried out adding toluene, stirring for several minutes, allowing the solids to settle and decanting the toluene solution The [(Me4C5) S? Me2N-t-Bu] [MgCl] 2 was left in R-2 as an off-white solid Part 3: Preparation of f (n5-Me4Cfi) SiMe7N-t-Bu1Ti ( n4-1.3-pentadiene) The materials in R-1 and R-2 were labeled in DME (the total volumes of the mixtures were approximately 5L in R-1 and 12L in R-2). The content of R-1 was transferred to R-2 using a transfer tube connected to the bottom valve of the 10 I flask and one of the upper openings in the 30 I flask. The remaining material in R-1 was washed using Additional DME. The mixture darkened rapidly to a dark red / brown color. After 15 minutes, 1050 ml of 1.3-pentadiene and 2.60 kg of 2.03 M n-BuMgCI in THF were added simultaneously. The maximum temperature reached in the flask during this addition was 53 ° C. The mixture was stirred for 2 hours, then approximately 11 l of the solvent was removed under vacuum. Hexane was added to the flask to a final volume of 22 I. The material was allowed to settle and the liquid layer (12 I) was decanted into another 30 I glass container (R-3). 15 additional liters of the product solution were recovered by adding hexane to R-2, stirring for 50 minutes, again allowing to settle and decanting. This material was combined with the first extract in R-3. The solvent in R-3 was removed under vacuum to give a red / black solid, which was extracted with toluene. This material was transferred in a storage cylinder. The analysis indicated that the solution (11.75 I) was 0.255 M in titanium; this is equal to 3.0 moles of [(? 5-Me C5) SiMe2N-t-Bu] Ti (? '' - 1,3-pentadiene) or 1095 g. This is a 74 percent yield based on the titanium added as TiCl3. Preparation of Polymers A-E Polymer A was produced according to the U.S. 5,272,236 and 5,278,272. The polymer products of Examples BE (the polymeric components in the case of Polymer D, which was a fusion mixture of two polymeric components) were prepared in a solution polymerization process using ISOPAR E as a solvent, using ethylene and octene as comonomers and using the reaction conditions indicated in the following Table Four. In Example A, the catalyst used was that of the Description of Catalyst One, while in each of Examples B-E, the catalyst employed was the catalyst of the Description of Catalyst Two. In each of the AE preparations, the cocatalyst was tris (pentafluorophenyl) borane, available as a 3 weight percent solution in hydrocarbon mixed with lsopar ™ -E, from Boulder Scientific, and aluminum was provided in the form of a modified methylaumoxane solution. (MMAO Type 3A) in heptane, which is available at a 2 percent aluminum concentration from Akzo Nobel Chemical Inc. Each of Examples BE used 35 ppm deionized water as a catalyst furnace. In the case of Polymer B, the octene flow was 5.06 kg / hr, the hydrogen flow was 60 SCCM and the solvent flow was 41.93 kg / hr.

Table Four * Polymer D is a melt mixture formed of 50 weight percent of each of the first and second components identified Polymer preparation A1-R1 The polymer products of Examples A1-R1 were produced in a solution polymerization process using a continuously stirred reactor Additives (eg, antioxidants, pigments, etc.) can be incorporated into the interpolymer products either during the pellet weight or after the manufacture, with a subsequent re-extrusion. Examples A1-11 each stabilized with 1250 ppm of calcium stearate, hidden polyphenol stabilizer of 500 ppm of Irganox ™ 1076 (available from Ciba-Geigy Corporation) and 800 of PEPQ (tetraquas diphosphonite (2,4-d? -t- but? lfen? l) -4,4'-b? phenol) (available from Clapant Corporation) Examples J1-R1 were each stabilized with 500 ppm Irganox ™ 1076, 800 ppm PEPQ, and 100 ppm water (as a catalyst kiln agent). Ethylene and hydrogen were combined in one stream before introducing into the diluent mixture, a mixture of saturated C8-C? hydrocarbons or, for example, Isopar-E hydrocarbon mixture (available from Exxon Chemical Company) and the comonomer In Examples A1-O1, the comonomer was 1-octene, in Examples Q1 and R1, the comonomer was 1-butene, and Example P1 had no comonomer. The reactor feed mixture was injected continuously into the reactor. The metal and cocatalyst complex were combined in a single stream and also injected continuously into the reactor. For Examples A1-11, the catalyst was prepared in the Catalyst Description One shown above. For Examples J1-R1, the catalyst was as prepared in the Description of Catalyst Two shown above. For Examples A1-R1, the cocatalyst was tris (pentafluorophenyl) borane, available as a 3 weight percent solution of hydrocarbon mixed with lsoparTM-E from Boulder Scientific. Aluminum was provided in the form of a solution of modified methylalumoxane (MMAO Type 3A) in heptane, which is available at a 2 percent by weight aluminum concentration of Akzo Nobel Chemical Inc. Sufficient residence time was allowed for the complex of metals and the cocatalyst will react before introduction into the polymerization reactor. For the polymerization reactions of Examples A1-R1, the reactor pressure was kept constant at 3380 kPa. The ethylene content of the reactor, in each of Examples A1-R1, after reaching the steady state, was maintained at the conditions specified in Table Five. After the polymerization, the reactor outlet stream was introduced into a separate one while the molten polymer was separated from the unreacted comonomer, unreacted ethylene, unreacted hydrogen and the stream of the diluent mixture. The molten polymer is cut into strips or formed into pellets subsequently, and after cooling in a water bath or pelletizer, the solid pellets are recovered. Table Five describes the polymerization conditions and the resulting polymer properties. r Ol O C? Cn TABLE FIVE -xl M in O in in TABLE FIVE CONTINUATION co co r in o I heard a. TABLE FIVE CONTINUATION CD r r in or in in TABLE FIVE CONTINUED or r in or in TABLE FIVE CONTINUATION * Calculated on the basis of the melt viscosity correlations according to the formula:, "^? log (?) - 6.6928) / - 1.1363. _ _ "__ l2 = 3.6126 (10 a" ') -9.3185, Where ^ = melt viscosity at 177 ° C The polymer products of Examples S1, T1 and U1 were produced in a solution polymerization process using a well-mixed recirculating cycle reactor. Each polymer was stabilized with 2000 ppm of hidden polyphenol stabilizer IRGANOX ™ 1076 (available from Ciba-Geigy Corporation) and 35 ppm deionized water (as a catalyst kiln agent). Ethylene and hydrogen (as well as any ethylene and hydrogen that was recycled from the separator) were combined in a stream before being introduced into the diluent mixture, a mixture of saturated C8-C? 0 hydrocarbons, for example ISOPAR ™ (available from Exxon Chemical Company) and the 1-octene comonomer. The metal complex and the cocatalysts were combined in a single stream and also injected continuously into the reactor. The catalyst was as prepared in Description of Catalyst Two shown above; the first cocatalyst was tri (pentafluorophenyl) borane, available from Bouder Scientific as a 3 weight percent solution in hydrocarbon mixed with ISOPAR-E; and the secondary cocatalyst was modified methylalumoxane (MMAO type 3A) available from Akzo Nobel Chemical Inc. as a solution in heptane having 2 percent aluminum. Sufficient dwell time was allowed for the metal complex and the cocatalyst to react before introduction into the polymerization reactor. The reactor pressure was kept constant at 3380 kPa.

After the polymerization, the reactor outlet stream was introduced into a separator where the molten polymer was separated from the unreacted comonomer, unreacted ethylene, unreacted hydrogen and diluent mixture stream, which in turn was recycled to the combination with resco comonomer. ethylene, hydrogen and diluent, for introduction into the reactor. The molten polymer was cut into strips or formed into pellets subsequently and after cooling in a water bath or pelletizer, the solid pellets were recovered. Table Six describes the polymerization conditions and the properties of the resulting polymer. TABLE SIX * Calculated on the basis of melt viscosity correlations according to the formulas: | 2 = 3.6126 (10log (?) "66928) /" 1 1363) -9.3185, Mn = 10l (l09'l + 10 6) / 356 ) l where? = = melt viscosity at 177 ° C. Except where noted, Examples V1, W1, and X1 were prepared according to the procedure set forth above with respect to Examples A1-R1. In particular, Examples V1 and W1 were prepared using a catalyst prepared according to Catalyst Method 2. The additives employed were 1000 ppm of hidden Irfanox ™ polyphenol stabilizer (available from Ciba-Geigy Corporation) and 100 ppm of water. In the case of example W1, ethylbenzene was used, instead of hydrocarbon mixed with Isopar ™ E as the solvent. Example X1 was prepared using a catalyst prepared according to Catalyst Procedure 1. The employed additives were 1250 ppm of calcium stearate, 500 ppm of hidden polyphenol stabilizer of Irganox ™ 1076 (available from Ciba-Geigy Corporation), and 800 ppm PEPQ (tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite) (available from Clariant Corporation). The operating conditions employed and a description of the resulting polymers are shown in the following Table Seven: TABLE SEVEN * Calculated on the basis of melt viscosity correlations according to the formulas: l2 = 3.6126 (10log (? > "66928)" 1 1363) -9.3185, Mn = 10 [(lo9? + 1 ° 46) 356) l where? = = melt viscosity at 177 ° C.

To a stirred 4 liter autoclave reactor, 8659 g of ISOPAR ™ E hydrocarbon (available from Exxon Chemical Company) and 8004 g of 1-octene were charged. The reactor was heated to 120 ° C and hydrogen was added from a cylinder. of 75 ce Hydrogen was added to cause a pressure drop of 1800 kPA in the cylinder The reactor was priced at 3200 kPA of ethylene The catalyst was added at the rate of 1 cc / mm The catalyst was prepared in the Catalyst Preparation One shown above and mixed with other co-catalysts of a ratio of 15 ml of a Catalyst Preparation one 0005 M, 15 ml of a 0015M solution of tr? s (pentefluorophen? l) borane in ISOPAR-E hydrocarbon mixture (a 3 percent by weight solution of tr? s (pentafluorophen? l) borane in ISOPAR-E hydrocarbon mixture is available from Boulder Scientific), 1.5 ml of a 0.05 M solution of modified methylalumoxane in a mixture of hydrocarbons of ISOPAR-E (MMAO Type 3A) (a solu of MAO Type 3A in heptane with an aluminum content of 2 percent by weight is available from Akzo Nobel Chemical Inc) and 19.5 ml of an ISOPAR-E hydrocarbon mixture. Ethylene was supplied on demand. The temperature and pressure of the reactor they were graduated at 120 ° C and 3200 kPa, respectively The reaction continued for 23 1 minutes At this time, the stirring was stopped and the contents transferred to a glass recovery vessel. The reactor product was dried in an oven. vacuum at night The ethylene / octene product thus prepared had a density of 67 g / cm3, and a l2 at 190 ° C of 842 g / 10 thousand.

Claims (1)

1. CLAIMS 1 A polymer composition comprising (a) a homogeneous ethylene / α-olefin interpolymer having a density of at least 0855 g / cm 3 and less than 0910 g / cm 3, (b) at least 1 weight percent of a wax having a crystalline melting point, as determined by differential scanning calorimetry, of at least 10 ° C greater than that of the homogeneous ethylene / α-olefin interpolymer, and (c) a nucleating agent Where the nucleating agent is provided in an effective amount such that the percentage of elongation at break of the polymer composition is at least fifty percent greater than the percentage of elongation at break of a comparative composition lacking nucleating agent The polymer composition of claim 1, further comprising a second homogeneous ethylene / α-olefin interpolymer which differs from the homogeneous ethylene / α-olefin interpolymer of the component (a) in terms of The polymer composition of claim 2, wherein the homogeneous ethylene / α-olefin interpolymer of component (a) has a density of 0855 g / cm 3 and a melt index (at least one of its density or molecular weight). 12) from 50 to 200 g / 10 min and wherein the second homogeneous ethylene / α-olefin interpolymer has a density of 0885 g / cm3 at 0. 900 g / cm and a melt viscosity at 176.6 ° C lower than 8000 centipoise. The polymer composition of claim 1, wherein the wax has a crystalline melting point that is at least 15 ° C higher than that of the homogeneous ethylene / α-olefin interpolymer of component (a). The polymer composition of claim 10, wherein the nucleating agent is provided in an amount of 0.01 to 10 weight percent of the polymer composition. 6. A hot melt adhesive formulation comprising: (a) a homogeneous ethylene / α-olefin interpolymer having a density of at least 0.855 g / cm3 and less than 0.910 g / cm3; (b) at least 1 weight percent of a wax having a crystalline melting point, as determined by differential scanning calorimetry, of at least 10 ° C greater than that of the homogeneous ethylene / α-olefin interpolymer; and (c) a nucleating agent. wherein the nucleating agent is provided in an effective amount such that the rupture-to-rupture rate of the polymer composition is at least 25 percent greater than the rupture-to-rupture rate of a comparative composition that lacks an agent of nucleation. 7. The hot melt adhesive formulation of claim 6, wherein the ethylene / α-olefin interpolymer is a homogeneous ethylene / α-olefin interpolymer. 8. The hot melt adhesive of claim 6, wherein the ethylene / α-olefin interpolymer is an interpolymer of ethylene and at least one comonomer selected from the group consisting of vinyl esters of a saturated carboxylic acid wherein the acid portion has up to 4 carbon atoms, unsaturated mono or dicarboxylic acids of 3 to 5 carbon atoms, a salt of the saturated acid, esters of the unsaturated acid derived from an alcohol having from 1 to 8 carbon atoms and mixtures, terpolymers or ionomers thereof. 9. The hot melt adhesive formulation of claim 6, further comprising a second homogeneous ethylene / α-olefin interpolymer which differs from the homogeneous ethylene / α-olefin interpolymer of component (a) in terms of at least one of its density or its molecular weight. The hot melt adhesive formulation of claim 9, wherein the homogeneous ethylene / α-olefin interpolymer of component (a) has a density of 0.855 g / cm3 to 0.880 g / cm3 and a melt index ( 12) from 50 to 200 g / 10 min, and wherein the second homogeneous ethylene / α-olefin interpolymer has a density of 0.885 g / cm3 at 0.900 g / cm3 and a melt viscosity at 177 ° C of less than 8000 centipoise. 11. The hot melt adhesive formulation of claim 6, wherein the wax has a crystalline melting point that is at least 15 ° C higher than that of the homogeneous ethylene / α-olefin interpolymer of component (a). 12. The hot melt adhesive formulation of claim 11, wherein the wax is provided in an amount of 1 to 40 weight percent of the hot melt adhesive formulation. The hot melt adhesive formulation of claim 6, wherein the nucleating agent is provided in an amount of 0.001 to 10 weight percent of the polymer composition. 14. The hot melt adhesive formulation of claim 10, characterized in that it has a percentage elongation at break of at least 4 MPa. 15. The hot melt adhesive formulation of claim 10, characterized in that it has a percentage elongation at break of at least 5.5 MPa. 16. The hot melt adhesive formulation of claim 14, further characterized by having a yield stress and a tensile stress, each of which is within 10 percent of the yield and tension tension of rupture, respectively, of a fusion adhesive formulation in comparative claliente lacking nucleating agent. 83