MXPA00002017A - Rheology modification of polymers prepared using metallocenes - Google Patents

Abstract

The invention includes a process of preparing a coupled polymer comprising heating an admixture containing:1) at least one polyolefin comprising ethylene and at least one comonomer which is selected from alpha olefins having at least 3 carbon atoms, dienes and 2) a coupling amount of at least one poly(sulfonyl azide). The polyolefin is the product of polymerization of ethylene and at least one other alpha-olefin in the presence of a single site catalyst (transition metal like Va or Cr, metallocene or constrained geometry).

Description

MODIFICATION OF REO OG1A OF PREPARED POLYMERS USING METALOCENE DESCRIPTION OF THE INVENTION This invention relates to the coupling of polyolefins, more specifically to the coupling of polyolefins using the insertion in carbon hydrogen bonds (C-H). As used herein, the term "rheology modification" means a change in the melt viscosity of a polymer as determined by dynamic mechanical spectroscopy. Preferably, the strength of the melt strength is increased while maintaining a high shear viscosity (ie, the viscosity measured at a shear stress of 100 rad / sec per DMS), so that a polymer exhibits more resistance to stretching during the elongation of the molten polymer under conditions of low shear stress (ie, a viscosity measured at a shear stress of 0.1 rad / sec per DMS) and does not sacrifice production at high shear conditions. Polyolefins are frequently modified in their rheology using non-selective chemistries that involve free radicals generated, for example, using peroxides or high-energy radiation. However, chemicals that involve the generation of free radicals at elevated temperatures also degrade molecular weight, especially in polymers that contain hydrogen. tertiary such as copolymers of polystyrene, polypropylene, polyethylene, etc. The reaction of polypropylene with peroxides and pentaerythritol triacrylate is reported by Wang et al., In Journal of Applied Polymer Science, Vol. 61, 1395-1404 (1996). These teach that the isotactic polypropylene branching can be carried out by grafting free radical of compounds and tri-vinyl onto polypropylene. However, this aspect can not work well in current practice since the higher speed of chain scission tends to dominate the limited amount of chain coupling that occurs. This happens because chain scission is an intramolecular process following first-order kinetics, while branching is an intermolecular process with kinetics that in a minimal form is second order. The chain cleavage results in a lower molecular weight and a higher melt flow rate than what would be observed if the chain coupling was not accompanied by cleavage. Since the cleavage is not uniform, the molecular weight distribution increases as lower molecular weight polymer chains are formed herein referred to as "ends or tails". The teachings of the U.S. Patent Nos. 3,058,944; 3,336,268; and 3,530,108 include the reaction of certain poly (sulfonyl azide) compounds with polypropylene or other polyolefins through the insertion of nitrene at the C-H bonds. The product reported in the patent of E. U. A. No. 3,058,944 is interlaced. The product reported in the U.S. Patent No. 3,530,108 is formed as a foam and cured with cycloalkane-di (sulfonyl azide) of a given formula. In the patent of E. U. A. No. 3,336,268 the resulting reaction products are referred to as "bridge polymers", since the polymer chains are "bridged" with sulfonamide bridges. The described process includes a mixing step such as grinding or mixing the poly (sulfonyl azide) and the polymer in solution to dispersion, then a heating step where the temperature is sufficient to decompose the poly (sulfonyl azide) (from 100). ° C to 225 ° C, depending on the decomposition temperature of the azide). The starting polypropylene polymer for the claimed process has a molecular weight of at least 275,000. The blends taught in U.S. Patent No. 3,336,268 have up to 25% ethylene-propylene elastomer. The patent of E. U. A. No. 3,631,182 teaches the use of azide formate for the interlacing of polyolefins. The patent of E. U. A. No. 3, 341, 418 teaches the use of sulfonyl azide and azido formate compounds to crosslink certain thermoplastics (PP (polypropylene), PS (polystyrene), PVC (poly (vinyl chloride)) and their mixtures with certain rubber (polyisobutene, EPDM, (rubber ethylene-propylene-diene)) Similarly, the teachings of the Canadian patent 797,917 (family member of NL 6,503,188) include the rheology modification using from 0.001 to 0.075% by weight of poly (sulfonyl azide) to modify the polyethylene homopolymer and its mixture with polyisobutylene It may be desirable to have polymers modified in their rheology rather than entangled (ie having less than 10% gel as determined by the extraction of xylene specifically by ASTM 2765.) Such polymers advantageously they are made using single-site catalysts, preferably single-site metallocene or single-site constrained geometry catalyst and, thus, desirably from a narrow molecular weight distribution (MWD = Mw / Mn, where Mw is the weight average molecular weight, and Mn is the number average molecular weight) (ie, having a MWD preferably less than or equal to 3.0, very preferably less than 2.5 Mw / Mn). The surprising results are especially evident when the starting material is high density polyethylene (density greater than 0.945 g / ml), (hereafter HDPE of narrow MWD), said polymers advantageously have a combination of good processability as indicated by a higher melt strength at a low, constant shear viscosity, eg, 0.1 rad / sec, measured through DMS, and higher tenacity, and elongation to stress than a high density polymer of a weight distribution molecular molecule treated with sulfonyl azide according to the practice of the prior art using the same equivalents (stoichiometry) of the reagent to polymer coupling, and a higher tenacity than that of the same starting material coupled or modified to rheology using the same equivalents of a free radical coupling agent. Desirably, the product could have a better organoleptic than the broader MWD HDPE coupled. Advantageously, the compositions may have a lower undesirable odor than the same starting materials coupled or modified in rheology using the same chemical equivalents of free radical generating agents. Preferably, a process of the invention could result in a more consistent coupling than coupling methods involving free radicals ie the use of the same reagents, quantities and conditions could result in consistent amounts of coupling or changes of ownership. consistent (reproducible), especially consistent amounts of gel formation. Preferably, a process could be less subject to effects from the presence of oxygen than what could be a coupling or modification of rheology involving agents that generate free radicals. In the case of polyethylene of medium and lower density (ie, polymers having a density of 0.94 g / cc to about 0.90 g / cc), they are advantageously copolymers of ethylene wherein the percentage of comonomer is preferably 0.5 to 5 mole comonomer based on the total polymer as determined by ASTM 5017, the polymers could desirably show a combination of improved processability over the starting material with toughness retention, low heat seal initiation temperature, low turbidity formation, High gloss or hot adhesion properties characteristics of the starting material. In the case of elastomeric polymers containing ethylene repeating units wherein the preferred comonomer content is 5-25 mol%, and preferably a density of less than 0.89 g / ml, it may be desirable to have better mechanical properties such as elongation and tensile strength that could be achieved in the starting material or through coupling using the same chemical equivalents of the free radical generating agent as a peroxide. It has now been found that polymers that have a narrow molecular weight distribution or are formed using single-site catalysts, especially polyolefins formed using transition metal catalysts other than Ziegler Natta catalysts, particularly wherein the molecular weight distribution is 3 or less are surprisingly and effectively coupled using poly (sulfonyl azide) coupling agents. The resulting coupled polymers have at least one of the desirable properties listed. The invention includes a process for preparing a coupled polymer, comprising heating a mixture containing (1) a polyolefin comprising ethylene and optionally at least one comonomer, which is selected from alpha olefins having at least three carbon atoms , dienes and combinations thereof, said polyolefin having a molecular weight distribution of less than or equal to 3 and (2) a coupling amount of at least one poly (sulfonyl azide) to at least the decomposition temperature of the poly (sulfonyl azide) during a sufficient period of decomposition of at least 80% by weight of the poly (sulfonyl azide) and sufficient to result in a coupled polymer; particularly when the polyolefin is the polymerization product of ethylene and optionally at least one other alpha-olefin in the presence of a single-site catalyst (eg, a transition metal such as V or Cr, metallocene or restricted geometry). The amount of poly (sulfonyl azide) is preferably 0.01 to 5% by weight of the polyolefin. The poly (sulfonyl azide) and the polyolefin preferably react at a temperature of at least the decomposition temperature and greater than 150 ° C. The invention also includes any composition made through the process of the invention and any article made from the composition, as well as processes for making the articles, particularly the fusion processing (especially where the article is formed from a bath of melting a composition of the invention) most preferably selected by molding, blow molding or blow molding under extrusion of the composition. The invention also includes the use of a composition of the invention in any of these processes. The practice of the invention can be applied to any polymerized thermoplastic polymer using a single-site catalyst, said polymer having at least one CH bond that can react with azide including homopolymers and copolymers with a narrow and broad comonomer distribution (including a bimodal) such as copolymers of ethylene with one or more alpha-olefin (C3 to C20), copolymers of ethylene with unsaturation (EPDM or EODM), ie ethylene-propylene-diene or ethylene-butene-diene), other polymers such as linear high-density polyethylene, styrene-based block copolymers (SBS, SEBS, SIS, ie, stretch no / butadiene / stretch no, stretch no / e tylene / butylene / stretch no (SEBS), styrene / isoprene / styrene), substantially random interpolymers of at least one alpha-olefin with at least one aromatic vinylidene or aliphatic hindered vinylidene comonomer including ethylene-styrene interpolymers, polystyrene syndiotactic eno, atactic polystyrene and combinations thereof. The polymers are advantageously prepared using single site catalysts and thus, advantageously have a narrow molecular weight distribution, MWD = Mw / Mn, ie, a MWD lower than a polymer of the same composition and average molecular weight made using a Ziegler-Natta catalyst, preferably less than or equal to 3. The term "bimodal" is used to refer to polymers that exhibit two peaks in a graphical representation of data from appropriate analyzes to measure the property discussed. For example, in the case of a molecular weight, a gel permeation chromatography (GPC) curve is used to determine the molecular weight distribution. These distributions are viewed statistically, that is, as statistical distributions. In this way, when there is only one peak, the distribution has a mode and is unimodal. The polymer that exhibits two peaks through this analytical method is termed as bimodal. Polymers that exhibit two or more are multimodal. In the case of a molecular weight distribution, the bimodal polymers are usually mixtures of two polymers with different number average molecular weights. The mixture optionally is a mixture in reactor or a mixture formed by passing a first polymer made in a first reactor to a second reactor, wherein the second polymer is produced. The bimodal polymers are illustrative of the multimodal polymers herein. That is, when discussing polymers that have a bimodal characteristic, the multimodal counterpart is also suitable. Those skilled in the art recognize that peaks frequently have overlapping areas and that mathematical analysis is sometimes necessary to distinguish multimodal curves from broad irregular curves. In this invention, when preferred molecular weight distributions (MWD) are given, those distributions denominated for MWD of at least one component are represented by a peak of the GPC curve. The component is preferably made using a single-site catalyst. Preferred polymers for use in the practice of the invention are polymers prepared from ethylene, advantageously ethylene in combination with other monomers polymerizable therewith. Such monomers include alpha-olefin and other monomers having at least one double bond. The polymer is a polyolefin, especially a homopolymer, copolymer or interpolymer. Preferably, the homo or copolymers contain repeating units of ethylene. In polyethylene copolymers, the comonomer content is preferably greater than 1% by weight as determined by 13C NMR (carbon 13 nuclear magnetic resonance), and most preferably greater than 3% by weight of any monomer copolymerizable with ethylene, preferably an alpha -olefin or cyclic olefin, most preferably an olefin of less than 20 carbon atoms, preferably 2 to 18 carbon atoms. The comonomer content is at least one comonomer polymerizable with ethylene, preferably less than 4 comonomers polymerizable with ethylene, most preferably less than 2 of said comonomers. The ethylene polymers optionally are any interpolymers of ethylene and at least one α-olefin. The preferred α-olefins are represented by the following formula: CH2 = CHR wherein R is a hydrocarbyl radical. R generally has from 1 to 20 carbon atoms. Suitable α-olefins for use as comonomers in a solution, gas phase or slurry polymerization process or combinations thereof, include 1-propylene, 1-butene, 1-iobutylene, 1-pentene, 1- hexene, 4-methyl-1-pentene, 1-heptene and 1-octene, as well as other types of monomer such as tetrafluoroethylene, vinyl benzocyclobutane, and cycloalkanes, for example, cyclopentene, cyclohexane, cyclooctene, and 5-ethylidene-2- norborneno (ENB). Preferably, the α-olefins will be 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexane, 1-heptene, 1-octene, or ENB, or mixtures thereof. Most preferably, the α-olefin will be 1-hexene, 1-heptene, 1-octene, or mixtures thereof. Most preferably, the α-olefin is 1-octene. The ethylene polymer with modified rheology according to this invention is preferably more a SLEP (defined below). These interpolymers preferably contain at least 2% by weight, most preferably at least 5% by weight of an α-olefin. Interpolymers useful in the practice of the invention optionally and in a preferred embodiment include monomers having at least two double bonds, which are preferably dienes or triplets. The diene and triene comonomers include 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 3,7,11-trimethoxy. -1, 6-10-octatriene, 6-methyl-1,5-heptadiene, 1,3-butadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1 , 10-undecadiene, bicyclo [2.2.1] hepta-2-5-diene (norbornadiene), or mixtures thereof, preferably butadiene, hexadiene, and octadienes, most preferably 1,4-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1,4-hexadiene, dicyclopentadiene, bicyclo [2.2.1] hepta-2-5-diene (norbornadiene) and 5-ethylidene-2-norbornene (ENB). Polyolefins are formed through means within the skill in the art. The α-olefin monomers and optionally other polymerizable addition monomers are polymerized under conditions within the skill of the art. Said conditions include those processes using metallocene and other single site catalysts such as those illustrated in US Nos. 4,937,299 (Ewen et al.), 5,218,071 (Tsutsui et al.), 5,278,272, 5,324,800, 5,084,534, 5,405,922, 4,588,794, 5,204,419, and the processes subsequently discussed in more detail. In one embodiment, the starting material polyolefins are preferable and substantially linear ethylene polymers (SLEPs). Substantially linear ethylene polymers (SLEPs) are homogeneous polymers having a long chain branching. These are described in the patents of E. U. A. Nos. 5,272,236 and 5,278,272. SLEPs are available as polymers made through the Insite ™ process and Catalyst Technology such as Engage ™ polyolefin elastomers (POEs) commercially available from DuPont Dow Elastomers LLC and Affinity ™ commercially available polyolefin plastomers (POPs) from The Dow Chemical Company. Specific examples of useful Engage ™ POEs include SM 8400, EG 8100, and CL 8001, and specific examples of Affinity ™ POPs include FM-1570, HM 1100, and SM 1300, each of which is commercially available from The Dow Chemical Company . The SLEPs can be prepared through solution, slurry or gas phase polymerization, preferably phase polymerization of ethylene solution and one or more optional α-olefin comonomers in the presence of a catalyst of restricted geometry such as the catalysts described in European patent application 416,815-A. The substantially linear ethylene α-olefin polymers are made through a continuous process using suitable restricted geometry catalysts, preferably restricted geometry catalysts as described in the patent of US Pat. No. 5., 132,380 and U.S. Patent Application Serial No. 545,403, filed July 3, 1990. The monocyclopentadienyl transition metal olefin polymerization catalysts taught in U.S. Patent No. 5,026,798, are also suitable for use in the preparation of the polymers of the present invention, provided that the reaction conditions are as specified below. Suitable cocatalysts for use herein include, but are not limited to, for example, polymeric or oligomeric alumoxanes, especially methyl aluminoxane, as well as ion-forming, uncoordinated, compatible, inert compounds. Preferred cocatalysts are boron compounds, without coordination, inert.

The term "continuous process" means a process in which the reagents are continuously added and the product is continuously removed, so that an approximation of a stable state is achieved, (i.e., a substantially constant concentration of reactants and the product while carries out the process). The polymerization conditions for manufacturing the substantially linear ethylene / α-olefin polymers of the present invention are generally those useful in the solution polymerization process, although the application of the present invention is not limited thereto. The slurry and gas phase polymerization processes are also believed to be useful, provided that appropriate catalysts and appropriate polymerization conditions are employed. Multiple reactor polymerization processes can also be used to make the substantially linear olefin polymers and copolymers that will be rheologically modified in accordance with the present invention, such as those described in the U.S.A. No. 3,914,342. The multiple reactors can be operated in series or in parallel, with at least one constrained geometry catalyst employed in one of the reactors. The term "substantially linear" means that, in addition to the short chain branches attributable to the incorporation of homogeneous comonomer, the ethylene polymer is further characterized by having long chain branches in the base structure of the polymer that is substituted with an average from 0.01 to 3 branches of long chain / 1000 carbons. Preferred substantially linear polymers for use in the invention are substituted with 0.01 long chain / 1000 carbon branches to a long chain / 1000 carbon branch, and most preferably 0.05 long chain / 1000 carbon branches to a long chain branch / 1000 carbons. In contrast to the term "substantially linear", the term "linear" means that the polymer lacks measurable or demonstrable long chain branches, ie, the polymer is substituted with an average of less than 0.01 long chain branches / 1000 carbons. For ethylene / α-olefin interpolymers, "long chain branching" (LCB) means a longer chain length than the short chain branching resulting from the incorporation of the α-olefin (s) into the base structure of the polymer. Each long chain branch has the same comonomer distribution as the base structure of the polymer and can be as long as the base structure of the polymer to which it is attached. The empirical effect of the presence of the long chain branching in the linear, substantial ethylene / α-olefin interpolymers used in the invention is manifested in its improved rheological properties, which are quantified and expressed herein in terms of rheometry of gas extrusion (GER) that results in a melt flow, l? 0 I2, in increments. The presence of short chain branching of up to 6 carbon atoms in length can be determined in ethylene polymers using 13C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method described by Randall (Rev. Macromol. Chem. Phys. ., C. 29, V. 2 &3, pp. 285-297). As a practical matter, current 13C nuclear magnetic resonance spectroscopy is difficult to distinguish the length of a long chain branch in excess of 6 carbon atoms. However, there are other known techniques useful for determining the presence of long chain branches in ethylene polymers, including ethylene / 1-ketene interpolymers. Two of these methods are gel penetration chromatography coupled with a low angle laser light diffusion detector (GPC-LALLS) and gel penetration chromatography coupled with a differential viscosimeter detector (GPC-DV). The use of these techniques for the detection of long chain branching and the underlying theories have been well documented in the literature. See, for example, Zimm, G. H. and Scockmayer, W. H., J. Chem. Phys., 17,1301 (1949) and Rudin, A., Modern Methods of Polymer Characterization, John Wiley &; Sons, New York (1991) pp. 103-112. A. Willem deGroot and P. Steve Chum, both of The Dow Chemical Company, at the October 4, 1994 conference of Federation of Analytical Chemistry and Spectroscopy (FACSS) in St.

Louis, Missouri, presented data demonstrating that GPC-DV is a useful technique for quantifying the presence of long-chain branches in SLEPs. In particular, deGroot and Chum found that the level of long-chain branches in homogeneous linear homogeneous homopolymer samples measured using the zimm-Stockmayer equation correlated well with the level of long-chain branches measured using 13C NMR. In addition, deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, as such, the increase in molecular weight attributable to short chain octene branches can be represented by knowing the mole percent of octene in the sample. By deconvolution of the contribution to molecular weight increase attributable to short-chain branches of 1-octene, deGroot and Chum showed that GPC-DV can be used to quantify the level of long-chain branches in substantially linear ethylene / octene copolymers . DeGroots and Chum also showed that a Log (l2) plot as a function of Log (Mw) as determined by GPC illustrates that the long chain branching aspects (but not the length branching degree) of the SLEPs are comparable with those of highly branched low density polyethylene, high pressure (LDPE) and are clearly distinct from ethylene polymers produced using Ziegler type catalysts, such as titanium complexes and ordinary catalysts to make homogeneous polymers such as hafnium and vanadium complexes . SLEPs are further characterized by having: (a) a melt flow relation l? 0 / l2 > 5.63, (b) a molecular weight distribution, Mw / Mn, as determined by gel permeation chromatography and defined by the equation: (Mw / Mn) < (l? o / l2) - 4.63, (c) a critical shear stress at the beginning of the raw melt fracture, as determined by gas extrusion rheometry, greater than 4 x 106 dynes (cm2) or a rheology of gas extrusion so that the critical shear rate at the start of the surface melt fracture for the SLEP is at least 50% greater than the critical shear rate at the beginning of the surface melt fracture for a linear ethylene polymer, the linear ethylene polymer has a l2, Mw / Mn and preferably density that are each within 10% of the SLEP and where the respective critical shear rates of SLEP and the linear ethylene polymer are measured at the same melting temperature using an extrusion rheometer, and preferably (d) a melting peak of individual differential scanning calorimetry, DSC, between -30 and 150 ° C. For the substantially linear ethylene / α-olefin polymers used in the compositions of the present invention, the ratio of I10 I12 indicates the degree of long chain branching, ie, the larger the I10 / I12 ratio. greater is the long chain branching in the polymer. Generally, the I10 I12 ratio of the substantially linear ethylene / α-olefin polymers is at least 5.63, preferably at least 7, especially at least 8 or more, and as high as 25. The melting index (as measured by ASTM D-1238 (190 ° / 2.16 kg of weight)) for the substantially linear olefin polymers useful herein, is preferably at least 0.1 grams / 10 minutes (g / 10 min), most preferably at least 0.5 g / 10 min and especially at least 1 g / 10 min up to preferably 100 g / 10 min, very preferably up to 50 g / 10 min, and especially up to 20 g / 10 min. The determination of the critical shear rate and the critical shear stress with respect to the melt fracture as well as other rheology properties such as the rheological processing index (Pl), is performed using a gas extrusion rheometer (GER). The gas extrusion rheometer is described by M. Shida, R. N. Shroff and L. V. Cancio in Polymer Enqineerinq Science. Vol. 17, No. 11, p. 770 (1977), and in Rheometers for Molten Plastics by John Dealy, published by Van Nostrand Reinhold Co. (1982) on p. 97-99. The GER experiments are generally performed at a temperature of 190 ° C, at nitrogen pressures of between 17,575 to 386.65 kg / cm2 m using a diameter of 0.0754 mm, a L / D die of 20: 1 with an inlet angle 180 °. For the SLEPs described herein, Pl is the apparent viscosity (in kpoise) of a material measured through GER at an apparent shear stress of 2.15 x 106 dynes / cm2. SLEPs for use in the invention include ethylene interpolymers and have a Pl on the scale of 0.01 kpoise to 50 kpoise, preferably 15 kpoise or less. The SLEPs used herein have a Pl less than or equal to 70% of the Pl of a linear ethylene polymer (either a polymer polymerized by Ziegler or a linearly uniform branched polymer as described by Elston in U.S. Patent No. 3,645,992) having an I2, Mw / Mn and preferably density, each within 10% of the SLEPs. The rheological behavior of SLEPs can also be characterized by the Dow Rheology Index (DRI) rheology, which expresses a "normalized" polymer relaxation time as the result of long chain branching. (See, S. Lai and G.W. Knight ANTEC '93 Proceedinqs, INSITE ™ Technology Polyolefins (SLEP) - New Rules in the Structure / Rheology Relationship of Ethylene to-Olefin Copolymers, New Orleans, La., May 1993). The DRI values range from 0 for polymers that do not have any measurable long chain branching (eg, Tafmer ™ products available from Mitsui Petrochemical Industries, and Exact ™ products available from Exxon Chemical Company) to 15, and are independent of the fusion. In general, for ethylene polymers of low to medium pressure (particularly lower densities), DRI provides improved correlations for melt elasticity and high shear flow capacity with respect to correlations of the same relationships attempted with flow ratios of fusion. For the SLEPs useful in this invention, the DRI is preferably at least 0.1, and especially at least 0.5, and most especially at least 0.8. The DRI can be calculated from the following equation: DRI = (3652879 * tc 1 00649 /? 0 -1) / 10 Where t0 is the characteristic relaxation time of the material and? 0 is the shear viscosity at 0 of the material. Both t0 and? 0 are the values of "better attachment" to the Cross equation, that is,? /? 0 = 1 / (1 + (? • t0) 1"n) where n is the index of the law of material energy, and? and? are the measured viscosity and the shear rate, respectively.The baseline determination of the viscosity and shear rate data is obtained using a rheometric mechanical spectrometer (RMS-800) under a dynamic sweep mode of 0.1 to 100 radians / second at 190 ° C and a gas extrusion rheometer (GER) 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 die with a diameter of 0.0754 mm, L / D 20: 1 at 190 ° C. Specific material determinations can be made from 140 to 190 ° C as required to adapt the melting index variations. a graph of apparent shear stress versus short stress velocity It is apparent to identify the phenomenon of fusion fracture and to quantify the critical shear rate and the critical shear stress of ethylene polymers. According to Ramamurthy in Journal of Rheology, 30 (2), 337-357, 1986), above a critical flow velocity, the irregularities of the extruded product observed can be broadly classified into two main types: Surface fusion fracture and raw fusion fracture. The surface fusion fracture occurs under seemingly stable flow conditions and varies in detail from specular film gloss loss to the more severe form of "shark skin." Here, as determined using the GER described above, the The beginning of the surface fusion fracture (OSMF) is defined as the loss of gloss in the extruded product.The loss of gloss in the extruded product is the point at which the rigidity of the surface of the extruded product can only be detected at Through a 40X amplification, the critical shear rate at the beginning of the surface fusion fracture for the SLEPs is at least 50% greater than the critical shear rate at the beginning of the melt fracture of a polymer surface. of linear ethylene having essentially the same l2 and Mw / Mn. The raw melt fracture occurs at unstable extrusion flow conditions and varies n Detail of regular distortions (alternating in rigid and soft, helical, etc.) to random. For commercial acceptance to maximize the performance properties of films, coating and molds, surface defects should be minimal, if absent. The critical shear stress at the beginning of the raw fusion fracture for SLEPs, especially those that have a density of >0.910 g / cc, used in the invention, is greater than 4 x 104 dynes / cm2. The critical shear rate at the beginning of the surface melt fracture (OSMF) and the beginning of the raw melt fracture (OGMF) will be used in the present based on changes in surface stiffness and product configurations. extruded through a GER. The SLEPs used in the invention are preferably also characterized by a single DSC fusion peak. The unique fusion peak is determined using a differential scanning calorimeter standardized with indium and deionized water. The method involves sample size of 3-7 mg, a "first heating" at 180 ° C, which is maintained for 4 minutes, cooling at 10 ° C / min. at -30 ° C, which is maintained for 3 minutes, and heat up to 10 ° C / min. at 140 ° C for the "second heating". The unique melting peak is taken from the heat flow curve of the "second heating" against temperature. The total melting heat of the polymer is calculated from the area below the curve. For polymers having a density of 0.875 g / cc to 0.910 g / cc, the single melting peak can show, depending on the sensitivity of the equipment, a "shoulder" or a "protrusion" on the low melting side that constitutes less of 12%, typically, less than 9% and more typically less than 6% of the total heat of fusion of the polymer. Such an artifact can be observed for other homogeneously branched linear polymers such as Exact ™ resins and is discerned based on the inclination of the single melting peak that varies monotonically through the melting region of the artifact. Said artifact occurs within 34 ° C, typically 27 ° C and more typically 20 ° C from the melting point of the single melting peak. The heat of fusion attributable to an artifact can be separately determined through specific integration of its associated area under the curve of heat flow versus temperature. The molecular weight distributions of ethylene / α-olefin polymers are determined through gel permeation chromatography (GPC) in a high temperature chromatographic unit at 150 ° C of Waters, equipped with a differential refractometer and three columns of porosity mixed The columns are provided by Polymer Laboratories and are commonly packaged with pore sizes of 103, 104, 109 and 106 A (10"4, 10" 3, 10"2 and 1 O" 1 mm). The solvent is 1, 2,4-trichlorobenzene, from which solutions of 0.3% by weight of the samples are prepared for injection. The flow rate is 1.0 mm / min, the operating temperature of the unit is 140 ° C and the size of the injection is 100 microliters. The determination of molecular weight with respect to the base structure of the polymer is deduced using polyethylene standards of narrow molecular weight distribution (from Polymer Laboratories), together with their elution volumes. The equivalent polyethylene molecular weights are determined using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Ward in Journal of Polymer Science, Polymer Letters, Vol. 6, page 621, 1968) to derive the following equation: "polyethylene = a + (Mpolystyrene) b In this equation, a = 0.4316 and b = 1.0 The weight average molecular weight, Mw, is calculated in a usual way according to the following formula: Mj = (S w¡ (M | J)) J; where w, is the fraction by weight of the molecules with a molecular weight M, eluting from the GPC column in the fraction i and J = 1 when calculating M and j = -1 when Mn. The density of substantially linear ethylene polymers (as measured according to ASTM D-792) for use in the present invention is generally less than 0.95 g / cm.sup.3 The density is preferably at least 0.85 g / cm.sup.3 and especially of at least 0.86 g / cm3, and of preference up to 0.94 g / cm3, and preferably up to 0.92 g / cm3. When the modified resins are going to be used for extrusion or injection molding, the polymer density is preferably at least 0.855 g / cm3, preferably at least 0.865 g / cm3, and still most preferably at least 0.870 g / cm3, preferably up to 0.900 g / cm3, preferably 0.885 g / cm3, and very preferably up to 0.880 g / cm3. The highly preferred density is determined primarily by the modulus of elasticity or flexibility desired in the molded article. The density remains substantially constant during the rheology modification according to this invention. In another embodiment, preferred polymers for starting materials in the practice of this invention are high density slurry ethylene homopolymers preferably made using single site catalysts with a narrow MWD, (preferably less than or equal to 3.0 Mw / Mn. , preferably a MWD less than 2.5, and most preferably with a density greater than 0.945 g / ml). The preferred melting index of the starting material depends on the desired application; however, the preferred melt index for injection molding is 0.5 to 50 g / 10 min; for film and thermoforming applications, the preferred melt index is 0.1 to 20 g / 10 min; and for blow molding applications, the preferred melt index is 0.01 to 20 g / 10 min. These polymers have a good balance of mechanical properties and processability. The most preferred polymers as starting materials for this invention are copolymers of ethylene with a narrow MWD, (ie, an Mw / Mn less than 3, preferably less than 3.0, and most preferably less than 2.5). These can be produced using at least one C3-C20 olefin comonomer. Most preferred for the copolymer is C3-C10. A 0.5-5 molar comonomer as determined by ASTM 5017 is preferred in the starting material. Polymers commercially available in this category are known as TAFMER ™ polymers available from Mitsui Petrochemical Industries, EXACT ™ polymers commercially available from Exxon Chemical Company, AFFINITY ™ olefin plastomer commercially available from The Dow Chemical Company, ENGAGE ™ polyolefin elastomer commercially available from DuPont-Dow Elastomers. For thermoplastic applications such as film and injection molding, the highly preferred comonomer content is between 3-25% by weight. For elastomeric applications, the preferred comonomer content is between 20-40% by weight. The most preferred terpolymer is an EPDM such as the ethylene / propylene / diene NORDEL ™ terpolymer, commercially available from DuPont-Dow Elastomers. Other very useful starting materials include polymers made through the processes described in WO 97/43323 and WO 97/44371. The melt index is measured according to ASTM D-1238, condition 190 ° C / 2.16 kg (formerly known as condition E).

For purposes of rheology modification or coupling, the polymer is reacted with a polyfunctional compound capable of insertion reactions at C-H bonds. Said polyfunctional compounds have at least two, preferably two functional groups capable of insertion of C-H. Those skilled in the art are familiar with C-H insertion reactions and functional groups capable of such reactions. For example, carbons such as those generated from diazo compounds, as described by Mathur, N. C; Snow, M.S .; Young, K.

M., and Pincock, J. A .; Tetrahedrom, (1985), 41 (8), p. 1509-1516, and nitrenes as those generated from azides, as described by Abramovith, R. A .; Chellathurai, T .; Holcomb, W. D; McMaster, I. T .; and Vanderpool, D. P .; J. Org. Chem., (1977, 42 (17), 2920-6, and Abramovitch, RA, Knaus, GN, J. Orq. Chem., (1975), 40 (7), 883-9) Compounds that have at least two sulfonyl azide groups (-SO2N2) capable of CH insertion under reaction conditions are referred to herein as "coupling agents." For the purpose of the invention, poly (sulfonyl azide) is any compound having at least two sulphonyl azide groups reactive with a polyolefin under reaction conditions Preferably, the (sulfonyl azides) have an XRX structure, wherein each X is SO2N3 and R represents an unsubstituted or inertly substituted hydrocarbyl, hydrocarbyl ether or a group containing silicon , preferably having enough carbon, oxygen or silicon, preferably carbon atoms to separate the sulfonyl azide groups sufficiently to allow an easy reaction between the polyolefin and the sulfonyl azide, most preferably at least 1, preferably at least 2 , very preferably at least 3 carbon, oxygen or silicon groups, preferably carbon atoms between the functional groups. Although there is no critical limit to the length of R each R advantageously has at least one carbon or silicon atom between the X's and preferably has less than 50, preferably less than 30, and most preferably less than 20 carbon atoms, oxygen or silicon. Within these limits, the larger the number is the better for reasons that include thermal and shock stability. When R is a straight chain alkyl hydrocarbon, preferably less than 4 carbon atoms exist between the sulfonyl azide groups to reduce the propensity of the nitrene to mix and react with itself. Silicon-containing groups include silanes and siloxanes, preferably siloxanes. The term "inherently substituted" refers to a substitution with atoms or groups that do not undesirably interfere with the desired reaction or desired properties of the resulting coupled polymers. Such groups include fluorine, aliphatic or aromatic ether groups, siloxane, as well as sulfonyl azide groups when more than two polyolefin chains are to be joined. Suitable structures include R as aryl, alkyl, arylalkyl, arylalkyl, siloxane or heterocyclic groups, and other groups that are inert and the sulfonyl azide groups are stopped as described. Most preferably, R includes at least one aryl group between the sulfonyl groups, preferably at least two aryl groups (such as when R is 4,4'-diphenylether or 4,4'-biphenyl). When R is an aryl group, it is preferred that the group has more than one ring, as in the case of naphthalene bis (sulfonyl azide). The poly (if oni I azide) include compounds such as 1,5-pentan bis (s ulf oni I azide), 1,8-octane bis (sulfonyl azide), 1,10-decan bis (sulfonyl azide), 1 , 10-octadecan bis (sulfonyl azide), 1-octyl-2,4,6-benzene tris (sulfonyl azide), bis (sulfonyl azide) of 4,4'-diphenyl ether, 1,6-bis (4 ') - sulfonazidophenyl) hexane, 2,7-naphthalene bis (sulfonyl azide), and mixed sulfonyl azides of chlorinated aliphatic hydrocarbons containing an average of 1 to 8 chlorine atoms and 2 to 5 sulfonyl azide groups per molecule, and mixtures thereof. Preferred poly (sulfonyl azides) include oxy-bis (4-sulfonylazidobenzene), 2,7-naphthalene bis (sulfonyl azido), 4,4'-bus (sulfonyl azido) biphenyl, bis (sulfonyl azide) ether 4, 4'-diphenylic and bis (4-sulfonyl azido phenyl) methane, and mixtures thereof. The sulfonyl azides are conveniently prepared through the reaction of sodium azide with the corresponding sulfonyl chloride, although the oxidation of sulfonyl hydrazines with various reagents (nitrous acid, nitrogen tetraoxide, nitrosonium tetrafluoroborate) has been used. Polyfunctional compounds capable of insertions into CH bonds also include carbene-forming compounds such as alkyl and aryl hydrazone salts and diazo compounds, and nitrene-forming compounds such as alkyl and aryl azides (R-N2), acyl azides (RC ( O) N2), azidoformates (ROC (O) -N3), sulfonyl azides (R-SO2-N3), phosphoryl azides ((RO) 2- (PO) -N3), phosphinic azides (R2-P (O) - N3) and silyl azides (R3-Si-N3). Some of the coupling agents of the invention are preferred because of their propensity to form a greater abundance of carbon-nitrogen insertion products. Said compounds such as hydrazone salts, diazo compounds, azidoformates, sulfonyl azides, phosphoryl azides and silyl azides are preferred, since they form electron products of individual state, stable carbenes and nitrenes), which perform carbon-hydrogen insertion reactions efficient, rather than substantially 1) re-dispose through such mechanisms as the Curtius-type redisposition, as is the case with acyl azides and phosphinic azides, or 2) quickly convert to the triplet state electron configuration, the which preferably undergoes hydrogen atom abstraction reactions, which is the case with alkyl and aryl azides. Also, selection among the preferred coupling agents is conveniently possible due to the differences in temperatures at which the different kinds of coupling agents are converted to the carbene or active nitrene products. For example, those skilled in the art will recognize that carbenes are formed through diazo compounds efficiently at temperatures below 100 ° C, while salts of hydrazones, azidoformates and sulfonyl azide compounds react at a convenient rate at temperatures above. of 100 ° C, up to temperatures of 200 ° C. (At convenient speeds it is meant that the compounds react at a rate that is fast enough to make commercial processing possible, while reacting slowly enough to allow adequate mixing and combining to result in the final product with the agent of coupling properly dispersed and located substantially in the desired position in the final product, said location and dispersion may be different from product to product, depending on the desired properties of the final product). The phosphoryl azides can be reacted at temperatures in an excess of 180 ° C to 300 ° C, while the silyl azides react preferentially at temperatures of 250 ° C to 400 ° C. To modify the rheology, also referred to herein as "coupling", the poly (sulfonyl azide) is used in an amount of rheology modification, ie an effective amount to increase the viscosity of low shear (at 0.1 rad / sec) of the polymer preferably at least 5% as compared to the polymer of starting material, but less than an amount of entanglement, ie, a sufficient amount which results in at least 10% by weight of gel as measured at through ASTM D2765, procedure A. Although those skilled in the art will recognize that the amount of azide sufficient to increase the viscosity of low shear and result in less than 10% by weight of gel, it will depend on the molecular weight of the azide used and the polymer, the amount preferably being less than 5%, preferably less than 2%, and most preferably less than 15 by weight of poi i (its If on il azide), based on in the total weight of the polymer when the poly (sulfonyl azide) has a molecular weight of 200 to 2000. In order to achieve the measurable rheology modification, the amount of poly (sulfonyl azide) is preferably at least 0.01% by weight, preferably at least 0.05% by weight, and most preferably at least 0.10% by weight based on the total polymer. For the rheology modification, the sulfonyl azide is mixed with the polymer and heated at least to the decomposition temperature of the sulfonyl azide. By the decomposition temperature of the azide, it is meant that the temperature at which the azide is converted to sulfinyl nitrene, eliminating nitrogen and heat in the process, as determined by differential scanning calorimetry (DSC). The poly (sulfonyl azide) starts to react at a kinetically significant rate (convenient for use in the practice of the invention), at temperatures of 130 ° C and almost completely reacts at 160 ° C in a DSC (scan at 10 ° C) / min). Accelerated velocity calorimetry (ARC), (scan at 2 ° C / hr) shows the start of decomposition at 100 ° C. The degree of reaction is a function of time and temperature. At the low levels of azide used in the practice of the invention, the optimum properties are not reached until the azide completely and essentially reacts. Temperatures for use in the practice of the invention are also determined through the softening or melting temperatures of the polymer starting materials. For these reasons, the temperature is advantageously greater than 90 ° C, preferably higher than 120 ° C, preferably higher than 150 ° C and most preferably higher than 180 ° C. Preferred times at the desired decomposition temperatures are times which are sufficient to result in the reaction of the coupling agent with the polymer (s) without the undesirable thermal degradation of the polymer matrix. The preferred reaction times in terms of the half-life of the coupling agent, i.e. the time required for the agent half to react at a pre-selected temperature, whose half-life is determined through DSC, is 5 half lives of the coupling agent. In the case of a bis (sulfonyl azide), for example, the reaction time is preferably at least 4 minutes at 200 ° C. The polymer mixture of the coupling agent is conveniently achieved by any means within the skill of the art. The desired distribution is different in many cases, depending on which Theological properties are going to be modified. In a homopolymer, it is desirable to have a distribution as homogeneously as possible, preferably achieving a solubility of the azide in the polymer melt. In a mixture, it is desirable to have a low solubility in one or more of the matrices of the polymer, so that the azide is preferentially in one or the other phase, or predominantly in the region between the two phases. Preferred processes include at least one of (a) dry blending the coupling agent with the polymer, preferably to form a substantially uniform mixture and adding this mixture to the fusion processing equipment, for example, a melting extruder for achieve the coupling reaction, at a temperature of at least the decomposition temperature of the coupling agent; (b) introducing, for example, by injection, a coupling agent in liquid form, for example dissolved in a solvent therefor or in a slurry for the coupling agent in a liquid, to a device containing the polymer , preferably a soft, melted or fused polymer, but alternatively in the form of particles, in solution or dispersion, most preferably in a fusion processing equipment; (c) forming a first mixture of the first quantity of a first polymer and a coupling agent, advantageously at a temperature lower than the decomposition temperature of the coupling agent, preferably by mixing under melting, and then forming a second mixture of the first mixture with a second amount of a second polymer (eg, a concentrate of a coupling agent mixed with at least one polymer and optionally other additives, conveniently being mixed in a second polymer or combination thereof optionally with other additives to modify the second polymer); (d) feeding at least one coupling agent, preferably in solid form, most preferably finely ground, eg, powder) directly to the soft or meltable polymer, for example in a fusion processing equipment, for example in a extruder; or combinations thereof. Among processes (a) to (d), processes (b) and (c) are preferred, process (c) being highly preferred. For example, (c) is conveniently used to make a concentrate of a first polymer composition having a lower melting temperature, advantageously at a temperature below the decomposition temperature of the coupling agent, and the concentrate is mixed under fusion to a second polymer composition having a higher melting temperature to complete the coupling reaction. Concentrates are especially preferred when the temperatures are sufficiently high to result in the loss of the coupling agent through evaporation or decomposition not leading to the reaction with the polymer, or other conditions that could result in that effect. Alternatively, some coupling occurs during the mixing of the first polymer and the coupling agent, but some of the coupling agent remains unreacted until the concentrate is mixed in the second polymer composition. Each polymer and polymer composition includes at least one homopolymer, copolymer, terpolymer or interpolymer, and optionally includes additives within the skill of the art. When the coupling agent is added to a dry form, it is preferred that it be mixed with the agent and the polymer in a soft or molten state below the decomposition temperature of the coupling agent, then heating the resulting mixture to a temperature at least equal to the decomposition temperature of the coupling agent. The term "melt processing" is used to represent any process wherein the polymer is softened or melted, such as extrusion, pelletizing, molding, thermoforming, film blowing, mixing in a polymer melt form, and spinning fiber. The polyolefin (s) and the coupling agent are suitably combined in any way that results in a desired reaction thereof, preferably by mixing the coupling agent with the polymer (s) under conditions that allow a mixed sufficiently before the reaction to avoid uneven amounts of localized reaction, then subjecting the resulting mixture to a heat sufficient for the reaction. Preferably, a substantially uniform mixture of the coupling agent and the polymer is formed prior to exposure to conditions where chain coupling occurs. A substantially uniform mixture is one in which the distribution of the coupling agent in the polymer is sufficiently homogeneous to be evidenced by a polymer having a melt viscosity after treatment in accordance with the practice of the invention at least one of (a) ) higher than a low angular frequency (for example 0.1 rad / sec) 0 (b) lower at the highest angular frequency (for example 100 rad / sec) than that of the same polymer that has not been treated with the coupling agent, but has been subjected to the same shear stress and thermal history. Thus, preferably, in the practice of the invention, the decomposition of the coupling agent occurs after sufficient mixing to result in a substantially uniform mixture of the coupling agent and the polymer. This mixing is preferably obtained with the polymer in a molten or fused state, ie above the crystalline melting temperature, or in a dissolved or finely dispersed condition instead of a solid mass or particulate form. The molten or fused form is more preferred to ensure homogeneity rather than localized concentrations on the surface. Any equipment is suitably used, preferably a device that provides sufficient mixing and temperature control in the same equipment, but advantageously the practice of the invention is presented in such devices as an extruder or a static polymer mixing device such as a Brabender mixer. The term "extruder" is used in its broadest meaning to include devices such as a device that extrudes pellets or a pelletizer. Conveniently, when there is a melt extrusion step between the production of the polymer and its use, at least one step of the process of the invention is taken in the melt extrusion step. Although it is within the scope of the invention that the reaction is present in a solvent or other medium, it is preferred that the reaction be in a bulk phase to avoid further steps to remove the solvent or other medium. For this purpose, a polymer above the crystalline melting temperature is advantageous for even mixing and to reach a reaction temperature (the decomposition temperature of the sulfonyl azide). In a preferred embodiment, the process of the present invention is presented in a single container, ie the mixing of the coupling agent and the polymer occurs in the same vessel as the heating at the decomposition temperature of the coupling agent. The container is preferably a twin-screw extruder, but also a single-screw extruder, an intermittent mixer, or a static mixing zone for mixing the polymer in the back and a production process is advantageous. The reaction vessel very preferably has at least two zones of different temperatures in which a reaction mixture can pass, the first zone advantageously being at a temperature of at least the crystalline melting temperature or the softening temperature of the polymer (s). ) and preferably lower than the decomposition temperature of the coupling agents and the second zone being at a temperature sufficient for the decomposition of the coupling agent. The first zone is preferably at a sufficiently high temperature to soften the polymer and allow it to combine with the coupling agent through a distribution mixture to a substantially uniform mixture. For polymers having softening points above the decomposition temperature of the coupling agent (preferably greater than 20 ° C), and especially when the incorporation of the lower melting polymer (such as in a concentrate) is undesirable, the Preferred embodiment for incorporation of the coupling agent is the solution mixture of the coupling agent in solution or mixture in the polymer, to allow the polymer to be imbibed (absorb or adsorb at least some of the coupling agent), and then evaporate the solvent After evaporation, the resulting mixture was extruded. The solvent is preferably a solvent for the coupling agent, and most preferably also for the polymer when the polymer is soluble such as in the case of polycarbonate. Such solvents include polar solvents such as acetone, THF (tetrahydrofuran) and chlorinated hydrocarbons such as methylene chloride. Alternatively, other non-polar compounds are used such as mineral oils wherein the coupling agent is sufficiently miscible to disperse the coupling agent in a polymer. To avoid the extra step and the resulting cost of re-extrusion and to ensure that the coupling agent is well mixed in the polymer, in an alternative preferred embodiment, it is preferred that the coupling agent be added to the post-reactor area of a polymer processing plant. For example, in a slurry process to produce polyethylene, the coupling agent is added either in powder or liquid form to the polyethylene powder after the solvent is removed by decanting and before drying and extrusion process by densification. In an alternative embodiment, when preparing polymers, in a gas phase process, the coupling agent is preferably added either in powder or liquid form to the powdered polyethylene prior to densification extrusion. In an alternative embodiment, when a polymer is made in a solution process, the coupling agent is preferably added to the polymer melt stream after devolatilization and prior to the pelletizing extrusion process. The practice of the process of the invention for modifying the rheology of polymers produces rheology modified or chain coupled polymers, ie the polymers having sulfonamide, amine, substituted or aryl substituted carboxamide, alkyl substituted or aryl substituted phosphoramide, coupling of methylene substituted alkyl or substituted aryl between different polymer chains. The resulting compounds advantageously show a higher viscosity of low shear stress than the original polymer, due to the coupling of the long polymer chains to the base structures of the polymer. Polymers of monomodal distribution of broad molecular weight (MWD of 3.0 or greater) and gel levels of less than 10% as determined by the extraction of xylene, show a smaller improvement than the dramatic effect observed in the narrow MWD polymer (per example MWD = 2.0) with gel less than 10% or as determined by xylene extraction. Alternatively, those skilled in the art will recognize that it is possible to prepare polymers with broader polydispersity (e.g., MWD greater than 2.0) by mixing low dispersity polymers, either through post-reactor mixing, or by preparing the polymers in a configuration of multiple reactors, wherein the conditions of each reactor are controlled to provide a polymer with the desired molecular weight and the MWD for each specific component resin of the final product. The rheology modification leads to polymers having controlled rheological properties, specifically improved melt strength as evidenced by the increased low shear viscosity, better ability to maintain oil, improved tear strength and usual wear, tack improved, improved green resistance (melting), greater orientation in high extension and high shear processes such as injection molding, film extrusion (blowing and casting), calendering, roto molding, fiber production, profile extrusion , foams and insulation of cables and wires as measured by delta as described below, elasticity by viscosity at 0.1 rad / sec and 100 rad / sec, respectively. It is also believed that this process can be used to produce dispersions having improved viscosity properties of lower shear stress than the unmodified polymer as measured by DMS. The rheology modified polymers are useful as blow molded articles, large due to the higher viscosity of low shear stress than the unmodified polymer and the maintenance of high shear viscosity for processability as indicated by high shear viscosity., foams for stable cell structure as measured by low shear viscosity, blow film for better bubble stability as measured by a low shear viscosity, fibers for better spinnability as measured by high shear viscosity, insulation of wires and wires for green resistance to avoid sinking of polymer formation in the cable as measured by low shear viscosity, which are aspects of the present invention. The modified rheology polymers according to the practice of the invention are superior to the corresponding unmodified polymer starting materials for these applications due to the viscosity rise, preferably at least 5% at low shear rates (0.1 rad / sec), sufficiently high melting strengths to avoid deformation during thermal processing (for example to avoid collapse during thermoforming) or to achieve bubble resistance during blow molding, and shear rate velocity viscosities high, low enough to facilitate molding and extrusion. These rheological attributes allow a faster filling of injection molds at higher speeds than the unmodified starting materials, the fixation of foams (stable cell structure) as indicated by the formation of closed cell density foam more low; preferably with higher tensile strength, insulation properties, compression set or combinations thereof than those obtained during the use of coupling or rheology modification using coupling agents that generate free radicals, due to the high viscosity of fusion. Advantageously, the resistance to the tenacity and tension of the starting material is maintained. The polymers resulting from the practice of the invention are different from those resulting from the practice of prior art processes as shown in CA 797,917. The polymers of the present invention exhibit improved melt elasticity, ie, higher tan delta as measured through DMS, better extraction capacity, higher melt strength as measured through melt tension, less swelling as measured by blow molding die swelling, and less shrinkage as measured by mold shrinkage than in unmodified polymer and broad MWD counterpart (greater than 3.0 Mw / Mn) in thermoforming and blow molding parts big. There are many types of operation by molding, which can be used to form articles or fabricated parts useful from the formulations described herein, including various injection molding processes (e.g., as described in Modern Plastics Encyclopedia / 89, Mid October 1988 Issue, Volume 65, Number 11, pp. 264-268, "Introduction to Injection Molding" and on page 270-271, "Injection Molding Thermoplastics", and blow molding processes (for example, as those described in Modern Plastics Encyclopedia / 89, Mid October 1988 Issue, Volume 65, Issue 11, pp. 217-218, "Extrusion-Biow Molding"), profile extrusion, calendering, and stretch extrusion Modified modified rheology modified ethylene polymers , processes to make them and intermediaries to make them of this invention are useful in the automotive area, industrial reticles, construction and buildings, electrical products (for example, coatings / insulation) of cables and wires) and tire products. Some of the manufactured items include automotive hoses, single-fold roof, and insulation and voltage jackets for cable and wire. The film and film structures particularly benefit from this invention and can be made using conventional heat blown film making techniques or other biaxial orientation processes such as laying frames or double bubble processes. Conventional heat blown film processes are described in, for example, The Encvclopedia of Chemical Technology, Kirk-Othmer, 3a. Edition, John Wiley & Sons, New York, 1981, Vol. 16, p. 416-417 and Vol. 18, p. 191-192. The manufacturing process of biaxially oriented film, such as that described in a "double bubble" process in US Patent 3,456,044 (Pahlke), and the processes described in US Patent 4,352,849 (Mueller), US Patent 4,597,920 (Golike), US Patent 4,820,557 (Warren), US Patent 4,837,084 (Warren), US Patent 4,837,084 (Warren), US Patent 4,865,902 (Golike et al.), US Patent 4,927,708 (Herran et al.), US Pat. US 4,952,451 (Mueller), US Patent 4,963,419 (Lusting et al.), And US Patent 5,059,481 (Lusting et al.), Can also be used to make film structures from the novel compositions described herein. The film structures can also be made as described in a lay-up frame technique, such as that used for oriented polypropylene. Other techniques for manufacturing multilayer films for food packaging applications are described in Packa inq Foods With Plastics, by Wilmer A. Jenkins and James P. Harrington (1991), p. 19-27, and in "Coextrusion Basics" by Thomas I. Butler, Film Extrusion Manual: Process. Materials. Properties p. 31-80 (published by TAPPI Press (1992)). The films can be monolayer or multi-layer films. The film made using this invention can also be co-extruded with the other layers or the film can be laminated onto other layers in a secondary operation, such as that described in Packaging Foods With Plastics, by Wilmer A. Jenkins and James P. Harrington (1991 ) or that described in "Coextrusion for Barrier Packaging" by WJ Schrenk and CR Finch, Society of Plastics Engineers RETEC Proceedings, June 15-17 (1981), p. 211-229. Whether a monolayer film is produced through a tubular film (i.e. blown film techniques) or flat die (ie, cast film) as described by KR Osborn and WA Jenkins in "Plástic Film, Technology and Packaging Applications "(Technomic Publishing Co., Inc., 1992), then the film must go through an additional post-extrusion step of adhesive or extrusion lamination to other layers of packaging material to form a multi-layer structure. If the film is a coextrusion of two or more layers (also described by Osborn and Jenkins), the film can still be laminated to additional layers and packaging materials, depending on other physical requirements of the final film. "Laminations vs. Coextrusion" by D. Dumbleton (Converting Magazine (September 1992), also describes lamination against coextrusion.The monolayer and coextruded films can also go through other post-extrusion techniques, such as a process of orientation Biaxial extrusion coating is still another technique for producing multi-layer film structures using the novel compositions described herein The novel compositions comprise at least one layer of the film structure. Extrusion is a flat die technique A sealant can be extrusion coated onto a substrate either in the form of a monolayer or a co-extruded extrudate, Generally for a multilayer film structure, the novel compositions described herein comprise minus one layer of the total multiple layer film structure. Other layers of the multilayer structure, but not limited to, barrier layers or combinations thereof, tie layers, and structural layers. Several materials can be used for these layers, with some of them being used as more than one film in the same film structure. Some of these materials include: aluminum foil, nylon, ethylene / vinyl alcohol copolymers (EVOH), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), oriented polypropylene (OPP), ethylene / vinyl acetate copolymers (EVA) ethylene / acrylic acid (EAA) copolymers, ethylene / methacrylic acid (EMAA) copolymers, LLDPE, HDPE, LDPE, nylon, graft adhesive polymers (eg, maleic anhydride grafted polyethylene), and paper. Generally, multilayer film structures comprise from 2 to 7 layers. Said articles comprising the polymer modified in the rheology of this invention can be made through processing under melting of the modified polymer in the rheology according to this invention. That process can include pellets or polymer processing pellets, which have been modified in the rheology according to this invention. In a preferred embodiment, the pellets or granules are substantially free of an unreacted coupling agent when the coupling agent comprises a heat-activated coupling agent. Said articles are also made through the processing under fusion of an intermediate comprising a homogeneous polymer, which substantially is not free of an unreacted coupling agent. Said intermediates are preferably treated with a coupling agent, but they are not subjected to a processing under subsequent fusion until the polymer is melted to make the article. The coupling agent can be either an entanglement agent activated by radiation or by heat. Polymers with modified rheology and intermediates used to make polymers with modified rheology can be used alone or in combination with one or more additional polymers in a polymer mixture. When additional polymers are present, they may be selected from any of the modified or unmodified homogenous polymers described above for this invention, and modified or unmodified heterogeneous polymers, or combinations thereof. The heterogeneous polyethylenes that are optionally combined with the modified rheology polymers according to this invention fall into two broad categories, those prepared with a free radical initiator at high temperature and high pressure, and those prepared with a high temperature coordination catalyst. and relatively low pressure. The former are generally known as low density polyethylenes (LDPE) and are characterized by branched chains of polymerized monomer units that depend on the base structure of the polymer. LDPE polymers generally have a density between 0.910 and 0.935 g / cc. Polymers and copolymers of ethylene prepared through the use of a coordination catalyst, such as a Siegler or Phillips catalyst, are generally known as linear polymers due to the substantial absence of branching chains of polymerized monomer units depending on the base structure. High density polyethylene (HDPE), generally with a density of 0.941 to 0.965 g / cc, is typically an ethylene homopolymer and contains relatively few branching chains relative to the various linear copolymers of ethylene and an α-olefin. HDPE is well known, commercially available in various grades and can be used in this invention. The density is measured according to the procedure of ASTM D-792. Linear copolymers of ethylene and at least one α-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms, are well known and commercially available. As is well known in the art, the density of a linear ethylene / α-olefin copolymer is a function of both the length of the α-olefin and the amount of said monomer in the copolymer in relation to the amount of ethylene, the more The larger the length of the α-olefin and the larger the amount of α-olefin present, the lower the density of the copolymer. Linear low density polyethylene (LLDPE) is typically a copolymer of ethylene and an α-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms (eg, 1-butene, 1-octene, etc. .), which has a sufficient content of α-olefin to reduce the density of the copolymer to that of the LDPE. When the copolymer contains even more of α-olefin, the density will fall below 0.91 g / cc and these copolymers are known as ultra low density polyethylene (ULDPE) or very low density polyethylene (VLDPE). The densities of these linear polymers generally vary from 0.87 to 0.91 g / cc. Both materials are made through free radical catalysts and through coordination catalysts that are well known in the art, since they are their methods of preparation. Linear heterogeneous ethylene polymers are available from The Dow Chemical Company as Dowlex ™ LLDPE resins and as Attane ™ ULDPE. The heterogeneous linear ethylene polymers can be prepared through the polymerization of solution, slurry or phase of ethylene gas and one or more optional α-olefin comonomers in the presence of a Ziegler Natta catalyst through processes such as described in US Patent No. 4, 076,698 of Anderson and others. Preferably, heterogeneous ethylene polymers are typically characterized by having molecular weight distributions, Mw / Mn on the scale of 3.5 to 4.1. Important discussions of both kinds of materials and their methods of preparation are found in the patent of E. U. A. No. 4,950,541 and the patents to which it refers. The compositions of the invention and the compositions produced through the practice of the invention are particularly useful because of their surprising properties. For example, the preferred medium density polyethylenes and ethylene copolymers (density 0.90 g / ml), comonomer content of 0.5-5 mol%) of the invention are particularly useful as blown films such as in garbage bags, bags for edibles, sealing layers, tie layers, produce bags, clothing bags, shipping sacks, medical films, stretch films, shrink films, agricultural films, construction films, geomembranes, or stretch cups, preferably garbage bags, films agricultural, construction films and geomembranes. Similarly, preferred embodiments of medium density are useful in cast films such as are useful in stretch films, diaper backsheets, industrial wraps, wrap production, meat wraps, consumer wraps, shrink films or films. elastic, preferably as elastic films. Preferred embodiments of high density polyethylene (density greater than 0.945 g / ml and preferably MWD less than or equal to 3.0) are particularly useful for thermoforming, preferably for use in refrigerator liners, thin-walled containers, medical blister packs , modified atmosphere packaging; and in the blow model (including extrusion blow molding) to form articles such as oil bottles, pipes, fuel tanks including fuel filler necks, milk, and activation bottles. Preferred embodiments of the low density ethylene copolymer (density less than 0.89 g / ml and a comonomer content preferably of 5-25 molar%) are particularly useful in extrusion such as to form coatings for cables and wires, pipe, profiles such such as gaskets and seals, lamination, extrusion coatings such as carpet backs, multi-layer gaskets, reinforcers, and impact modifiers for polymer blends, preferably for cable and wire lining, reinforcers and impact modifiers. Preferred low density embodiments are also particularly useful for calendering to form materials such as lamination, packaging films and non-packaging films; for foams, particularly cushion packaging, toys, building and construction uses, automotive uses, cartons, airplane seats, floral and boat applications, preferably cushion packaging, buildings and construction, automotive uses and cartons; and for adhesives and sealants, particularly hot melt adhesives, pressure sensitive adhesives (if applied in solvents or by heat fusion), caulking and as thickeners in other compositions. The practice of the present invention increases the utility of ethylene polymer, particularly high density polyethylene and propylene polymers in the automotive field. With increased melt strength, it becomes possible to produce automotive articles such as instrument panels, shock absorber absorbers, shock absorber links, door guard panels, door cartridges, seat backrests, seat trays, head rest cores, head restraints, head energy absorbing inserts (EA), pillars, instrument panels, instrument panel guards, reinforcements, glove boxes, doors, consoles, ducts, shelves, hat shelves, load floors, oscillating panels, fenders and combinations thereof using such means as blow molding, injection molding, thermoforming, and gas assisted injection molding. In addition, such automotive articles as carriage supports, external door panels and seat guards and combinations thereof can be produced using such means as blow molding, injection molding and thermoforming. Said articles are roof linings, underlying terminations (underlying protections), bed collection liners, and tire liners can be conveniently reduced through thermoforming; while items such as fuel filler necks and fuel tanks can be produced using blow molding, rotational molding or injection molding. Injection-molded, thermoforming and gas-assisted injection molding are useful for producing impact gates in doors. Items such as shock absorber links, door impact strips, heater guards, roof linings, ducts, bed collection liners, fuel filler necks, fuel transport lines, and driving fuel systems are conventionally produced through extrusion or co-extrusion too. The co-extrusion is also useful for oscillating panels and shock absorbers. The driving fuel systems are also optionally roto-molded or blow molded. Rotomolding is also useful for EA door inserts, seat backs, head rest cores, headrest EAs, instrument panel restraints, reinforcements and ducts; while blow molding is also useful for EA door inserts. further, the foaming is useful for shock absorber energy absorbers, shock absorber links, door guard panels, EA door inserts, seat guard, head rest cores, head restraint, roof linings, EA of bedside, pillars, shelter of instrument panel, reinforcements, and collection bed linings. Compression thermoforming, ie thermoforming at a pressure greater than 240 kPa, is useful for producing items such as shock absorber beams, cross braces for cars, door impact beams, external door panels, door cartridges, seat backs, seat trays, head rests, roof linings, instrument panel cover, reinforcements, ducts, shelves, hat shelves, load floors, swing panels, fenders, underlying terminations, bed liners, tire liners and combinations thereof. The practice of the invention advantageously facilitates blow molding, thermoforming and foaming of ethylene and propylene polymers which without reaction with the polysulfonylurea could not be conveniently configured using those methods and which have a fractional melting (as measured to through the procedure of ASTM-D1238 using a weight of 5 kg and at 109 ° C) of at least an order of magnitude less than the starting material before coupling. The following examples serve to illustrate the invention and not limit it. The relationships, parts and percentages are by weight unless otherwise indicated. The examples (Ex.) Of the invention are designated numerically, while the comparative samples (M.C.) are designated alphabetically and are not examples of the invention.

Test Methods: A dynamic mechanical spectrometer Rheometrics, Inc. RMS-800 with parallel plates with a diameter of 25 mm was used to determine the dynamic rheological data. A frequency sweep with 5 logarithmically separated points per decade was operated from 0.1 to 100 rad / s at 190 ° C. The resistance was determined within the linear viscoelastic regime by performing a resistance sweep at 0.1 rad / s and 190 ° C, through a resistance sweep of 2 to 30% resistance in 2% steps to determine the minimum required tension to require torque within the transducer specification; Another resistance sweep at 100 rad / s and 190 ° C was used to determine the maximum strength before non-linearity occurred according to the procedure described by JM Dealy and KF Wissbrun, "Melt Rheology and Its Role in Plastics Processing", Van Nostrand, New York (1990). All tests were performed on a nitrogen purge to minimize oxidative degradation. A Perkin Elmer thermomechanical analyzer model TMA 7 was used to measure the higher service temperature. A probe force of 102 g and a heating rate of 5 ° C / min were used. Each test specimen was a disk with a thickness of 2 mm and a diameter prepared by compression molding at 205 ° C and cooling with air at room temperature. The extraction of xylene was carried out by loading samples of 1 g of polymer. The samples were transferred to a mesh basket, which was then placed in boiling xylene for 12 hours. After 12 hours, the baskets of the samples were removed and placed in a vacuum oven at 150 ° C in 28 in Hg vacuum for 12 hours. After 12 hours, the samples were removed and allowed to cool to room temperature for a period of 1 hour and then weighed. The results are reported as a percentage of the polymer extracted. Percentage extracted = (initial weight-final weight) / initial weight according to ASTM D-2765 Procedure "A". The samples were prepared using either a commercially available mixer from Haake, Inc. Under the trade name HaakeBuchler Rheomix 600 mixer with roll style blades, attached to a rheometer commercially available from Haake, Inc., under the trade name Rheometer. of Torque HaakeBuchler Rheocord 9000, or using a Brabender mixer (type REE No. A-19 / SB) with a mixing bowl of 50 grams. All instruments were used according to the manufacturer's directions.

Examples 1 and 2 and Comparative Sample A: A 43 g sample of a substantially linear homogeneous ethylene-octene copolymer (6 mol% octene, estimated based on the equation of Kale et al., In Journal of Plastic Film and Sheeting. Vol. 12, January 1996, pp. 27-40) with Mw / Mn = 2.19 and Mw = 93,600, melt index 1 (MI), density of 0.903 g / cc commercially available from The Dow Chemical Company under the trade name of AFFINITY PL 1880 (containing 500 ppm of a commercially available polyphenol antioxidant available from Ciba Geigy Corporation under the trade name Irganox 1076, and 800 ppm of an antioxidant that is believed to be tetrakis- (2,4-butyl-tertiary-phenol) - 4,4'-biphenyl phosphonite commercially available from Sandoz Chemical Company under the tradename P-EPQ) was mixed in a Haake mixer. The polymer was melted at 100 ° C for 2 minutes until all the pellets were melted. Then, 0.05% by weight of 4,4'-oxybis (benzenesulfonyl azide) (hereinafter BSA) CAS # [7456-68-0] was mixed in the molten polymer for 2 minutes. After achieving intimate mixing, the temperature was adjusted to 170 ° C and the rotational speed was increased from 20 to 40 rpm for a period of 7 minutes to reach a maximum of 180 ° C. The mixture was maintained at this upper temperature and at a high rotational speed for 12 minutes, and then cooled to 150 ° C. The sample was removed from the Haake mixer and allowed to cool to room temperature. For Example 2, the procedure of Example 1 was repeated but using 0.01% by weight of 4,4'-oxybis (benzenesulfonyl azide) (BSA). The rheological properties (viscosity and tan delta) were measured for each sample plus an unmodified control (comparative sample A) at 190 ° C on a frequency scale of 0.1 to 100 rad / second using a Rheometics mechanical spectrometer equipped with plates with a diameter of 25 mm parallel according to the directions of the manufacturer. The low shear viscosity is the viscosity measured at the lowest frequency. The viscosity of high shear stress was determined by NSC at 100 rad / sec. The results of these tests are shown in Table 1.

Examples 3 and 4 and Comparative Sample B The procedure of Example 1 was repeated using a linear homogeneous ethylene-butene copolymer of 6.6 mol% comonomer with Mw / Mn = 1.9 and Mw = 118,600 MI = 1.2, density 0.9021, flux fusion of 1.20 g / 10 minutes at 190 ° C, melting temperature 92 ° C, commercially available from Exxon Chemical Company under the trade name of EXACT 3028 reporting that it is made using a metallocene catalyst using 0.05% by weight of BSA for the Example 3, 0.1% by weight for Example 4 and no poly (suifonyl azide) for comparative samples B.

Examples 5 and 6 and Comparative Sample C The following is an example for using a multimodal polymer with a total MWD of > 3.00, but for which at least one component of the product has a MWS < 3.0 and it is reported that it is done using a metallocene catalyst. The procedure of Example 1 was repeated using terpolymer of ethylene (69% by weight), propylene (30.5% by weight), diene (0.5% by weight) with a specific gravity of 0.88, a Mooney viscosity of 20 (through ASTM D-1646), Mw / Mn = 3.5 and Mw = 146,200, commercially available from DuPont Dow Elastomers LIC under the trade name of Nordel IP NDR 3720, hydrocarbon rubber (containing 1000 ppm of Irganox 1076 as a stabilizer) and using 0.05% in weight of BSA for Example 5, 0.1%) by weight of BSA for Example 6 and none of poly i (sulfonylidene) for comparative samples C.

Comparative Samples D, E and F The procedure of Example 1 was repeated using an ethylene terpolymer (72% by weight, propylene (22% by weight), diene (6% by weight), with a specific gravity of 0.87 to 22.4 °. C, Mw / Mn = 3.65 and Mw = 115, 200, Mooney viscosity of 20, UU I, I Wl WIMIN-II K- U '«C" "> "V" - < - "- < •"! "• L- W .VE l_llaßsv > tloWmIIIeV.rIs - L < -CC V ba" j jo the commercial name of hydrocarbon rubber Nordel 2722 (reported to be made using a Ziegler Natta catalyst) with 0.0% by weight of BSA for CS D, 0.05% by weight of BSA for CS "E", - and - 0.1% by weight of BSA for CSF Comparative Samples 6, H e 1 It was repeated in the procedure of Example 1 using a terpolymer of ethylene (71% by weight), propylene (23% by weight), diene (6% by weight) with Mw / Ms = 2.98 and Mw = 173,200, Mooney viscosity of 45 + 6 by means of ASTM D 1646, commercially available from DuPont Elastomers under the tradename of hydrocarbon rubber Nordel 2744 (reported to be made using a Ziegler Natta catalyst) with 0.0, 0.05 and 0.10% by weight of BSA for CS G, CS H, and CS I, respectively.

Examples 7 and 8 v Comparative Sample J The procedure of Example 1 was repeated using a substantially linear ethylene / octene copolymer with 12 = 1 g / 10 minutes and a density of 0.870 g / cm3, Mw = 111, 400 and Mw / Mn = 2.062, commercially available from DuPont Dow Elastomers LIC under the trade name of ENGAGE EG8100 (reported to be made using a constrained geometry catalyst) with 0, 0.05 and 0.1%) by weight of BSA for CS J, Example 7 and Example 8, respectively.

Examples 9 and 10 and Comparative Sample K The procedure of Example 1 was repeated using a linear ethylene-propylene copolymer with Mw / Mn = 2.02, Mw = 122,000 l 2 = 1.1 g / 10 minutes and a density of 0.87 g / cm3, Mw = 116,000 and Mw / Mn = 1878, commercially available from Mitsui Petrochemical Industries under the tradename Tafmer P0480 with 0.05 and 0.1% by weight of BSA for CS K, Example 9 and Example 10, respectively.

Comparative Samples L, M and N The procedure of Example 1 was repeated using a linear low density ethylene / octene copolymer (2.5 mol% octene, estimated based on the equation of Kale et al., J. Plástic Film Sheeting. 12, pp. 27-40, January 1996) with Mw / Mn = 3.96, Mw = 114,800 l2 = 1.0 g / 10 minutes and a density of 0.92 g / cm3, commercially available from The Dow Chemical Company under the trade name of Dowlex 2045 (containing 1250 ppm of calcium stearate, 200 ppm of commercially available polyphenol antioxidant available from Ciba Geigy Corporation under the trade name Irganox 1010) with 0.0, 0.05 and 0.10% by weight of BSA for CS L, CS M, and CS N, respectively.

Examples 11 and 12 and Comparative Sample P The following is an example of rheology modification of a multimodal polymer product with total MWD of > 3.0, but for which at least one of the components has a MWD of < 3.0 and it is reported that it is done using a metallocene catalyst. The procedure of Example 1 was repeated using an ethylene-octene copolymer with a melt index of 0.85% g / 10 min (through ASTM D 1238, 190 ° C / 2.16 kg), density of 0.920 g / cc (by ASTM D 792), Mw / Mn = 3.45 and Mw = 130,300; commercially available from The Dow Chemical Company under the tradename Elite 5100 (containing 1250 ppm of calcium stearate, 500 ppm of the antioxidant Irganox 1076 and 800 ppm of the antioxidant P-EPQ) with 0.05 and 0.1% by weight of BSA for CS P, Example 11, and Example 12, respectively.

Example 13 and Comparative Sample The procedure of Example 1 was repeated using an ethylene-octene copolymer with a melt index of 1.0 g / 10 minutes (through ASTM D 1238, 190 ° C / 2.16 kg), density 0.909 g / cc (by ASTM D 792), Mw / Mn = 2,265 and Mw = 86,100, commercially available from The Dow Chemical Company under the trade name Affinity PL 1840, containing 750 ppm by weight of 3,5-di-tert-butyl Octadecyl-4-hydroxyhydrocinnamate, CAS # 002082-79-3, and 1200 ppm of a mixture of tetrakis (2,4-di-tert-butyl-phenyl) -4-4 ', CAS # 038613-77-3, and biphenylene diphosphonite, CAS # 119345-01-6 (commercially available from Sandoz Chemical Company under the tradename P-EPQ) treated with 0.0% by weight and 0.10% by weight of BSA for CS Q and Example 13, respectively.

Example 14 and Comparative Sample R The procedure of Example 1 was repeated using an ethylene-octene copolymer with a melt index of 0.80 g / 10 minutes (through ASTM D 1238, 190 ° C / 2.16 kg), density 0.905 g / cc (by ASTM D 792), Mw / Mn = 4.04 and Mw = 120,500, commercially available from The Dow Chemical Company under the tradename ATTANE 4203, containing tetrakis (methylene (3,5-di-tert-butyl- 4-hydroxyhydrocinnamate)) methane, CAS # 006683-19-8, 1200 ppm weight percent; and calcium stearate, CAS # 001592-23-0, 1200 ppm by weight treated with 0.0% by weight and treated with 0.10% by weight of BSA for C. S. R and Example 14, respectively.

Example 15 and Comparative Sample S The procedure of Example 1 was repeated using an ethylene-butene copolymer with a melt index of 1.2 g / 10 minutes (through ASTM d 1238, 190 ° C / 2.16 kg), density 0.910 g / cc (by ASTM D 792), Mw / Mn = 2,304 and Mw = 118,700 commercially available from Exxon Chemical Company under the trade name of EXACT 3025, treated with 0.0% by weight and 0.10% by weight of BSA for CS S and Example 15, respectively.

TABLE 1 Viscosity Measurements in English Units co TABLE 1B Summary of Rheological Results of Melting in Metric Units (all viscosities in Pa-S (Pascal Seconds) O) co co o The efficiency of the rheology modification is surprisingly influenced by the distribution of molecular weight, molecular weight, comonomer type and the comonomer content. In general, the tendency is that narrow distribution polymers or polymers with higher comonomer content show a better rheology modification efficiency. The degree of efficiency depends on the type of polymer, and this is discussed below. These significant changes as the MWD becomes narrower, become unexpected. For the three EPDM samples (Example 6, C.S. F and C. S. I), the largest degree of rheology modification was seen for Example 6, which was prepared using a metallocene catalyst. (These discussed results are at a 0.1% azide level). The low shear viscosity (viscosity of 0.1 rad / s) was increased to 103% over that of the base polymer with the highest shear viscosities increasing to less than substantially 3% at 100 rad / s and 22% at 1000 1 / s. In this way, a substantial increase in low shear viscosity (100% at 0.1 rad / s) was observed which can be correlated with increases in melt strength for a metallocene-based EPDM with substantial minor changes in viscosity of high shear stress (3% >; at 100 rad / s) reflecting good processability. The C.S. I of higher molecular weight showed a significant modification with a low shear viscosity increase of 63% with increases in high shear viscosity being 4% > at 100 rad / s. The lowest molecular weight, C.S. F showed more changes of less than 13% in the low shear viscosity and a change of 13% > in the viscosity of high shear stress. The tan delta at a change of 0.1 rad / s was also substantially reduced from 3% to -29% > to -61% > from C.S. E and C.S. F for Examples 5 and 6. (Note: C.S. D and C.S.E with 0.05% azide were re-operated to verify that a small cavity existed at the low shear viscosity with 0.05% azide). For the substantially linear, narrow-distribution copolymers (Example 1 and 2 and Examples 7 and 8), the higher comonomer content polymer Examples 7 and 8) have a better rheology modification efficiency, probably due to a higher comonomer content . For example, at 0.1% by weight of coupling agent, the viscosity changes at 0.1 rad / sec. They are 241% > for Example 2 and 36% for Example 8. For narrow-distribution linear copolymers (Examples 3 and 4 and Examples 9 and 10) the rheology modification efficiency is high due to the combination of narrow MWD and high comonomer content . For a given density, the comonomer content used for these polymers (ie, butene and propylene respectively) is higher than an ethylene-octene copolymer of corresponding density. For example, a coupling agent at 0.1% by weight, viscosity changes at 0.1 rad / sec are 241% for Example 2 and 2214%) for Example 4.

The result of C.S. M is absolutely amazing. Although the MWD of this polymer is wider, the rheology modification efficiency is very high. For example, a coupling agent at 0.1% by weight, the viscosity changes at 0.1 rad / sec are 142% for Example 2 and 648% for C.S. M. The C.S. E and C.S. F showed a minor coupling effect in terms of minor changes in storage modulus and Tg. No displacement of the Tg was observed for C.S. H and C.S. I, with slight increases in the module with an increasing azide level. Examples 5 and 6 showed a significant shift in the storage module increasing to 38% at 25 ° C and 157% at 153 ° C. The Tg was also increased to 7 ° C and to a level of 0.1%. In the Examples of polyethylene, Examples 1 and 2 showed an enlargement and increase of the Tg with coupling and a significant increase in the modulus (60% >) in the melting rate (temperature greater than 100 ° C). Examples 7 and 8 showed no significant shift in Tg, a significant increase in the modulus at room temperature and a large increase in the high temperature modulus (471% >). Examples 3 and 4 showed an increase and increase in Tg with coupling with significant increase in the module at room temperature (43%) and a module at high temperature (5914%). Examples 9 and 10 showed an increase in Tg of 3 ° C, an increase in the modulus at room temperature of 30% > and an increase in the high temperature module of 1017%). C.S. M and C.S. N did not show any significant increase in Tg, but an increase in the intensity of the alpha transition (fusion), an increase in the module at room temperature of 40% and a module at a high temperature of 605%). Examples 11 and 12 showed a similar increase in intensity of the alpha transition, no change in the modulus at room temperature and a 510% increase in the highest temperature modulus. In summary, the rheological melting behavior shows the major differences between the comparative examples (not subjected to coupling reactions) due to the coupling in the practice of the invention.

Claims (12)

1. - A process for preparing a coupled polymer wherein a mixture containing (1) at least one polyolefin comprising the polymerization product of ethylene and optionally at least one comonomer that is selected from alpha olefins having at least three atoms is heated of carbon, dynes and combinations thereof, in the presence of a single-site catalyst, said polyolefin having a molecular weight distribution, Mw / Mn, less than or equal to 3 and (2) a coupling amount of minus one poly (sulfonyl azide) to at least the decomposition temperature of the poly (sulfonyl azide) for a sufficient period of decomposition of at least 80% by weight of the poly (sulfonyl azide) and sufficient to result in a coupled polymer, the coupled polymer characterized by an increase in the shear viscosity low (at 0.1 rad / sec) of the polymer of at least 5, compared to the polymer of part material gone but having less than 10% > by weight of the gel, based on the weight of the coupled polymer, as measured by ASTM D 2765, method A.

2. The process according to claim 1, wherein the polyolefin has a molecular weight distribution, Mw. / Mn, less than or equal to 2.5.

3. The process according to claim 2, wherein the polyolefin has a density of at least 0.945 g / ml.

4. - The process according to claim 1, wherein the amount of pol i (sulfonyl azide) is from 0.01 to 5% > by weight of the polyolefin.

5. The process according to any of claims 1-4, wherein the coupling agent comprises at least one poly (sulfonyl azide), which has a structure, XRX, wherein each X is SO2N3, and R represents an unsubstituted or inertly substituted hydrocarbyl, and hydrocarbyl ether or a group containing silicon.

6. The process according to any of claims 1-5, wherein at least one pol i (sulfonylidene) has at least 3 but less than 50 carbon atoms, silicon or oxygen between the sulfonyl groups azide, and wherein R includes at least two aryl groups or wherein R is an aryl group, and the group has more than one ring.

7. The process according to any of claims 1-6, wherein the poly (sulfonyl azide) is selected from 1,5-pentan bis (sulfonyl azide), 1,8-octane bis (sulfonyl azide), 1, 10-decan bis (sulfonyl azide), 1, 10-octadecan bis (sulfonyl azide), 1-octyl-2,4,6-benzene tris (its Ifonyl azide), bis (sulfonyl azide) ether, 4,4 ' -diphenyl, 1, 6-bis (4'-sulfonazidophenyl) hexane, 2,7-naphthalene bis (sulfonyl azide), mixed sulfonyl azides of chlorinated aliphatic hydrocarbons containing an average of 1 to 8 chlorine atoms and 2 to 5 groups sulfonyl azide per molecule, and mixtures thereof

8. The process according to any of claims 1-7, wherein the poly (sulfonyl azide) and the polyolefin react at a temperature of at least the temperature of decomposition and greater than 150 ° C. 9.- A composition that is the product of any of the processes of claims 1-8 10.- An article comprising a composition of the claim

9. Use of any composition of claim 9 in a process for molding, blow molding or extrusion blow molding. 12. The article according to claim 10, which is a bottle, pipe, fuel tank, fuel filler neck, or milk jug.