MXPA99008670A - Polyolefin blends used for non-woven and adhesive applications - Google Patents

Abstract

The invention relates to methods for preparing a fiber, thread or yarn including a polymer blend of a predominantly atactic flexible polyolefin polymer having a high weight average molecular weight of at least about 100,000 and aheat of fusion of about 15 to 60 J/g with an isotactic polypropylene polymer, and forming the polymer blend into a fiber, thread or yarn, wherein the flexible polymer is present in an amount sufficient to increase the elasticity of the fiber, thread or yarn to inhibit substantial breakage thereof, for use in non-woven products. The invention also relates to the fiber, thread or yarn including the polymers, as well as non-woven products prepared therefrom. Moreover, the invention relates to composite articles including the fiber, thread or yarn in combination with adhesive compositions, and polymer blends used for such adhesive compositions.

Description

POLYOLEFINE MIXTURES USED FOR APPLICATIONS IN NON-WOVEN PRODUCTS AND ADHESIVE COMPOSITIONS CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation in part of application number 08 / 822,865 filed on March 24, 1997, now US Pat. No. 5,723,546, a continuation in part of application number 08 / 878,129 filed on June 10, 1997. This application also claims priority over provisional application number 60 / filed on February 20, 1998 entitled "POLYOLEFIN BLENDS FOR NON-OVEN APPLICATIONS" (Polyolefin mixtures for non-woven applications), which is believed to have the same inventors as this application. TECHNICAL FIELD This invention relates to fibers, threads, and yarns made from polymer blends, and to methods for use in various non-woven products such as, for example, fabrics, films, and foams. More particularly, the invention relates to polymer blends of p < - lyalfaolefin including a novel flexible polyolefin component and an isotactic polypropylene component. BACKGROUND OF THE INVENTION The use of hot melt adhesives as substitutes, or replacements, for conventional solvent based adhesives in various applications has been increasingly favored due to environmental concerns caused by the emission of volatile organic compounds (VOCs). , the well-being of workers in the workplace, and hardening times faster than solvent-based adhesives. Various formulations of hot melt adhesives, polymeric modifiers and other applications include an amorphous polyalphaolefin (APAO). In these formulations, it is important that the polymer has characteristics such as a range of tightly controlled BROOKFIELD ® melting viscosities (MVs), needle penetrations (NPs) and ring and ball softening points (RBSPs, or R and B SPs), controllable and predictable long opening time (OTs), flexibility at low temperatures, adhesion on various substrates and compatibility with various binders and waxes. It is desirable to employ these raw materials with reproducible specifications in order to obtain consistent properties in the formulations employed in adhesive and other formulations. It is known that crystalline polypropylene generally has an isotactic or syndiotactic structure, and that amorphous polymers, such as atactic polypropylene, generally have a considerable atactic structure having a low crystallinity. U.S. Patent Nos. 3,112,300 and 3,112,301, for example, describe an isotactic polypropylene and provide structural formulas for isotactic and syndiotactic polypropylene polymers. The first is a straight chain of propylene units where the methyl groups are all aligned on one side of the polymer chain. In the second, the methyl groups alternate from one side of the chain to the other.

Atactic polypropylenes, on the other hand, have methyl chains placed randomly on opposite sides of the polymer chain. In the isotactic and syndiotactic polypropylenes of the aforementioned patents, the regularity of the structure tends to result in a more highly crystalline material. Low molecular weight atactic polypropylene polymers typically result in rubber-like materials that have minimal tensile strength. Isotactic or syndiotactic polymers have several disadvantages, such as low elongation capacities and no open time, due to their high crystallinity, making them undesirable in hot melt adhesive formulations. Most commercially produced polypropylene is crystalline isotactic polypropylene. Conventional polymers of this type typically have a crystallinity, or heat of fusion, of 70 J / g or more, and more typically 90 J / g or more. These polymers are well known and have been the subject of many patents and articles. APAO polypropylenes, which have very low strength, are used commercially in adhesives and asphalt additives, for example. Conventional atactic polypropylenes that tend to have a crystallinity of less than 20 J / g typically have an extremely high melt flow rate of about 2,000 g / 10 min or more (at 230 ° C). Generally, these atactic polypropylene polyolefins are sticky, which limits their possible use in commercial products. Conventional LMW APAOs have not found much use in applications where high tensile strength and high elongation values are required, because these APAOs do not have these characteristics. High molecular weight APAOs ("HMW"), also known as flexible polyolefin polymers or FPO polymers herein, such as for example amorphous propylene homopolymers and copolymers, are important for their use in various products. The wide utility of these materials is largely due to the unique combination of chemical and physical properties, such as their chemically inert nature, softness, flexibility, etc., which these materials show. Conventional amorphous polypropylene, or atactic polypropylene, is different from crystalline polypropylenes in terms of its spherical micro structure, and usually lacks stress resistance as for example. It is also known that the combination of different polymers to obtain polymer blends for particular uses, however, makes conventional blends which tend to have several disadvantages, such as low melt viscosities, absences of mixing capacity that provides an optical clouding and two independent melting points (mp), and / or glass transition temperatures (Tg), independent, and a limited or no opening time. Several references present certain mixtures of conventional polymers, some of which are discussed below. As used herein, the word "mixture" or "mixtures" includes mechanical polyblends, mechanochemical polyblends, chemical polyblends, solution melted polyblends and latex polyblends described in Kirk-Othmer Concise Encyclopedia of Chemical Technology chemistry of Kirk-Othmer), volume 24, third edition pages 920-922 (Wiley & amp; amp; amp;; Sons, NY, ISBN 0-471-86977-5), which is incorporated herein by reference. The word "mixture" also includes physical mixtures of at least two polymeric materials. U.S. Patent No. 3,963,659 presents homogeneous thermoplastic bituminous compositions containing up to 25 parts by weight of a crosslinkable ethylene-alpha-olefin rubber, and methods for the preparation of said rubber, in order to offer improved properties for use in applications in asphalt. The crosslinkable rubbers in bituminous compositions provide end products with high tensile strength. U.S. Patent 4,022,728 discloses hot melt pressure sensitive adhesives made of amorphous polyolefin blends, a substantially amorphous LMW polymer, a liquid agglomeration resin, and a crystalline polypropylene in order to provide good adhesive properties at low temperatures . U.S. Patent No. 4,075,290 discloses blends of polymers having a greater amount of isotactic polybutene-1 having a molecular weight of 500,000 to 1,750,000 with a lower amount of low pressure ethylene with a polypropylene copolymer or butene-1 having a molecular weight of 200,000 to 350,000, where the mixtures supposedly exhibit excellent welding capacity and superior resistance to tearing and breaking. U.S. Patent No. 4,650,830 discloses a thermoplastic elastomeric composition which presumably has a good melt-bondability by injection and good surface gloss properties, made of the amorphous ethylene / alpha-olefin copolymer and (i) a low crystallinity copolymer of propylene with an alpha-olefin having at least 4 carbon atoms, (ii) a polymer composed primarily of 1-butene, or (iii) a combination of the low crystallinity copolymer or of the 1-butene polymer primarily with a high crystallinity polymer made mainly of propylene and where at least some of the components present crosslinking. U.S. Patent No. 4,960,820 discloses a blend of less than about 10% by weight? Isotactic poly-1-butene polymer, of LMW having a melt index greater than 100 to 1000, and at least about 90% by weight of a propylene polymer having a melt index of less than 60. U.S. Patent No. 5,468,807 has a resin composition which includes from 20 to 80% by weight of an amorphous polyolefin having a propylene and / or butene-1 component. at least 50% by weight, and from 20 to 80% by weight of a crystalline polypropylene, which is supposedly well balanced in terms of mechanical strength and flexibility. U.S. Patent No. 5,478,891 discloses mixed polymer compositions of (a) a HMW copolymer of ethylene and an alphaolefin having at least 4 carbon atoms, and (b) an amorphous polypropylene and / or amorphous polyolefin, or mixtures thereof. , for use in hot melt adhesives, coatings, sealants, asphalt or tar modifiers, and plastic additives. Component (a) is described as generally rigid at room temperature and component (b) is described as having a molecular weight within a range of 300 to 60,000 where the mixtures have a viscosity comprised between about 650 and 46,000 cPs. U.S. Patent No. 5,512,625 discloses a thermoplastic hot melt adhesive from a blend of polymers of (a) an oligomer of an alpha olefin having at least 8 carbon atoms in the monomer and an oligomer of molecular weight less than 5,000, and (b) a mixture of a substantially amorphous polyalphaolefin and a substantially crystalline polyalphaolefin in order to provide supposedly improved impact resistance, viscosity between about 130 and 18, 000 cPs from 180 ° C to 200 ° C, and flexibility at low temperatures. It is also known to employ certain types of polymers and polymer blends in fibers for use in non-woven applications such as, for example, fabrics, films, foams, and the like. For example, EP No. 0,586,937 Al discloses a non-woven fabric made with multi-component polymer strands including a blend of polyolefin and elastomeric thermoplastic material on one side or as the cover of multi-component polymer strands. U.S. Patent No. 5,719,219 discloses a melt-extrudable, moisture curable thermoplastic polymer produced from a silane-modified elastomeric polymer. U.S. Patent No. 5,714,256 discloses methods for the production of non-woven fabrics with a wider bond window by forming the fabric from blends of thermoplastic polymers having from 0.5 wt% to 25 wt% of sidotactic polypropylene. Said fabrics can then be joined on the non-woven fabric, and have a bond window at least 10 ° F wider than the bonding window of a similar fabric without syndiotactic polypropylene. It would be beneficial, however, to produce blends of polyolefins that have improved properties, such as processing characteristics and durability, for use in non-woven products. It is also desirable to produce a blend of polymers for use in a nonwoven product where the blend has a sufficiently high melt viscosity to provide tensile strength, however it has a low crystallinity and a high elongation capacity. It is also desired to obtain mixtures of polymers having an open "sufficiently high" to provide adhesive characteristics It is also desired to produce a blend of polymers for use in adhesives by employing miscible polymers having similar crystallinity, in such a manner that the resulting polymer blend has substantial transparency and a single melting point and transition point to glass, for example, These characteristics are desired in the case of polymer blends to create polymers having several new uses and improved capabilities, including non-woven and adhesive products COMPENDIUM OF THE INVENTION The invention relates to a method for preparing a fiber, strand, or yarn, by preparing a polymer mixture of a predominantly atactic flexible polyolefin polymer having a high molecular weight average of approximately 100,000 and a fusion heat of about 0.4 J / ga 75 J / g and an isotactic polypropylene polymer, and the formation of the polymer mixture in a fiber, strand or yarn, where the flexible polymer is present in an amount sufficient to increase the elasticity of the fiber , strand or yarn to inhibit any substantial rupture in order to produce fibers having an increased elongation and a reduced modulus of tension. In one embodiment, the flexible polyolefin polymer is prepared by polymerizing propylene with at least one second monomer of a C2-C20 polyalphaolefin in a preferred embodiment, selected as the second monomer, ethylene. In another embodiment, the second monomer is provided in the polymer blend in an amount of about 2 to 20% by weight of the weight of the flexible polyolefin polymer. In a preferred embodiment, the second monomer is provided in the polymer blend in an amount of about 6 to 14% by weight of the weight of flexible polyolefin polymer. In another embodiment, the isotactic polypropylene polymer is prepared by the polymerization of propylene with at least one second monomer of a C2-C2o polyalphaolefin. In a preferred embodiment, the second monomer is selected from ethylene. In another embodiment, the second monomer is provided in the polymer blend in an amount of about 1.5 to 20% by weight of the weight of atactic polypropylene polymer. In another modalityThe at least one of the flexible polyolefin polymer or isotactic polypropylene polymer is a propylene homopolymer. In a further embodiment, the flexible polyolefin polymer is provided in an amount of about 3 to 80% by weight of the weight of the polymer blend. In another embodiment, the polymer blend has an elongation at break of between 300 and 669%. In another embodiment, the fibers, strands or threads are formed by spinning, melting, spraying, or carburizing. In a preferred embodiment, the fiber, strand, or yarn is formed into a non-woven product. In another embodiment, the non-woven product is selected as at least one of a fabric, film, foam, or laminate. In another embodiment, the fibers, strands or threads are configured in a repetitive pattern. The invention also relates to a fiber, strand, or yarn of a polymer blend that includes a predominantly atactic flexible polyolefin polymer having a high average molecular weight of about 100,000, a melt flow rate of between about 0.3 g / 10 minutes at 30 g / 10 minutes at a temperature of 230 ° C, a polydispersity index of less than about 10, and a melting temperature of about 0.4 J / g to 75 J / g and an isotactic polypropylene polymer. The invention also relates to a nonwoven product that includes the fiber, strand or yarn. In one embodiment, the fibers are arranged in a repetitive pattern. In another embodiment, at least one of the flexible polyolefin polymer or the isotactic polypropylene polymer is a propylene homopolymer. In another embodiment, the flexible polyolefin polymer includes a polymerized propylene with at least one second monomer of a C2-C20 polyolalfaolefin. The invention relates to an article composed of a plurality of the fibers, strands, or yarns in contact with an adhesive having an adhesive polymer blend of a predominantly atactic flexible polyolefin polymer having a high average molecular weight of at least about -100,000 and a heat of fusion of about 0.4 J / g to 75 J / g and an atactic polyolefin polymer polymer having a low average molecular weight of less than 25,000, and a heat of fusion of about 0.1 to 20 J / g, wherein the high molecular weight polymer and the low molecular weight polymer are sufficiently miscible to provide a single glass transition temperature and an open time to the polymer blend, and the low molecular weight polymer is present in a sufficient amount to provide a melt viscosity greater than about 8,000 cPs at room temperature and a crystallinity below a approximately 28 J / g to the adhesive polymer mixture. The invention further relates to a composite article that includes fibers, strands or yarns arranged in a non-woven pattern, and an adhesive component that includes a predominantly atactic flexible polyolefin polymer having a high average molecular weight of at least about 100%. , 00 and a heat of fusion of about 0.4 J / g to 75 J / g, and an atactic polyolefin polymer having a low average molecular weight of less than 25,000 and a heat of fusion of about 0.1 to 20 J / g, wherein the high molecular weight polymer and the low molecular weight polymer are sufficiently miscible to provide a single glass transition temperature and an opening time for the polymer mixture, and the low molecular weight polymer is present in a sufficient amount to provide a melt viscosity greater than about 8,000 cPs at room temperature and a crystallinity below about 28. J / g to the polymer mixture. The invention further relates to a polymer blend that includes a predominantly atactic flexible polyolefin polymer that includes propylene copolymerized with ethylene present in an amount of about 1 to 40% by weight of the polymer, wherein the polymer has a high average molecular weight of at least about 100,000 and a heat of fusion of about 0.4 J / g to 75 J / g and an atactic polyolefin polymer having a low average molecular weight of less than about 25,000 and a heat of fusion of about 0.1 to 20 J / g, where the high molecular weight polymer and the low molecular weight polymer are sufficiently miscible to provide a single glass transition temperature and an opening time to the polymer mixture, and the polymer of low molecular weight is present in an amount sufficient to provide a melt viscosity greater than about 8,000 cPs at room temperature and a crystallinity below about 28 J / g to the polymer blend. The invention also relates to adhesives that include these polymer mescal. In another embodiment, ethylene is present in an amount of about 1.5 to 20% by weight of the flexible polymer. In a preferred embodiment, ethylene is present in an amount of about 2 to 12% by weight of the flexible polymer. In another embodiment, the atactic polyolefin polymer includes a propylene copolymerized with a second monomer comprising C2-C20 polyalphaolefin. In a preferred embodiment, the second polymer is present in an amount of about 2 to 70% by weight of the atactic polyolefin polymer. DETAILED DESCRIPTION OF THE INVENTION It has now been found beneficially by Huntsman Polymer Corporation that when certain polymers of flexible polyolefins (FPOs) as described in the North American application number 08 / 878,129 and, part of the blends in the North American patent number 5,723,546, mixed with isotactic polypropylene polymers provide beneficial polymer blends having improved hysteresis, better strength, reduced decay under stress condition, and improved filtration properties compared to prior art materials, which makes the Mixtures are particularly useful for preparing fibers, strands, or yarns for use in various non-woven products. It has been found that the mixture of HMW APAOs, low crystallinity, with low molecular weight APAOs ("LMW") provides the desired high melt viscosity, open time, tensile strength with low crystallinity, I, after desirable properties discussed here. Polymer blends also have a high elongation capacity and flexibility even at low temperatures, however they have superior resistance at elevated temperature. The new polymer blends also have a sufficiently long "open time" to provide the desired adhesive characteristics, and are substantially transparent (i.e., with excellent clarity) and preferably have only a glass transition temperature due to the mixing ability of the components of two polymers. These adhesive mixtures can also be used advantageously in combination with mixtures of non-woven products to form compounds. PREPARATION OF FLEXIBLE POLYOLEPHINS (FPOe) Several different families of propylene-based polymers, for example, can be prepared in a polymerization reactor. Some examples of these polymer families include, but are not limited to: isotactic propylene homopolymers, isotactic propylene / ethylene copolymers, amorphous poly-alpha-olefin polypropylene homopolymers ("APAO"), copolymers. of propylene of APAO / ethylene, propylene copolymers of APAO / butene, propylene homopolymers of FPO, propylene copolymers of FPO / ethylene, and propylene copolymers of FPO / butene. After the polymerization reaction the conventional processing technology required the addition of large amounts of water to transport the polymer to bulk storage tanks for further processing. The FPO polymers can be processed in a conventional manner, or they can be transported directly from the polymerization reactor to the final extruder through a kneader-extruder device, which helps to devolatilize the unreacted monomer or monomers. A preferred device, which maintains a substantially constant inventory of polymer there, is presented in co-pending applications Nos. 08 / 598,820 and 08 / 630,800, the filings of which are expressly incorporated herein by reference. The polymer is fed, either from conventional storage tanks or from the novel kneader-extruder, to the final extruder. In the extruder, the polyolefin material is typically mixed with small amounts of water to deactivate any remaining catalyst in the material and antioxidant. The heating of the material further removes any unreacted monomer, antioxidant solvents as well as excess steam added during this step. Finally, the polyolefin material is typically transferred to a pelletizer where it is formed into pellets for storage and / or use. The FPO polymers are typically propylene homopolymers, but may also be propylene in a mixture with at least one other monomeric raw material, such as for example C2-12 alkene the other monomeric raw materials are alphadefines in a preferred embodiment, such as ethylene, 1-butene, 1-pentene and 1-octene. A component particularly for use in the propylene FPO polymer is an ethylene copolymer, typically in an amount of about 1 to 40% by weight, preferably in an amount of about 5 to 20% by weight, and more preferably in an amount of about 6 to 14% by weight, of the polymer composition. In one embodiment, ethylene is increased in the monomeric raw material to substantially inhibit or eliminate the effects of the external donor in various degrees, that is, to inhibit the ability of the external donor to increase the salinity of the propylene domains within the polymer. of polyolefin. The FPO polymers are characterized by several properties. The most important of these properties is the degree of crystallinity and the degree of polymerization. The crystallinity, or heat of fusion (deltas Hf) is typically measured according to ASTM method D-3417 (DSC). The polymers of the present invention have a heat of fusion that can be located within a range of about 0.4 J / g to 75 J / g, preferably from 15 J / g to 60 J / g, and more preferably from about 25 J / g. ga 55 J / g, and a melt flow rate between 0.3 and 15 g / min (at a temperature of 230 ° C). More preferred melt flow rates are discussed here. Products produced with FPO polymers advantageously tend to have a softer, smoother and silkier appearance to the touch, instead of being stiffer, more sticky and stopping a slightly sticky appearance as in the case of products produced using conventional catalysts. The lower degree of tack is achieved, it is believed, by increasing the average molecular weight, and, particularly, by reducing the low molecular weight portions and decreasing the molecular weight band. This provides improved processing characteristics to the flexible polyolefin polymers. It is also believed that this is achieved by the use of an internal modifier present in the catalyst procatalyst portion present when the polyolefin polymers of the present invention are polymerized. An example of an internal modifier is the nitrogen-based electron donor of the present invention, preferably 2, 6-lutidine and 6-chloro-picoline.

When it is desired to alter the crystallinity of the polyolefin polymers, an external silane modifier may be added. MRF is measured in accordance with ASTM-D1238, method A / B (2.16 kg / 230 ° C), as for example in a Kayness Galaxy I fusion indexer. The methyl ethyl ketone solution ("MEK") was determined by extracting about 5 g of polymer with 100 ml of boiling methyl ethyl ketone for 6 hours. Stress tests (ASTM-D638) were carried out on an Instron 1125 with Type I injection molded tension bars at a test speed of 2 inches / minute. The VICAT softening point was measured in accordance with ASTM-D1525. The hardness was determined Shore D in accordance with ASTM-D2240. Percent strain was measured by tension after an extension of 300% and calculated by the following equation: Percentage of permanent deformation by tension = (Lf - LJ (Ln - L x 100% Where Lx is the initial separation, Ln is the extension, and Lf is the final separation Several other characteristics can be used to describe such polymers, such as for example VICAT softening point of about 40 ° C to 75 ° C, and preferably 45 ° C to 70 ° C; Shore D of about 30 to 6, and more preferably of about 40 to 55, tensile modulus, tensile stress, a melting inflation ratio of about 1.6 or less, preferably of about 1.5 or less, and especially 1.4 or less, and the like The VICAT softening point and the Shore D hardness vary according to the speed of the melt flow, heat of fusion, and the like in the polymer product.The properties vary according to the polymer Specific FPO produced which depends on the exact proportions of Al: i (between co-catalyst and pro-catalyst) and Si: i (between external modifier and pro-catalyst), as well as the specific silane or other similar compound used in the procatalyst and the external modifier. Thus, these polymers are defined primarily through their crystallinity, or heat of fusion, their melt flow rate, and their molecular weight distribution or polydispersity index ("MWD" or "PDI"). The molecular weight distribution, or polydispersity index, of the FPO polymers is about 10 or less, preferably about -or less, and about about 8.5 or less. The PDI is a ratio between the average molecular weight (Mw) and the average molecular number (Mn the melt swelling ratio is measured by the ratio in the diameter of an extruded polymer strand and the diameter of the hole through which it was extruded A lower melt swelling ratio is an indicator of a lower PDI, which in turn indicates a narrower molecular weight distribution and, consequently, a less sticky FPO polymer product. combined with a low melt flow rate advantageously provided the polymers of the present invention with characteristics desired in the art.For example, an MFR is characteristic of a reduced tackiness associated with polymer processing, both during production and as a product. final for consumer or indial use, in addition, the MFR below the FPO polymers tend to result in high melt strength. n and a higher viscosity, which greatly facilitates the production of various useful articles, such as expanded films. The terms "reduced tack" and "tack reduction", as used herein, are typically measured by the soluble MEK fraction of the polymer. A polymer having a reduced tack is generally where about 1 to 12% by weight, preferably about 2 to 5% by weight of the polymer is soluble in MEK. Although we do not wish to be bound by a particular theory, it is believed that the FPO polymer softens the isotactic polypropylene polymer, that is, it reduces the crystallinity, and increases the elasticity of the mixture, that is, elongation. Various additives can be included in the FPO polymers, such as, for example, antioxidant, antiblocking agents, anti-slip or anti-slip antiaditives, UV stabilizers, pigments, and the like. The addition and removal of hydrogen during the polymerization described herein can affect the MFR of the FPO polymers, while having a minimal impact on the degree of crystallinity. All the polymeric FPO materials mentioned herein, or in the applications or patents incorporated herein by reference, are useful in all polymer blends of the invention. These FPO materials are typically prepared using the novel catalyst material described herein and in the incorporated material from US applications number 08 / 878,129 and 08 / 779,772, the presentation of which is expressly incorporated herein by reference. It will be noted, however, that the silane component employed in a type of catalyst for the preparation of the FPO polymers also includes any aryl, preferably C5-12 aryl compounds instead of only C6-6 aryl compounds. Thus, the FPO material or the FPO materials can be combined or mixed with any of several amorphous polyolefin materials of the prior art in order to obtain novel and useful mixing formulations. suitable for use in various applications, such as adhesives, non-woven products, and fibers, strands or yarns used here, for example. The discovery of the catalyst materials presented here has allowed several novel blend formulations, including FPO polymer. In a preferred embodiment, the polymer blend is employed in a nonwoven product, wherein the mixture contains from about 3 to 80% by weight, preferably from about 20 to 50% by weight, and more preferably from about 25 to 45% by weight. % by weight of FPO polymer produced as described herein. Another type of catalyst that has been widely employed in recent years for the polymerization of olefins are two metallocene catalysts. In general terms, the catalysts of the catalyst include a transition metal atom, typically, zirconium, hafnium, vanadium or titanium having at least one cyclopentadienyl ligand attached thereto. Frequently, the transition metal atom is positioned between two cyclopentadienyl ligands, where it is said that the metal atom is "sandwiched" between the ligands. The famous compound known as ferrocene is an example of such an arrangement. In the field of olefin polymerization catalysis, a very creative work has been undertaken regarding the modification of the basic structure of ferrocene. The replacement of the iron atom by one of the transition metals mentioned above has provided a basic framework for researchers to make modifications with the hope of producing polymers that have beneficial physical properties to date not known. Through the substitution of several organic and inorganic portions in the position of the hydrogen atoms of the basic structure, several compounds useful in the polymerization of olefins were discovered, almost each of them with its own unique effect on the polymers produced using it as a catalyst . Examples of North American patents that have been generated as a result of these types of modifications to the basic structure include: 5,594,080; 4,769,510; 4,808,561 4,871,705; 4,935,397; 5,578,690 5,132,262 5,208,357 5,232,993; 5,280,074; 5,314,973 5,322,902 5,349,100 5,496,781; 5,525,690; 5,585,108 5,631,202 5,637,744 5,329, -33; 5,243,001; 5,241,025 5,278,264 5,227,440 5,214,173; 5,162,466; 5,145,819 5,120,867 5,103,030 5,084,534; 5,064,802; 5,057,475 5,055,438 5,017,714 5,008,228; 4,937,299; 5,081,322, and 5,036,034, the entire contents of which, including patents and publications mentioned herein, are incorporated herein by reference for the purpose of presenting the current state of the art of the polymerization of various polymer products using metallocene catalysts. That is, it is not a critical factor for the production of the mixtures according to the present invention if a given polypropylene that is mixed with the FPO polymers of the present invention is produced using Ziegler / Natta type catalysts or metallocene type catalysts. Thus, any polymer product of FPO or mixture including said FPO polymer, produced from any type of catalyst can be used for the production of a non-woven product, composite, or a fiber, strand or yarn, according to the invention . Preferably, however, the Ziegler / Natta type catalysts discussed herein are employed to polymerize the FPO polymer component of the various mixtures of the invention. MIXES OF POLYMER POLYMERS FPO / ISOTACTIC POLYPROPYLENE In order to produce the blends of the present invention, the FPO polymer and either an isotactic polypropylene polymer or a low molecular weight atactic APAO are combined in the following manner. The various polymer components are provided, preferably in their pellet form, and mixed together. One method to accomplish this is to first mix the pellets of different materials in the dry state in a dump chamber in which the pellets are agitated repeatedly by virtue of the rotation of the chamber around an ej perpendicular to the forces of gravity during a period of time. sufficient time to effect a good mixing, ie to provide a degree of uniformity known to persons with certain knowledge in the field. The mixture may also contain other additives considered desirable for the application as described herein known by persons with certain knowledge in the art. Once the components have been mixed in the dry state, they are typically fed into an extruder, such as Haake Model TW-100, where the materials are co-melted together, fed through the extruder through a screw single or several screws and pushed through a die equipped with a blade, whereby pellets of homogeneous polymer blend compositions are formed in accordance with this invention. For example, examples 100 to 104 below indicate some mixtures resulting from the invention. Various additives may be included in either the flexible polyolefin polymer or a polymer mixed therewith, or during the mixing of the FPO and another polymer to form a polymer blend. Suitable additives include antioxidants, UV stabilizers, pigments, binders, waxes, plasticizers, anti-slip agents, and the like. Preferred antiperspirant agents, when employed, include IRGAFOS 1010 commercially available from Ciba-Geigy or DOVERFLOU S9228, commercially from Dover Chemical Inc. The addition of hydrogen removal during the described polymerization can affect the MFR of the FPO polymers, while it has a minimal impact on the degree of crystallinity. The effects of hydrogen addition or hydrogen removal are known and understood by persons of certain skill in the art. The polymer blends of FPC / isotactic polypropylene polymer of the present invention, which preferably also has improved hysteresis, reduced effort reduction, and improved filtration properties, are processed in a beneficial way in product, tissues. Such non-woven products include fabrics, films, foams, laminates, and various other useful forms known to persons with certain knowledge in the art. These non-woven products have a wide range of uses, including agricultural, processing and storage uses, particularly, perishable products such as food, medical products, clothing such as diapers, personal care products, and the like. The mixtures presented here can be spun bonded, melt expanded, melt sprays, carded and the like, to produce multiple filaments, fibers, or yarns of the composition, which can also be prepared in non-woven fabrics or other products discussed here. or known by people with certain knowledge in the field. Non-woven fabrics that typically have improved processability and durability due to the materials of the present invention can be obtained by using materials that have a high elasticity, such as for example the polymer blends discussed herein. As used herein the terms "non-woven fabric" or "non-woven structure" or "non-woven product" are used to mean a material fabric formed from the polymer blends discussed herein. The material has individual fibers, strands, or threads (collectively "fibers") that are interwoven in some way but not woven. The fibers can be combined by means of a non-identifiable interlace (non-repetitive pattern) or an identifiable one (repetitive pattern). Various methods of preparing fibers, threads and yarns from mezoles for use in non-woven products in accordance with the present invention are presented in U.S. Patent Nos. 5,719,219 and 5,714,256 and in EP Publication No. 0,586,937 Al, the contents of which are expressly incorporated herein by reference. here by reference for this purpose. The invention also includes any other means for preparing fibers, strands and yarns from mixtures for use in known nonwoven products by persons having certain knowledge in the art. The isotactic polypropylene polymer employed in the mixture can be any isotactic polypropylene suitable for use in a mixture with other conventional polymers. The polypropylene polymer is typically present in an amount of about 20 to 97% by weight, preferably about 50 to 80% by weight and more preferably about 55 to 75% by weight, of the polymer blend. produced as described here. The crystallinity of the polypropylene polymer is typically from about 40 J / g to 100 J / g, preferably from about 60 J / g to 90 X / g, even though the crystallinity of an isotactic polypropylene polymer is readily determinable by a person. with certain knowledge in the matter. The isotactic polypropylene polymer can also be copolymerized with at least one C2-C2 alkylene. The alkene is preferably another alpha-olefin, for example ethylene, 1-butene, 1-pentene, and 1-octenc. A particularly preferred component for use in the isotactic polymer portion of the FPO polymer / isotactic polypropylene blend is a copolymer of ethylene or 1-butene, any of them, being typically present in an amount of about 1 to 40% by weight. weight, preferably from about 1.5 to 20% by weight, and more preferably from about 2 to 12% by weight, of the polymer composition. Exemplary isotactic polypropylene homopolymers suitable for use in the present invention include 41E4, 31S4 and 11SIA, all of which are commercially available from Huntsman Polymers Corporation of Odessa, TX. Exemplary copolymers of isotactic polypropylene with an ethylene copolymer suitable for use herein include 13R9A and 23N10, also commercially available from Huntsman Polymers Corporation. LMW FPO / APAO POLYMERS FOR ADHESIVES Mixtures of low crystallinity HMM APAOs (FPOs) with LMW APAOs discussed below provide the desired high melt viscosity, open time, tensile strength with low crystallinity, and other properties. desirable commented here. Polymer blends also have a high capacity for elongation and flexibility, even at low temperatures, and yet have superior strength at high temperatures. The new polymer blends also have a sufficiently long "open time" to provide desired adhesive characteristics, and are substantially transparent (i.e., excellent clarity), and preferably have only a glass transition temperature due to the miscibility of the two. polymer components. Thus, these polymer blends are especially useful as adhesive compositions, or in combination with any conventional adhesive composition to provide an improved adhesive composition. The APAO blends of the present invention expand and increase the range of melt viscosities available in conventional polymer blends. As the molecular weight of APAO blends increases, they become stiffer with improved tensile strength properties and more significant elongation (deformation at stress cracking). Even though the viscosity of the melt and the crystallinity are increased in the blends of the invention, the blends typically have RBSP, OT, and highly controlled melt viscosity properties. These blended products have improved retention power and improved cut adhesion failure temperature values, as well as good "strength before curing", which beneficially improves their desirability for non-required applications, adhesive melt applications in hot, polymeric modifiers, roof components, as well as modified tar roof membrane or an integrated roof formulation, and in asphalt and other modified tar applications. Several different families of propylene-based polymers, for example, can be employed for the preparation of the polymer blends, methods, and compounds, of the present invention. Examples of these APAO polymer families include, but are not limited to: APAO homopolymers, propylene copolymers of APAO / ethylene, propylene copolymers of APAO / butene, propylene homopolymers of FPO, propylene copolymers of FPO / ethylene, and propylene copolymers of FPO / butene. Typically, any combination of ethylene, propylene, and butene can be used in the polymers of APAO of LMW or HM? (FPO) that combine to form the polymer mixture. The LMW APAO polymer employed in the mixture can be any of the polymer families described above, provided that the polymer has the appropriate characteristics discussed herein, such as molecular weight, crystallinity, melt viscosity, and the like. Preferably, the APAO polymer of LMW predominantly includes ethylene, propylene, butepo, or copolymers or mixtures thereof. More preferably, the polymer of APAO of LMW is an ethylene / propylene copolymer or a butene / propylene copolymer, and more preferably, the LMW APAO polymer is from about 1 to 20% by weight of ethylene and about 80 to 99% by weight of propylene copolymer, or from about 2 to 70% by weight of butene, preferably from 30 to 65% by weight of butene, in a copolymer with from about 30 to 98% by weight of propylene, preferably from about 35 to 70% by weight of propylene. The APAO polymer of LMW preferably has an average molecular weight of from about 4000 to 16,000 g / mol, more preferably from about 6,000 to 12,000 g / mol, and especially from about 8,000 to 12,000 g / mol. The APAO polymer of LMW has a crystallinity, or heat of fusion of about 0.1 to 20 J / g, preferably about 0.5 to 15 J / g, more preferably about 1 to 10 J / g, as measured by DSC (ASTM D-3417). In addition, the LMW APAO can typically be chosen within a wide range of melt viscosities of approximately 400 to 20,000 cPs (at a temperature of 190 ° C). Since higher melt viscosities are a desired characteristic in the mixture of polymers and products formed with said mixture, it is preferable to employ higher melt viscosities in the LMW APAO. The REXTAC ® polymer series (LMW APAO), as well as several other polymers discussed herein are commercially available from Huntsman Polymers Corporation of Odessa, TX and are useful for the APAO portion of LMW? And polymer blends. Any of the polymer families listed above can also be used for the HMW APAO polymer (FPO), provided that the family has the appropriate characteristics discussed herein, such as molecular weight, crystallinity, melt flow rate, and the like. Polymers of FPO types, including polymers of predominantly ethylene, propylene, butene or copolymers or mixtures thereof, are preferred for the HMW APAO polymer (FPO) used in the polymer blend, since they are characterized by a variety of desirable properties described here. The most important of these properties are the degree of crystallinity and the degree of polymerization, as measured by the heat of fusion and the rate of flow in fusion. The heat of fusion (delta Hf) is typically measured by DSC using a method of the ASTM standard. The FPO polymers (HMW APAOs) of the present invention have a heat of fusion that can be located within a range of about 15 to 60 J / g, and a melt flow rate of between about 0.3 and 100 g / g. min (at a temperature of 230 ° C). Manufactured products made with FPO polymers alone advantageously tend to have a softer, softer and silkier appearance to the touch, instead of being stiffer and drier to the touch, as is the case with products produced using polypropylenes conventional isotactic The FPO polymers used in the mixture typically have an Mn of about 15,000 g / mol to 30,000 g / mol, preferably from about 20,000 to 25,000 g / mol, and more preferably from about 21,000 to 24,000 g. / mol. The specific Mn varies according to the APAO of the particular HMW used, which depends on the desired final properties and the application applied to the polymer mixture. The average molecular weight varies more dramatically according to the APAO of HMW used, even though it is generally above 100,000, preferably between about 130,000 g / mol to 230,000 g / mol, and especially between about 150,000 a 200,000 g / mol. The use of FPO polymers having a low crystallinity, which can be prepared by the use of a catalyst system that produces polymers with well-defined physical properties, facilitates the production of polymer blends having the required reproducible specifications of adhesive and other formulations. applications. Said catalyst system and various low crystallinity HMW APAO polymers produced therewith and suitable for use in the present invention are presented in copending US Patent Application No. 08 / 779,762, the disclosure of which is expressly incorporated herein by reference.

The polymers discussed herein are preferred HMW APAOs for use in the polymer blends of the present invention since they advantageously have a low crystallinity required for the present invention in the range of about 15 to 60 J / g, while also having a melt flow rate between about 0.3 and 100 g / 10 min, and each integer between these limits. Preferably, the melt flow rate (at a temperature of 230 ° C) of the HMW APAOs of the present invention is between about 0.4 and 50 g / 10 min, more preferably between approximately 0.5 and 20 g / 10 juin, and especially between approximately 1 and 15 g / 10 min, and each whole number between these limits. The MFR can be varied according to the variation of the catalyst recipe, as presented here. These HMW APAO polymers ("FPO polymers") are also described as flexible polyolefins, and are profitably produced by the use of a catalyst containing a procatalyst capable of providing a polymer with a crystallinity of about 15 J / g. a low melt flow rate, an organometallic compound, and optionally, an external modifier to increase the low crystallinity to 60 J / g, depending on the amount and type of external regio control modifier included in the catalyst. Several of these preferred HMW APAO polymers are available from Huntsman Polymers Corporations, Odessa, TX, under the designations "FPO polymer" or "FPD" such as FPD-100, FPD-400, FPD-2300, FPD- 1700, FPD-1710, FPD-1720, FPD-1800, FPD-1810, and FPD-1820. All of these HMW APAO polymers have a crystallinity of between about 15 and 75 J / g and all are preferred HMW APAOs for use herein, even though the FDP-100, FDP-400 and FDP-2300 are the most preferred types of APAO polymers from HMW. Even when a crystallinity, or heat of fusion, between about 15 and 60 J / g is suitable for use in the polymer blends of the present invention, it is preferable to employ an APAO of HMW having a lower degree of crystallinity for provide a reduced crystallinity in the polymer mixture. Preferably, the heat of fusion is between about 18 and 50 J / g, more preferably between about 20 and 35 J / g, and especially the heat of fusion is between about 22 and 30 J / g. . HMW APAOs, preferably elastomeric, with high melt viscosity and low crystallinity values, are mixed with the LMW APAOs, which also preferably have a high melt viscosity, to obtain the desired characteristics described herein. These individual polymers, as well as mixtures produced with them, can be characterized following the standard test methods established by the American Society for Testing and Materials (ASTM) which are widely used in the adhesives industry. fusion- hot. These test methods are generally the following. The melt viscosity, MV (cPs or mPa * s), is typically determined in accordance with ASTM D-3236, measures the internal friction of the molten or liquid polymer, i.e., its resistance to flow. This distinctive property determines the flow capacity and the degree of wetting, or penetration, of a substrate by the melted polymer; it provides an indication of its processing capacity. A melt viscosity is generally directly related to the molecular weight of the polymer, and is reported in a thousand pascal x sec (mPa-sec), or, centipoise, using a THERMOSEL RVT DE BROOKFIELD ® viscometer. Needle penetration, NP (dmm) is usually measured in accordance with ASTM D-1321. With thermoplastics and elastomers, this test method, which measures the depth at which a needle with weight penetrates the surface of the polymer and determines the resistance of the polymer to the deformation by penetration, it is frequently used as a: - simple edition of rigidity (or softness). The ring and ball softening point (RBS) (° C / ° F), is typically measured in accordance with ASTM E-28 due to the predominantly amorphous nature of the APAO polyolefins here, the melting does not take place at a defined, precise temperature. On the contrary, as the temperature rises, these APAO polymers gradually change from the solid state to a soft state and then to a liquid state. This test method generally measures the precise temperature at which a polymer sample disk immersed in a glycerin bath and heated at a rate of 5.5 ° C / min (10 ° F / min) is sufficiently softened to allow the object test, a steel ball, fall through the sample. The softening point of a polymer, reported in ° C (° F) is important, because it typically indicates the polymer's resistance to heat, application temperature and solidification point. The open time, OT (sec), is typically measured according to ASTM D-4497, which measures the time, in seconds, between the application of a thin film of the hot melt adhesive and the time just before the melt film in hot lose its wetting capacity (adhesion) due to solidification. More particularly, this can be measured by stretching a thin film of polymer and applying one-inch-wide strips of paper on the film with a two-pound roller at specific time intervals. Generally, the paper strips are applied at 10, 20, 40, 60, 90, 120 and 240 seconds after stretching of the film. After waiting for approximately 5 (5) minutes, the paper strips are removed from the film.

When the paper breaks, there is an open time. According to the ASTM method, at least 50% of the paper must remain so that there is an open time. However, under the stricter REXENE ® method employed in this application, at least 90% of the fiber must remain in the polymer. Other standard test methods were used to determine polymer melting heat and melting point of polymer (ASTM D-3417), glass transition temperature (ASTM D-3418), stress improprieties (ASTM D-638) . The polymer blends of the present invention can be prepared by any conventional method or suitable for combining polymers. For example, the LMW APAO and the HMW APAO can be combined by mixing in a batch mixer or kneading with a sigma blade kneader, designated by the sigma-shaped blade that virtually scrapes the sides of the container with the object to facilitate the mixing of the polymer. The selection of the APAO polymers of LMW and HMW is crucial to obtain the polymer blends of the invention, obviously, even when to be properly mixed, the APAOs must simply be in a melted state when combined by mixing or kneading. Another suitable way to combine the APAOs of LMW and HMW is in an extruder. When extrusion is used, the APAO polymers must be heated above the softening point. Naturally, the temperature at which LMW and HMW APAOs soften or melt varies according to the particular APAOs selected. It will be understood that once the polymers have been selected, a person with certain skill in the art can determine the temperature at which the polymers will melt or soften as required for proper mixing. Polymer blends useful as adhesives or in compounds typically contain from about 2 to 40% by weight of HMW APAO polymer with about 60 to 98% by weight of APAO polymer from LMW. Preferably, the polymer blends contain from about 5 to 35% by weight of HMW APAO, more preferably from about 10 to 30% by weight of the APAO of the HMW, the remainder being APAO of LMW. The amount of one or both polymers of APAO of HMW and LMW can be correspondingly reduced if an additive is included, typically in an amount of about 5% by weight of the total polymer mixture. The polymers of the present invention can be described by several characteristics, which are set forth below.

For example, it is desired that the polymer blends have a broad molecular weight distribution. A high tensile stress to the break is desired, and this value is typically from about 20 psi to 800 psi, preferably preferably from about 50 psi to 700 psi, and more preferably from about 100 psi to 600 psi. A large open time is typically desired, at least about 10 seconds, preferably at least about 30 seconds, more preferably at least about 50 minutes, and especially at least about 100 seconds. It is also desired a high / melt viscosity, typically between about 8,000 and 340,000 cPs, preferably between about 15,000 and 320,000 cPs, more preferably between about ,000 and 300,000 cPs, and more preferably between approximately 50,000 and 250,000 cPs, and each whole number of thousand between these values. The melting point of the polymer blends is typically between about 95 ° C and 155 ° C, preferably between 137 ° C and 153 ° C, and especially between about 139 ° C and 151 ° C. Preferred polymer blends are mixtures where there is only a melting point, which indicates that the APAO polymers of LMW and HMW are substantially miscible. The most preferred polymer blends have only one melting point, which falls within the range of most preferred melting points, and the mixtures contain minimal crosslinking, if any. The glass transition temperature is an even better indicator of the mixing capacity between the HMW APAOs and the LMW APAOs than the melting point, and the glass transition temperature is typically between about -5 ° C and - - 35 ° C, preferably between about • 10 ° C -30 ° C, especially between about -15 ° C and -25 ° C. The optical appearance of the polymer blends is also important, with substantially clear mixtures being preferred. The use of substantially miscible HMW and LMW APAOs in the polymer blends will substantially reduce the cloudy appearance typically found in incompatible polymer blends. The polymer blends are relatively soft and are measured on the Shore A scale between about 40 and 80, preferably between about 50 and 70, and more preferably between about 55 and 75. On the Shore D scale, mixtures of Polymers of the present invention are typically between about 6 and 14, preferably between about 7 and 13, and especially between about 8 and 12. The stress strain at break is typically between an elongation of about 30% in the case of mixtures of MW polymers lower until a "no break" deformation, ie, no break in the polymer blend is observed at an elongation of about 310%. Even when the mixtures are relatively soft, the voltage modulus at 23 ° C is between approximately 500 psi and 20,000 psi, or approximately 100 to 1400 kg / square centimeters. Preferably, the voltage module is comprised between about 750 psi and 15,000 psi, and more preferably between about 1,000 psi and 10,000 psi. The polymer blends also have a relatively low crystallinity, typically a heat of fusion of less than about 28 J / g, preferably less than about 20 J / g, and especially less than about 10 J / g. Such blends are typically obtained by the use of HMW APAO components having a low crystallinity. The composite articles of the present invention include the above-described polymer blends of FPO and atactic polyolefin polymers as an adhesive component together with a non-woven product. It will be understood that any adhesive component can also be employed with the fiber, strand or yarn of the present invention, just as any nonwoven product can be employed with the adhesive composition of the present invention to obtain a composite article of the present invention. The non-woven products may be conventional non-woven products known to those of ordinary skill in the art, even though the non-woven products described herein are preferably a mixture of polymers of FPO and polymers of isotactic polypropylene. For example, composite articles include any of the nonwoven products, such as a garment, which includes an adhesive composition. An example of a composite article is a disposable non-woven layered diaper having adhesive between the layers. It will be understood that all ranges of quantities, characteristics, properties, and the like described herein include all integers within each described range. EXAMPLES The polymer blends used in the present invention are further defined with reference to the following examples which describe in detail the preparation of the compounds and compositions useful in the blended products presented herein. It will be apparent to persons skilled in the art that many modifications, both in terms of materials and methods can be practiced without departing from the purpose and interest of this invention. Several catalysts were prepared and tested in the preparation of FPO polymers. Polymerization tests were carried out in liquid polypropylene in a 1.0 L stainless steel auto key equipped with a stirrer. After having purged the reactor completely with nitrogen to remove any contamination, such as moisture and oxygen, 10 mg of a solid procatalyst component was charged to the reactor as a 1% by weight mixture in dry mineral oil, followed by the addition of triethylaluminum cocatalyst in a prescribed amount to obtain a molar ratio to Al / Ti of approximately 200: 1. S then charged 300 g of liquid propylene in the reactor and the polymerization was carried out at a temperature of 60 ° C for one hour under sufficient stirring to mix the components. At the end of the hour, the unreacted propylene was removed by ventilation and the polymer product was recovered. The "C donor" was cyclohexylmethyldimethoxysilane, and the "D donor" was dicyclopentyl dimethoxysilane. EXAMPLES 1-2: Conventional Catalysts A conventional catalyst can be prepared in accordance with that presented in U.S. Patent No. 4,347,158. Example 1 of the '158 patent describes said catalyst preparation in the following manner. Anhydrous MgCl 2 was prepared by drying at a temperature of 350 ° C for -i hours under a layer of HCl. 25 grams of this anhydrous MgCl2, 4.34 grams of A1C13, and 7.01 g of anisole were charged under a nitrogen atmosphere in a vibratory ball mill having a capacity of 0.6 L which contained 316 stainless steel balls with a total weight of 3250 g each with a diameter of 12 mm. This mixture was crushed for 24 hours without temperature control. Precomplexes of titanium tetrachloride were formed with ethyl benzoate (EB) in n-heptane at a temperature of about 50 ° C. 6.19 g of this TiCl4EB complex were then charged into the vibratory bead mill after the previous 24 hours of grinding the other materials, and the resulting mixture was co-crushed for an additional 20 hours at room temperature and under an inert atmosphere. This produced a solid catalyst component that can be employed without requiring extraction or catalyst washing. Another conventional catalyst was prepared, for comparison purposes, with the catalysts of the present invention, approximately as follows: 30g (0.315 mol) of MgCl2 were cotriturados with 5.22 g (0.0391 mol) of A1C13 during 24 hours in RBM under a nitrogen atmosphere. Then, 4.02 g (0.0212 mol) of Ticl4 was added. The ball milling continued for approximately 24 hours. 30 g of a yellow procatalyst powder was collected. The titanium component was calculated to be about 2.6% by weight, the aluminum component about 2.7% by weight, the magnesium component about 19.3% by weight, and the Mg: Al: Ti ratio was about 8: 1: 0.5. . EXAMPLES 3-19: Effect of Internal Type I Donors Several procatalysts and catalysts were prepared to examine the effect of type I internal donors on the effective surface area and catalyst activity: Example 3: Same as in Example 6 below, except that 1.18 g of EtOBz were used. Calculated: Your% = 2.50; EB / Mg? 0.025 (mol / mol). Example 4: 30 g of MgCl2. 5.25 g of A1C13 and 2.36 g of EtOBz (0.0158 mol) were milled in ball mill (VBM) during 16 hours, then TiCl4 of 4.02 g was added and the mixture was milled in a ball mill for an additional 16 hours.

Calculated: Ti% = 2.43; EB / Mg = 0.05 (mol / mol). Example 5: Same as in Example 6, except that 4.72 g of EtOBz was used. Calculated: Ti% = 2.31; EB / Mg = 0.10 (mol / mol). Example 6: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 1.55 g (0.0131 mole) (EtO) SiMe 3 and 4.02 g TiCl 4 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 7: 30 g of MgCl2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 3.1 g (0.0263 mol) (EtO) SiMe3, and 4.02 g of TiCl4 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 8: 30 g of MgCl2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 6.15 ml (0.0394 mol) (EtO) SiMe3 and 4.02 g of TiCl were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 9: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 2.47 g (0.0131 mol) of C donor and 4.02 g of TiCl 4 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 10: 30 g of MgCl2 and 5.25 A1C13 were milled in ball mill (RPM) for 24 hours, and then 7.42 g (0.0394 mol) of C donor and 4.02 g of TiCl4 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 11: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 3.0 g (0.0131 mol) of D donor and 4.02 g of TiCl 4 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 12: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 9.0 g (0.0394 mol) of D donor and 4.02 g of TiCl were added. The mixture was subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst. Example 13: 5 g of Example 2 were suspended in 100 ml of toluene, stirred for one hour at a temperature of 60 ° C, filtered and suspended in 20 ml of fresh toluene. 16.5 ml of TiCl4 and 0.74 ml (3.2 mmoles) of D (dicyclopentyl dimethoxysilane) donor were added. The mixture was stirred at a temperature of 90 ° C for 1 hour, filtered (dark brown solid), washed with heptane (turned yellow green) and toluene (return to dark brown), suspended again in 30 ml of toluene . 17 ml of TiCl4 was charged and the mixture was stirred at a temperature of 90 ° C for an additional 1 hour. The solid was removed by filtration and washed thoroughly with heptane. Example 14: 1) MgCl2 30 g, A1C13 5.25 g and (EtO) 3SiMe 7.02g (0.0394 mol) were placed in a ball mill during 24 hours. 2) 5 g of the aforementioned precursor were suspended in 100 ml of toluene, with stirring at a temperature of 60 ° C for 1 hour, filtered, the solids were washed with heptane, toluene, and then suspended in 30 ml of fresh toluene. 16.5 ml (150 mmoles) of TiCl ^ (the paste turned brown) was charged. The paste was stirred at a temperature of 90 ° C for 1 hour, filtered, the solids were washed with heptane, toluene, and then the solids were suspended again in 30 ml of toluene. 10.5 ml of TiCl4 was charged and a reaction was obtained for 1 hour at a temperature of 90 ° C. The solid was washed with heptane. The solid presented an orange-red color in toluene but turned yellow after washing with heptane. Example 15: 30 g of MgCl2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 6.69 g (0.0394 mol) of SiCl4 and 4.02 g of TiCl4 were added. The mixture was subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst. Example 16: 30 g of MgCl 2, 5.25 g of A1C13 and 2.76 g of dibutyl palato were subjected to milling together in a ball mill for 24 hours, then 4.02 g of TiCl were added. The mixture was subjected to milling in a ball mill for an additional 24 hours in order to provide the procatalyst. Example 17: 30 mg of MgCl2 and 2.76 g of dibutyl phthalate were subjected to milling in a ball mill for 24 hours, and then 4.02 g of TiCl4 were added. The mixture was subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst. Example 18: 30 g of MgCl 2 and 5.25 g of A1C13 were subjected to milling in a ball mill (RBM) for 24 hours, and then 7.68 g (0.0212 mol) of di-ethyl phthalate and 4.02 g (0.0212) were charged. mol) of TiCl4 and subjected to grinding in a ball mill for an additional 24 hours. Example 19: Same as in Example 14, except that without (EtO) 3 SiMe but with dropwise addition of 1.17 ml of diheptyl phthalate (it became dark) before reacting at a temperature of 90 ° C for 1 hour. These procatalysts were used in a catalyst for the polymerization of polypropylene in order to produce polymers for use as a complement of flexible polymer having the characteristics mentioned in Tables I and II below: TABLES I and II Composition No. Donator Donator /You Example 1 TiCl4 / MgCl2 / AlCl3 / EB & nd EB / Anisole Anisole TiCl4 / MgCl2 / AlCl3 / None (BM) TiCl4 / MgCl2 / AlCl3 / Benzoate 0. 37 EB (BM) Ethyl TiCl4 / MgCl2 / AlCl3 / Benzoate 0. 74 EB (BM) ethyl TiCl4 / MgCl2 / AlCl3 / Benzoate of 1. 48 EB (BM) ethyl TiCl 4 / MgCl 2 / AlCl 3 / (EtO) Si 0. 62 (EtO) SiMe 3 (BM) Me 3 TiCl 4 / MgCl 2 / AlCl 3 / (EtO) Si 1.24 (EtO) SiMe 3 (BM) Me 3 TiCl 4 / MgCl 2 / AlCl 3 / (EtO) Si 1. 86 (EtO) SiMe3 (BM) Me 3 TiCl4 / MgCl2 / AlCl3 / donor C 0.62 donor C (BM) 10 TiCl4 / MgCl2 / AlCl3 / donor C 1.86 donor C (BM) 11 TiCl4 / MgCl2 / AlCl3 / donor D 0.62 donor D (BM) 12 TiCl4 / MgCl2 / AlCl3 / donor D 1.86 donor D (BM) 13 TiCl4 / MgCl2 / AlCl3 / donor D nd donor D (solution) 14 TiCl4 / MgCl2 / AlCl3 / (EtO) 3SiMe nd (EtO) 3SiMe (solution) 15 TiCl4 / MgCl2 / AlCl3 / SIC14 1.86 SiCl4 (BM) 16 TiCl4 / MgCl2 / AlCl3 / Phthalate 0.47 DBP (BM) dibutyl 17 TiCl4 / MgCl2 / DBP Phthalate 0.47 (BM) dibutyl 18 TiCl4 / MgCl2 / AlCl3 / DHP (BM) phthalate dibutyl 19 TiCl4 / MgCl2 / AlCl3 / Phthalate of nd DHP (Solution) dibutyl No. of No. of C.E. ? Hf p.f. MFR MEK Example Exp. G / g-cat J / g ° C g / 10 sol% Poly. min 1 2507-39 11900 42.9 155.9 11 nd 2 2536-1 16500 30 154 11 11 3 2536-25 17600 31.8 153.8 10.3 12.5 4 2536-21 18500 35.1 154.5 9.6 11.1 5 2536-27 13800 39.2 154.7 7.4 12.2 6 2540-31 18800 36.1 153.9 8.4 10.4 7 2536-99 23300 39.6 153.5 8.9 7.6 8 2536-97 21000 43.9 152.4 15.3 7.8 9 2540-7 19400 33.7 153.1 8.6 7.8 10 2536-95 13400 40.9 152.8 7.5 5.5 11 2540-6 19800 35.9 153.7 9.9 5.7 12 2536-93 13800 36.9 154.4 3.6 4.7 13 2536-62 27300 37.7 154.2 12.7 9.4 14 2536-54 18200 51.1 155.2 4.6 7.9 15 2536-91 17500 34.2 153.6 13.7 7.1 16 2541-59 13900 46.9 1586.0 4.2 8.4 17 2541-62 9900 44.2 155.4 4.0 6.8 18 2536-58 10700 49.7 156.1 0.75 4.5 19 2536-56 9700 49.7 156.7 1.2 7.1 nd = not determined polymerization conditions: 10 mg of catalyst; 300 g of propylene; At / Ti = 200; 60 ° C for 1 hour. Examples 3-19 illustrate a variety of type I donors and their effects on polymer properties. They were typically co-ground with catalyst supports (MgCl2 / AlCl3) before addition of TiCl, except in the case of catalysts made through a solution process. The effect of donors produced by the ball mill method on productivity indicates that silane donors are more effective than other donors in increasing productivity at low dosages.

These donors prepared by the solution process indicate an improvement in productivity which, with increasing donor dosage, also indicates an increased heat of fusion of the polymer. The desired donors are the donors that provide the greatest increase in productivity while causing the least change to the heat of fusion. Silane donors usefully meet the criteria more effectively. Examples 20-31: Effect of Type II Internal Donors Several of these catalysts were examined for type II internal donor characteristics in an attempt to locate a catalyst that produces a lower amount of the low molecular weight FPO polymers compared to the usual Example 20: see example 2. Example 21: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 4.46 g (0.0394 mol) of 2,6-dimethylpiperidine cis were added, and 4.02 g of TiCl. The mixture was subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst. Example 22: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 5.56 g (0.0393 mol) of 2, 2, 6,6-tetramethylpiperidine and 4.02 g were added. of TiCl4. The mixture was then subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst. Example 23: 30 g of MgCl 2 and 5.25 g of A1C13 were subjected to grinding in a ball mill (RBM) for 24 hours, then 4.19 ml (0.0394 mol) of 2,5-dimethylfuran and 4.02 g of TiCl4 were added. The mixture was then milled in a ball mill for an additional 24 hours in order to obtain in procatalyst. Example 24: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 3.95 g (0.0394 mol of 2,5-dimethyltetrafuran and 4.02 of TiCl 4) were added. milled in a ball mill for an additional 24 hours to provide the procatalyst Example 25: 30 g of MgCl 2 and 5.25 g of A1C13 were subjected to grinding in a ball mill (RBM) for 24 hours, and then 3.67 g were added ( 0.0394 mol) of 2-picoline and 4.02 g of TÍCI 4. The mixture was then ground in a ball mill for an additional 24 hours in order to obtain the procatalyst Example 26: 21.4 g of MgCl 2 and 3.75 g of A1C13 were ground in a ball mill (RBM) for 24 hours, then 5.0 g (0.0281 mol) of 4-chlorokquinaldine and 2.85 g of TÍCI4 were added.The mixture was then subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst Example 27: 30 g of MgCl2 and 5.25 g of A1C13 fu They were milled in a ball mill (RBM) for 24 hours, then 4.59 ml (0.0394 mol) of 2,6-Lutidine and 4.02 g of TÍCI4 were added. The mixture was subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst. Example 28: 30 g of MgCl 2 and 5.25 g of A1C13 were subjected to milling in a ball mill (RBM) for 24 hours, and then 4.77 g (0.0393 mol) of 2, 4, 6-collidine and 4.02 g were added. TiCl4. The mixture was subjected to milling in a ball mill for an additional 24 hours to provide the procatalyst, Example 29: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 5.05 g (0.0394 mol) of 6-chloro-2-picoline and 4.02 g of TÍCI4 were added. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst.

Example 30: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 5.83 g (0.0393 mol) of 2,6-dichloropyridine and 4.02 g of TiCl 4 were added. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 31: 30 g of MgCl 2 and 5.23 g of A1C13 were milled in a ball mill (RBM) for 24 hours, and then 9.33 g (0.0394 mol) of 2,6-dibromopyridian and 4.0 g of TÍCI were added. The mixture was then milled in a ball mill for an additional 24 hours in order to obtain the procatalyst. These catalysts were used in the polymerization of polypropylene to obtain polymers with the characteristics presented in the following tables: TABLE III and IV No. of Donor No. of C. E. ? Hf P.F. MFR Exp. Exp. of g / g-cat h J / g ° C g / 10 Polin. min 20 None 2536-1 16500 30 154 11 21 2, 6-dimethyl-2536-79 7900 35.9 154.3 11 piperidine 22 2,2,6,6- 2540-51 7400 51.1 156.4 0.68 Tetramethyl- Piperidine 23 2, 5-dimethyl - 2536-76 14000 35.1 154.1 6.4 furan 24 2, 5-dimethyl-2536-80 14700 28.4 153.6 18.4 tetrahydrofuran 25 2-picoline 2540-84 13700 27.8 153.6 7.3 26 4-chloroquinal-2536-86 6500 30.2 154.4 3.6 dyna 27 2,6-Lutidine 2536-3 6800 27.5 155.0 1.4 28 2,4,6-coli 2540.37 9000 29.7 154. 1.22 'dyne 29 6-chloro-2 -2536-83 9300 27.5 154.5 1.2 picoline 30 2,6-dichloro- 2540-35 9100 26.9 154.4 3.1 pyridine 31 2, 6-dibromo- 2540-86 9300 27.6 153.6 2.1 pyridine No. of MEK Mn Mw PDI Example Sol% xlO-3 xlO-3 20 11 21 209 9.9 21 6.0 28 239 8.47 22 5.9 33 385 12.2 23 8.4 27 277 9.6 24 9.2 20 201 9.9 25 11.0 22 214 9.7 26 7.6 25 239 9.4 27 4.8 36 283 7.8 28 4.62 29 3.8 36 280 7.8 30 8.1 32 26.5 8.29 31 8.9 29 295 10.3 a - general catalyst composition: TiCl4 / MgCl2 / AlCl3 / donor, ground in ball mill, Donor / Ti = 1.86. b - polymerization conditions: 10 mg of catalyst: Al / Ti = 200; 60 ° C for 1 hour Examples 20-31 illustrate a variety of type II donors, including Lewis base donors based on sterically hindered, aromatic nitrogen. It was desired to obtain a higher molecular weight indicated by minor MRF, while having a minimal effect on crystallinity. The above results suggest that: (1) nitrogen-based donors are generally more effective in increasing molecular weight than oxygen-based donors (examples 23 and 24, for example); (2) Lewis bases based on non-aromatic nitrogen, for example, examples 21 and 22, had a more pronounced effect on the heat of fusion of polymers than aromatic derivatives, the latter being weaker Lewis bases; and (3) the steric hindrance around the nitrogen atom seems important to increase the steric hindrance of 2-picoline to 2,6-glutidine to 2,6-dibromopyridine, with the low molecular weight fractions decreasing first, then increasing again . 2, 6-glutidine and 6-chloro-2-picoline were more effective in reducing the LMW fractions. These polymers are intended to be employed as the flexible polyolefin polymer component of the various blends of the invention. Examples 32-44: combinations of type I and type II donors Several catalysts were prepared and tested in order to obtain good productivity, while providing higher molecular weight and lower crystallinity: Example 32: 30 g MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 5 hours, 1.55 g were added (0.0131 mol) (EtO) SiMe; and it was subjected to grinding in a ball mill for 19 hours, then 4.22 g was added. (0.0394 mol) of 2, 6-lutidine and 4.02 g of TiCl4. The mixture was then milled in a ball mill for an additional 24 hours in order to obtain the procatalyst. Example 33: 30 g of MgCl2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 3.1 g (0.026 mol) (EtO) SiMe3 and 4.02 of TiCl4 were added. The mixture was then milled in a ball mill for an additional 24 hours. 10 g of this mixture were suspended in 30 ml of toluene, to which were added 33 ml of TÍCI4 and 0.75 ml (0.0064 mol) of 2,6-Lutidine. The mixture was stirred at a temperature of 90 ° C for 1 hour, then filtered (orange filtrate) and washed with heptane 3 times to give the yellow procatalyst. Example 34: 30 g of MgCl 2, 5.25 g of AlCl 3 and 0.74 g of diethoxydimethylsilane were milled in a ball mill for 24 hours, and then 1.41 g of 2,6-lutidine and 4.02 g of TiCl 4 were added. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 35: 30 g of MgCl 2, 5.25 g of A1C13 and 0.95 g of donor C were milled in a ball mill (RBM) for 24 hours, then 1.41 g (0.0131 mol) of 2,6-lutidine and 4.02 were added. g of TÍCI4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 36: 30 g of MgCl 2 / 5.25 g of A1C13 and 1.23 g of dicyclopentyldimethoxysilane were milled in a ball mill for 24 hours, then 1.41 g of 2,6-glutidine and 4.02 g of TiCl 2 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 37: 30 g of MgCl 2, 5.25 g of A1C13 and 1.38 g of dibutyl phthalate were ground in a ball mill for 24 hours, then 1.41 g of 2,6-lutidine and 4.02 g of TiCl 4 were added. The mixture was milled in a ball mill during 24 additional hours to provide the procatalyst. Example 38: 30 g of MgCl 2, 5.25 g of A1C13 and 0.95 g of donor C were milled in a ball mill (RBM) for 24 hours, then 1.66 g (0.0131 mol) of 6-chloro-2-picoline were added. and 4.02 g of TiCl 4. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 39: 30 g of MgCl2, 5.25 g of A1C13 and 0.95 g of donor C were milled in a ball mill (RBM) for 24 hours, then 3.32 g (0.0262 mol) of 6-chloro-2-picoline were added and 4.02 g of TiCl4. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 40: 5 g of the procatalyst of the example were suspended in 100 ml of toluene and stirred at a temperature of 60 ° C for 1 hour. The solid was removed by filtration and resuspended in 30 ml of toluene. 16.5 ml of TiCl4 and 0.1 ml (0.0005 mole) of C donor were added to the suspension. The mixture was then stirred at a temperature of 90 ° C for one hour, filtered and washed with heptane and then toluene. The solid was resuspended in 30 ml of toluene and mixed with 16.5 ml of TiCl4 and 0.41 g (0.0032 mol) of 6-chloro-2-picoline. The mixture was reacted at a temperature of 90 ° C for an additional hour, and then filtered and washed with heptane 3 times to provide the procatalyst. Example 41: 5 g of the procatalyst of Example 2 were suspended in 100 ml of toluene, and stirred at a temperature of 60 ° C for one hour. The solid was removed by filtration and resuspended in 30 ml of toluene. 16.5 ml of TiCl4 and 0.25 ml (0.001 mole) of D donor were added to the suspension. The mixture was then stirred at a temperature of 90 ° C for 1 hour, filtered and washed with heptane 2 times. The solid was resuspended in 30 ml of toluene and mixer with 16.5 ml of TiCl4 and 0.41 g (0.0032 mol) of 6-chloro-2-picoline. The mixture was reacted at a temperature of 90 ° C for 1 hour and then filtered and washed with heptane 3 times to provide the procatalyst. Example 42: 5 g of the procatalyst from example 2 were suspended in 100 ml of toluene and stirred at 60 ° C for 1 hour. The solid was removed by filtration and resuspended in 30 ml of toluene. 16.5 ml of TiCl4 and 0.1 ml were added (0.0004 mol) of D donor in the suspension. The mixture was then stirred at a temperature of 90 ° C for 1 hour, filtered and washed with heptane and then with toluene. The solid was resuspended in 30 ml of toluene and mixed with 16.5 ml of TiCl and 0.41 g (0.0032 mol) of 6-chloro-2-picoline.

The mixture was reacted at a temperature of 90 ° C for an additional hour, and then filtered and washed with heptane 3 times to provide the procatalyst. Example 43: 30 mg of MgCl2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 1.55 g (0.013 mol) of (EtO) SiMe3 and 4.02 g of TiCl4 were added. The mixture was milled in a ball mill for an additional 24 hours. 5 g of this mixture were suspended in 100 ml of toluene and stirred at a temperature of 80 ° C for 1 hour. The solid was removed by filtration and resuspended in 30 ml of toluene. 16.5 ml of TiCl4 and 0.41 g (0.0032 mol) of 6-chloro-2-picoline were added to the suspension. The mixture was then stirred at a temperature of 90 ° C for 1 hour, filtered and washed with heptane to provide the procatalyst. Example 44: 5 g of the mixture of example 43 were suspended in 100 ml of toluene and stirred at a temperature of 80 ° C for one hour. The solid was removed by filtration and resuspended in 30 ml of toluene. 16.5 ml of TiCl4 and 0.0032 mol of 2,6-dichloropyridine were added (dissolved in toluene) in the suspension. The mixture was then stirred at a temperature of 90 ° C for 1 hour, filtered and washed with heptane 3 times to provide the procatalyst. These procatalysts were used in catalysts for the polymerization of propylene in order to produce flexible polymers having the characteristics presented in the following tables: TABLE V and VI No. of Donor Type-A Donor Type-B No. of Example (Donor / Ti) (Donor / Ti) exp. of polim. 32 (EtO) SiMe3 2, c-Lutidine 2540-24 (BM) Si / Ti = 0.62 N / _i = 186 33 (Et =) SiMe3 2, 6-Lutidine 2540-39 (solution) Si / Ti nd N / i nd 34 (EtO) 2SÍMe2 2, 6-Lutidine 2541-53 (BM) Si / Ti = 0.23 N / Ti = 0.62 35 donor-C 2, € -Lutidine 2540-91 (BM) Si / Ti = 0.23 N / i = 0.62 36 donor-D 2, -Lutidine 2541.51 (BM) Si / Ti = 0.23 N / Ti = 0.62 37 Dibutyl 2 phthalate, € -Lutidine 2541-23 (BM) DBP / Ti = 0.23 N / Ti = 0.62 38 C-donor 6-clcro -2-picoli- 2540-96 (BM) Si / Ti = 0.223 na N / Ti = 0.62 39 donor-C 6-chloro-2-picoli- 2540-98 (BM) Si / Ti = 0.23 na N / Ti = 1.24 40 donor-C <; 6-chloro-2-picoli- 2540-77 [solution] Si / Ti n.d. na N / Ti n.d. 41 donor-D 6-chloro-2-picoli- 2540-53 (solution) Si / Ti n. d. na N / Ti n. d. i 42 donor-D 6-chloro-2-picoli- 2540-67 (solution) Si / Ti n.d. na N / Ti n.d. 43 (EtO) SiMe3 6-chloro-picoli- 2540-47 (solution) Si / Ti n.d. na N / Ti n.d. 44 (EtO) SiMe3 2, 6-dichloropi-2540-49 (solution) Si / Ti n.d. pidina N / Ti n.d. No. of C.E. ? Hf P P..FF .. M MFFRR MEK Example g / g-cat h J / g ° C g / 10 min Sun 32 4500 36.8 153.5 1.2 7.1 (BM) 33 10900 42.6 155.3 1.3 4.4 (solution) 34 14300 36.6 154.2 1.9 7.2 (BM) 35 15500 28.3 152.9 1.6 8.0 (BM) 36 14000 38.3 154.5 1.3 5.3 (BM) 37 10500 32.9 154.5 nd 7.4 (BM) 38 14700 29.6 153.7 3.1 7.4 (BM) 39 10500 27.8 153.8 1.2 7.0 (BM) 40 9300 26.7 154.1 1.0 6.5 (solution) 41 15700 29.7 153.3 1.8 5.7 (solution) 42 9700 28.1 155.0 1.7 5.7 (solution) 43 8300 35.7 155.4 1.0 6.8 (solution) 44 19100 36.1 154.1 4.2 6.9 BM = ball mill grind The objective of Examples 32-44 was to obtain a catalyst with good productivity, while providing a higher molecular weight and a lower crystallinity. Examples 32-44 illustrate the combinations of these donors both by ball milling and by the solution process. It seems that the most promising combinations are the combinations between C donors, D donors, and 2,6-lutidine, 6-chloro-2-picoline. The donor of D and 2, 6-lutidine appeared to cause a slightly higher heat of fusion. Likewise, the solution process seemed less profitable compared to the ball mill process. Examples 45-53: optimization of catalyst formulation with C (type I) and 2,6-lutidine (type I) donor. Probable candidates for catalysts having all the desired properties were selected to optimize all the characteristics in the catalyst and resulting SPO polymer: Example 45: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 4.59 ml (0.0394 mcl) of 2,6-lutidine and 4.02 g were added. of / TiCl4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 46: 30 g of MgCl 2 and 5.25 g of A1C13 were milled in a ball mill (RBM) for 24 hours, then 2.81 g (0.0262 mol) of 2,6-lutidine and 2.02 g were added.

TÍCI4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 47: 30 MgCl 2 and 5.25 g A1C13 were milled in a ball mill (RBM) for 24 hours, and then 1.41 g (0.0131 mol) of 2,6-lutidine and 4.02 g of TiCl 4 were added. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 48: 30 g of MgCl 2 and 5.25 g of AICI 3 were milled in a ball mill (RBM) for 24 hours, and then 0.074 g (0.0069 mol) of 2,6-lutidine and 4.02 g of TiCl 4 were added. The mixture was milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 49: 30 g of MgCl 2 and 5.25 of A1C13 were milled in a ball mill (RMB) for 24 hours, then 1.41 g (0.0131 mol) of 2,6-lutidine and 8.04 g of TiCl 4 were added. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 50: 30 g of MgCl2 / 5.25 g of A1C13 and 0.95 g of donor C were milled in a ball mill (RBM) for 24 hours, then 1.41 g (0.0131 mol) of 2,6-lutidine and 8.04 g were added. of TiCl4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 51: 30 g of MgCl 2, 5.25 g of A1C13 and 0.48 g of donor C were milled in a ball mill (RBM) for 24 hours, then 1.41 g (0.0131 mol) of 2,6-lutidine and 4.02 were added. g of TiCl4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. Example 52: 30 g of MgCl 2, 5.25 g of A1C13 and 0.95 g of donor C were milled in a ball mill (RBM) for 24 hours, then 1.41 g (0.0131 mol) of 2,6-lutidine and 4.02 were added. g of TiCl4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst.

Example 53: 30 g of MgCl 2, 5.25 g of A1C13 and 1.43 g of donor C were milled in a ball mill (RBM) for 24 hours, then 1.43 g (0.0131 mol) of 2,6-lutidine and 4.02 were added. g of TiCl4. The mixture was then milled in a ball mill for an additional 24 hours to provide the procatalyst. These pro-catalysts were used in catalysts for the polymerization of polypropylene in order to produce polymers that had the characteristics established in the following table: TABLE VII No. of Ti% donor 2,6- No. of C.E. ? Hf P.F. ej • de C Lutidina exp. of g / g- J / g ° C (Si / Ti) (N / Ti) Poly. cat h 45 2.41 0 1.86 2540-1 6400 31.8 154.8 46 2.41 0 1.24 2540-71 8800 27.4 154.2 47 2.50 0 0.62 2540-75 12700 27.3 153.4 48 2.54 0 0.32 2540-82 15900 29.5 152.6 49 4.54 0 0.31 2540-80 12600 32.7 154.6 50 4.47 0.118 0.31 2540-89 15100 38.8 154.0 51 2.47 0.118 0.62 2541-6 14300 29.5 153.6 52 2.44 0.23 0.62 2540-91 15500 28.3 152.9 53 2.41 0.35 0.62 2541-8 15000 37.1 153.5 No. of MFR MEK Mn Mw PDI Ejeniplo g / 10 Sun% xlO-3 in 45 1.5 6.8 36 283 7.78 46 1.6 7.2 40 299 7.45 47 1.9 6.9 32 273 8.4 48 3.2 10.1 26 247 9.41 49 1.9 6.6 31 242 7.74 50 2.4 5.5 36 263 7.37 51 2.3 8.0 52 1.6 8.0 32 274 8.48 53 1.8 5.9 Examples 45-53 illustrate the optimization of the donor dosage by locating a point at which the MFR is sufficiently low, but the catalyst productivity is acceptable for polymerization, as well as optimizing the maintenance of improved productivity while obtaining a low heat of fusion. Example 52 appears as the beneficial procatalyst having the optimum recipe, with a relatively high productivity of 15,500 g / g catalyst, relatively low Hf of approximately 28.3 J / g and MFR significantly lower than approximately 1.6 g / 10 min than in the case of the other catalyst formulations. EXAMPLE 54: METHOD FOR THE PREPARATION OF A PREFERRED CATALYST 120 pounds of magnesium magnesium chloride ("MgCl2") and 21 pounds of solid aluminum chloride ("A1C13") were charged to a 250 L vibrating ball mill and mixed I for about 15 minutes. Next, 3.8 pounds of cyclohexylmethyldimethoxysilane were sprayed into the stainless steel vessel. Alternatively, the silane could have been added with the other two components before milling in the ball mill. The mixture was then milled in the ball mill for 16 hours at room temperature. Subsequent to the initial milling in the ball mill, 3.7 pounds of liquid 2,6-glutridine and 16.1 pounds of liquid titanium tetrachloride (TiCl) were added to the mixture. An alternative heterocyclic aromatic amine, such as 4.5 pounds of liquid 6-chloro-2-picoline, may have been substituted. The lutidine was added directly to these components, even though a spray addition of the two liquid components in the existing mixture over a period of about 2 to 3 hours would have been adequate. The five (5) components were then milled in a ball mill for an additional 16 hours. The milling in the wave mill involved steel balls in vibration to shred the component articles, providing heat to the ball mill container; however, the container was maintained at a controlled temperature of about room temperature during grinding in the ball mill.

In the preparation of several FPO polymers, the productivity of the catalyst of the present invention was within a range of about 30 to 55% increase, compared to conventional catalysts. Example 55-62: Pilot Plant Continuous Process Flexible polyolefin polymers were prepared in a large scale continuous pilot plant operation, where monomers, hydrogen and catalyst components were separately and continuously charged to a stirred reactor.

The total monomer feed rate corresponded to a residence time of about 1.8 hours in the reactor. Triethylaluminium ("TA") and external modifier cyclohexylmethyldimethoxysilane ("CMDS") were pumped into the reactor as solutions in heptane at 5% by weight and 0.25% by weight, respectively. The solid catalyst components had a titanium content of approximately 2.2% by weight and was prepared according to Example 54. The solid catalyst component was pumped into the reactor as a 25% by weight mixture in petrolatum. The catalyst components were added at rates directly proportional to the rates of polymer production, and in amounts sufficient to maintain the concentration of polymer solids in the reactor slurry at values typically in the range of about 30 to 50% by weight. The catalyst productivity (pounds of polymer / pounds of solid catalyst) was calculated from the polymer solids removal rate and the rate of solid catalyst component addition. The polymer products were separated from the unreacted, deactivated, stabilized monomers, and formed into pellets, followed by a test in order to determine the polymer characteristics. The following table summarizes the relevant conditions of operation and the results of the physical test of the polymer characteristics. TABLE VIII Example 55 56 57 58 59 60 61 temp. of reactor - 135 135 135 135 135 135 140 Propylene 138 154 136 146 142 147 147 (Ibs / hr) Ethylene - - 1.5 1.1 (Ibs / hr) Hydrogen - 0.028 - 0. 028 0. 026 0. 040 0. 027 (Ibs / hr) Catalyst 0.0045 0.0038 0.0029 0.0026 0.00450.0048 0.0055 solid (Ibs / hr) Al / Ti 162 210 256 364 155 184 161 Molar ratio CMDS / Ti 0.77 0.87 Molar ratio Productivi- 9880 11600 16110 16890 9630 10420 8480 dad (Ibs / hr) Ethylene-% weight - 2.2 2.6? Hf (J / g) 26.6 23.8 17.8 18.2 33.5 36.1 50.4 MFR (g / 10 4.6 13.6 4.9 15.8 7.4 30 4.8 min) Module of 11 20 20 40 tension (kpsi) Effort of 1330 935 983 660 1400 1087 2100 Stress at 311% - psi% of def. 36/23 34/19 31/17 30/17 46/31 45/29 63/45 tension 0/24 hr softening 58 46 41 42 66 57 95 VICAT (° C) Hardness 46 45 38 34 51 50 61 Shore D Example 62 Temp. Reactor. ° 140 Propylene (lbs / hr) 135 Ethylene (lbs / hr) Hydrogen (lbs / hr) 0.04 Solid catalyst 0.0046 (Ibs / hr) molar ratio Al / Ti 191 molar ratio CMDS / Ti 2 Productivity (Ibs / hr) 10090 Ethylene - % in weigh ? Hf (J / g) 53.4 MFR (g / 10 min) 25.9 Stress module 43 (kpsi) Stress strain @ 1720 311% - psi% def. by tension 69/50 0/24 hr softening VICAT 97 (° C) Shore D hardness 62 EXAMPLES 63-71: Preparation Xe various polymers The polymerization of several polymers of FPO, which are not in any way indicative of the broad range of polymers that This invention is encompassed by the use of the ground ball mill catalyst of the present invention. The characteristics of some of these polymers are presented below: TABLE IX Example No. 63 64 65 66 67 68 69 70 Pro-cat. , mg 10 10 10 10 10 10 10 10 Co-catalyst TEA TEA TEA TEA TEA TEA TEA TEA Al / Ti, mol / mol 200 200 200 200 200 200 200 200 200 Modifier CMDS CMDS Modifier / Ti, 1 1 mol / mol H2, psig 0 0 5 5 0 0 0 0 Ethylene, 0 0 0 0 0.27 0 0 0 g / mine) Propylene, mL 660 660 660 660 660 610 460 610 1-Buteno, L 0 0 0 0 0 50 200 0 1-pentene, mL 0 0 0 0 0 0 0 50 EC. g / g cat / h 15300 10400 17500 13100 19600 11000 10600 9400 HF, J / g 32.2 57.2 34.8 62.7 25.6 21.8 13.8 21.9 pf, ° C 153.7 156.4 155.9 158.3 146.7 137.3 109.7 141.0 MFR, g / 10 min 2.16 0.3 12.0 21.9 2.24 4.1 6.3 4.4 Example No. 71 Pro-cat., Mg 10 Co-catalyst TEA Al / Ti, mol / mol 200 Modifier Modifier / Ti, mol / mol H2 / psig 0 Ethylene, g / mine 0 Propylene, mL 460 1- butene, mL 0 1-pentene, L 200 CE g / g cat / h 8000 H.F., J / g 6.6 p.f, ° C 126.9 MFR, g / 10 min 10.2 One liter autoclave batch polymerization, 60 ° C, for one hour, a) The ethylene was fed continuously during a reaction time of one hour. EXAMPLES 72-83: Preparation of several copolymers Each of the FPO polymer products in Examples 72 to 83 presented in the following Table were prepared in general by the process described in the preceding Examples. Initially, a clean one-liter stainless steel autoclave reactor equipped with a nitrogen stirrer was purged in order to remove impurities. Then triethylaluminum was added to the reactor in an amount sufficient to provide an Al: Ti atomic ratio of approximately 200: 1 followed then by the addition of a mineral oil suspension containing approximately 10 mg of solid procatalyst according to that described herein. The mixed monomer charges, including 660 ml of liquid volume, were subsequently introduced into the reactor under an effective pressure and under thermal control in order to maintain a reaction temperature of 60 ° C for 1 hour. Donors "C" and "D" were the donors previously employed. After one hour, the unreacted monomer was removed by ventilation and the polymer product was recovered using conventional techniques. The characteristics of some of these FPO polymer products are presented below: TABLE X Example No. 72 73 74 75 76 77 78 Propylene, L 640 610 560 460 640 610 560 1-butene, mL 20 50 100 200 0 0 0 1-pentene, mL 0 0 0 0 20 50 100 1-octene, mL 0 0 0 0 0 0 0 EC. g / g-cat / h 13200 11000 10600 10700 13000 10400 10300% by weight C4-8a 1.8 5.9 11.4 28.7 3.5 4.2 8.9 nc3 69.7 21.8 11.3 4.6 65.7 39.8 19.5 HF, J / g 28.3 25.4 18.3 7.4 23.9 18.4 16.9 pf, ° C 149.0 136.6 131.6 110.1 146.5 139.9 132.5 Tg, ° C -1.5 -3.0 -5.1 -9.8 -2.1 -3.4 -3.9 MFR, g / 10 min 3.2 4.0 2.8 6.6 3.8 5.0 6.8 Density, 0.873 0.865 0.869 0.864 0.871 0.868 0.866 g / cm3 MEK sol- 8.1 6.8 5.2 4.6 8.0 7.2 8.2 Example No. 79 80 81 82 83 Propylene, mL 460 640 610 560 460 1-Butene, mL 0 0 0 0 0 1-Pentene, mL 200 0 0 0 0 1-Octene, mL 0 20 50 100 200 C.E. g / g-cat / h 8000 12600 12200 12300 11000 Wt% C4-8a 26.4 1.2 3.0 8.5 13.8 nc3 8.0 186.2 84.7 32.7 17.4 nc4-8 1.6 1.1 HF, J / g 10.4 26.2 24.0 19.9 14.3 pf, ° C 130.0 150.5 147.2 144.2 144.4 Tg, -6.8 -2.8 -3.0 -5.6 -11.9 MFR, g / 10 min 10.2 2.9 3.8 5.3 8.9 Density, g / cm3 0.856 0.87 0.874 0.866 0.863 MEK sol% 6.1 7.6 8.1 7.4 7.1 Table X Autoclave batch polymerization of a liter. Catalyst 10 mg; TEA / Ti 200; Total charge of liquid monomer: 60 ml; 60 ° C; 1 hour. a) percentage by weight of incorporation of comonomer. b) Average sequence length in number for propylene units. c) Average sequence length in number for comonomero units. EXAMPLES 84-99: Polymers of ethylene comonomers The following examples illustrate various types of polymers of FPO produced in accordance with the present invention by using relatively high amounts of ethylene and at least one other comonomer as a monomeric raw material. Values in the column "Entalpia" in the various graphs appear as a value of positive energy and a value of negative energy, since the value to the left is the heat of fusion and the value more to the right is the heat of crystallinity. It will be understood that all of the FPO polymers discussed herein may be employed in any of the various mixtures, yarns, products, and methods of the invention. HIGHEST ETHYLENE FPO PRODUCTS TABLE XI Example No. 84 85 86 87 Melt Flow 5.3 5 5.8 5.7 LOT g / lOmin @ 230 ° C Content of 2.2 3.8 5.7 7.3 Ethylene,% by weight DSC Mp / fp (° C) 147.2 / 93.8 144.5 / 92.2 136.6 / 88.1 132.0 / 85.3 Enthalpy (J / g) 17.5 / 21.6 14 / -19.7 14.1 / -13.1 11.5 / -12.6 Density, g / cm3 - 0.8683 - DSC Tg, ° C -6.7 -9.3 -16.2 MEK Solubles,% 9.03 9.42 7.89 7.67 by weight Ether solution 31.5 35.9 41.5 Dietary 45.2, weight Solution of 39.5 45.6 51.8 62.6 Hexane% by weight Shore hardness, 377- 337- 28/85 25/81 Scales A / D Shrinkage test : Length (in / in) - 0.0363 - Width (in / in) 0.0016 - Molecular weight measurements: GPC Mn (xlOOO) 27 26 27 27 Mw (xlOOO) 219 221 222 224 Mz (1000) 792 836 873 889 PDI 8.1 8.5 8.22 8.3 I.V. of polymer 1.48 1.96 1.24 1.63 clean, dl / g I.V. of fraction 0.826 0.87 0.61 0.82 soluble in ether dl / g Film emptied 1 thousand. in. by 6 inches: Measured thickness 1.6-2.1 1.6-1.7 (thousandths of an inch) Machine direction: Effort @ 733 NY yield point (psi) Effort to 1761 1468 break (psi) Deformation @ 549 568 break (%) Cross Direction: Effort @ Item 539 401 transferor (psi) Effort @ NB (989) NB (728) break (psi) Deformation to NB (> 700) NB (> 700) break (%) Voltage module 5.1 3.8 2.6 2.2 (kpsi) Deformation of NY NY NY NY tension to yield point (%) NY NY NY deformation tension to yield point (psi) NB deformation NB NB NB tension to break (%) NB deformation NB NB NB tension to break (psi) Deformation of 936 844 699 626 tension to deformation max. (311%) (psi) def. by tension 31/16 30/17 30/15 29/15 after extension of 300% (%) (0 / 24h) Temperature of 40 40 40 39 softening of VITAC (° C) Proportion of 1.502 1.52 1.55 1.566 swelling in fusion (210 ° C / 5 kg) Viscosity of 9675 8823 8312 8796 zero cut (Pa-s) Crossover module 22044 22277 22461 22800 (Pa) PDI = 100,000 / Gc 4.54 4.49 4.45 4.38 Frequency of 21.09 23.2 25.6 25 junction, rad / s Example No. 88 89 90 91 Melt flow 5.5 5.3 4.7 5 LOT g / 10 min @ 230 ° C Content of 9.7 9.6 14.8 17 ethylene% by weight DSC Mp / Fp (° C) 127.6 / 84.4 127.9 / 84.5 123.3 / 80.9 118.9 / 77.6 Enthalpy (J / g) 7.9 / -10.6 8.1 / -9.6 5.1 / -1.1 4 / -4.4 Density, g / cm3 - 0.8597 0.8446 DSC Tg, ° C - -17.7 -24.1 -26.1 MEK soluble, 7.07 6.77 6.8 7.2 % by weight ether solution 47 45.5 48.2 47.4 diethyl, weight solution 70.5 68.6 77.3 81.6 hexane% by weight Shore hardness, 20/75 20/76 15/67 12/61 Scales A / D Shrinkage test: Length (in / in.) - 0.0669 0.0838 Width (in / in) - -0.0078 -0.0065 Molecular mass width: GPC Mn (xlOO) 27 27 27 28 Mw (xlOOO) 222 226 218 207 M-z (xlOOO) 905 916 968 850 1 PDI 8.22 8.4 8.1 7.4 I.V. of polymer 1.25 1.67 1.37 1.23 clean, dl / g I.V. of fraction 0.87 0.79 0.9 0.91 Soluble ether, dl / g Film emptied 1 mole. in. by 6 inches: Measured thickness - 1.3 1.7-1 (thousandths of an inch) Machine direction: Effort @ point - NY NY yield (psi) Effort @ rom- - 1052 870 pepper (psi) Deformation @ - 415 656 break ( %) Transverse direction: Effort @ point - NY NY surrender (psi) Effort @ rom- - NB (516) NB (516) pepper (psi) Deformation @ - NB (> 700) NB (> 700) break (psi) ) (%) Stress module 1.6 1.6 1.2 0.87 (kpsi) Deformation of NY NY NY NY stress to transferor point (%) Deformation of NY NY NY NY tension to transferor point (psi) Deformation of NB NB NB NB voltage to breakage (%) Deformation of NB NB NB NB tension to rom-Pepper (psi) Deformation of 550 547 359 270 strain to max (311%) (psi) Temp. 9/13 29/13 35/13 38/13 after extension of 300% (%) (0 / 24h) Temperature of 43 43 23 23 softening of VITAC (° C) Proportion of 1.524 1.536 1.486 1.49 melting inflation (210 ° C / 5 kg) Viscosity of 8456 8624 8713 7945 Zero cutting (Pa-s) Crossover module 4509 24638 29304 31881 (Pa), PDI = 100,000 / Gc 4.08 4.06 3.41 3.14 Frequency of 27.75 27.99 34.04 40.21 crossing, rad / s Example No. 92 93 Melt flow LOT g / 10 min 5.5 5.2 @ 230 ° C Ethylene content,% by weight 15 16.6 DSC MP / FP (° C) 120.5 / 77.7 114.9 / 73.5 Enthalpy (J / g) 5.2 / -6.8 4.5 / -4.9 Density, g / cm3 DSC Tg, ° C MEK soluble,% by weight - Diethyl ether solution, weight Hexane solution,% by weight 80.6 82.3 Shore hardness D 15/66 12/62 A / D Scales Shrinkage test: Length (in / in) Width (in / in) Width of molecular mass: GPC Mn (xlOOO) 32 27 Mw (xlOOO) 219 203 Mz (xlOOO) 857 821 PDI 6. 8 7. 5 I.V. of clean polymer, dl / g I.V. of soluble fraction of ether, dl / g Film emptied 1 thousand. by 6 inches Thickness measured (thousandths of an inch) Machine direction: Effort @ yield point (psi) Effort @ break (psi) Deformation @ break (%) Cross direction: Effort @ yield point (psi) Effort @ break (psi) Deformation @ breaking (%) Voltage module (kpsi) 1.11 0.88 (kpsi) Deformation of tension to point NY NY cedant (%) Deformation of tension to point NY NY Cement (psi) Deformation of tension at break-NB NB (%) Deformation of tension at break- NB NB mieno (psi) Deformation of tension to deform- 354 291 max. (311%) (psi) def. by tension after 36/14 36/13 300% (%) (0 / 24h) Temp. VITAC softening 23 23 (° C) Melting inflation ratio 1.498 1.46 (210 ° C / 5 kg) Zero cutting viscosity (Pa-s) 7984 7740 Crossing module (Pa) 29641 30252 PDI = 100,000 / Gc 3.37 3.31 Cross frequency, rad / s 37.17 39.79 TOP ETHYLENE FPO PRODUCTS WITH ADDED DONOR TABLE XII Example No. 94 95 96 97 Melt flow, 5.5 8.4 4 4.8 LOT g / 10 min at 230 ° C Content of 9.7 6.2 14.7 12.3 ethylene% by weight DSC Mp / Fp (° C) 132.2 / 86.6 136.3 / 93/1 121.9 / 81.1 126 / 84.6 Enthalpy (J / g) 27.3 / -30.7 23 / -24.7 14.6 / -19.4 17.8 / 20.3 Density, g / cm3 - - MEK soluble, 4.96 6.31 3.4 % by weight Ether solution 2.3 27.7 29.5 Diethyl,% by weight Shrink test: Length (in / in) - 0.0125 0.0181 Width (in / in) 0.0137 0.0143 I.V. of Polymer 1.9 1.3 1.65 clean, dl / g I.V. of fraction 0.57 0.37 0.8 Soluble in ether, dl / g Film emptied 1 mil in. by 6 inches: Measured thickness 1.4-1.5 1.4-1.7 1.4-1.5 (thousandths of an inch) Direction of the machine: Effort @ point 1047 959 1356 assignor (psi) Effort @ break-up 2760 2043 552 ment (psi) Deformation @ 538 653 break (%) Cross direction Effort @ point 733 774 566 assignor (psi) ) Effort @ rom- NB (1500) NB (1510) NB (1190) pepper (psi) Deformation @ NB NB NB break (%) Example No. 98 99 Melt flow LOT g / 10 5.6 6.9 min. @ 230 ° C Ethylene content% in 9.8 9.8 weight DSC MP / FP (° C) 130.8 / 88.8 130.8 / 87.5 Enthalpia (J / g) 21 / -18.9 29.4 / -30.7 Density, g / cm3 0.874 0.878 MEK Soluble,% by Weight Soluble Diethyl Ether Solution,% by Weight Shrink Test: Length (in / in) 0.0131 0.0125 Width (in / in) 0.0133 0.0136 I.V. of clean polymer dl / g I.V. of soluble fraction of ether, dl / g Film emptied 1 mil in. by 6 inches: Thickness measured (thousandths of an inch) Machine direction: Effort @ yield point (psi) Effort @ break (psi) Deformity @ break (%) Cross direction: Effort @ yield point (psi) Effort @ break ( psi) Deformation @ break (%) EXAMPLES 100-104: Mixtures for non-woven applications Various polymer blends were prepared which are useful in products, fabrics, or compounds according to the present invention. All of the commercially available polymers discussed in these examples below are available commercially from Huntsman Polymers Corporation of 2502 S. Grandview Avenue, Odessa, TX. The preparation of these useful mixtures is described below. Example 100 was prepared by mixing 28 pounds of W209, produced in accordance with Example 88 with a copolymer containing 10% ethylene, with 72 pounds RT 2780. Example 101 was prepared by mixing 15 pounds of E201, an alloy polypropylene copolymer having 2% by weight of ethylene, with 85 pounds of E-21. Example 102 was prepared by mixing 10 pounds of propylene homopolymer W110 cor. 90 pounds of RT2780. Example 103 was prepared by mixing 100 pounds of W209 with 90 pounds of E-21. Example 104 was prepared by mixing 65 pounds of RT2780 with 35 pounds of W209. EXAMPLES 105-108: Preferred Mixtures for Use as Adhesives Various polymer blends were prepared for use as adhesives and in composite nonwovens including adhesives according to the invention. All commercially available polymers discussed in these examples below are available commercially from Huntsman Polymers Corporation for 2502 s. Grandview Avenue, Odessa, TX. Table XIII: Physical properties of the mixture APAO / FPO PROPERTIES Ex. 105: Ex. 106: Ex. 107: Ex. 108: PHYSICAL RT 2780 + RT2780 + E21 + E21 + AR #: 13868 28% W209 10% W110 15% W201 12% W209 Module of 2.5 2.7 15.2 14 tension (kpsi) Deformation 32 15 10 11 by tension to yield point (%) Effort of 99 72 439 420 tension to yield point (psi) Deformation by 258 40 42 30 tension to break ( %) stress 101 NA 312 363 stress at breaking (psi) shore hardness 69/16 70/15 96/35 95/32 (A / D) Viscosity in 115,000 12,500 16,500 17,500 fusion (centipoise) Penetration 16 13 5 needle (dmm) Open time 10 30 90 50 (sec) Softening point 275 239 267 223 ring and ball (-) The polymer blends presented in the table above have a suitably high adhesion capacity in accordance with the measured open time and ring softening point and ball. EXAMPLES 109-119: Ethylene copolymer of LMW / propylene mixed with propylene of HMW An ethylene copolymer of APAO of LMW / propylene was mixed with a propylene of APAO of HMW, of low crystallinity (designation FPD) to form certain mixtures of polymers of the present invention. REXTAC ® 2385 is a LMW APAO of about 7.5% by weight of ethylene and 92.5% by weight of propylene. The HMW APAO of FPD-100 has a heat of fusion of approximately 23-27 J / g. The HMW APAO of FPD-400 has a heat of fusion of approximately 17-20 J / g. The HMW APAO of FPD-2300 has a heat of fusion of approximately 33-37 J / g. The heats of fusion are given as ranges, because they vary slightly according to the denomination method. The characteristics of a LMW APAO polymer (example 109) and various polymer blends of LMW APAO and HMW APAO of the present invention (example 110-119) are presented below in Table XIV. The mixtures are useful in the compounds and adhesive compositions of the invention. TABLE XIV: Physical and mechanical properties of high viscosity molten ethylene / propylene APAOs MV Type NP R &; B SP OT Mod. Tens. polymer (cPs) (dmm) ° C (° F) (sec) Mpa (psi) (% by weight) mPa x s 100% REXTAC® 8,500 20 141 (285) 20 6.9 (1000) 2385 97.5% 2385 / 10,800 21 141 (286) 10 (1000) 2. 5% FPD-400 92.5% 2385 / 21,000 18 142 (288) 10 7.6 (1100) 7.5% FPD-400 85% 2385 / 50,800 17 149 (300) 10 (1600) % FPD-400 80% 2385 / 81.00 17 149 (301) 10 (1600) % FPD-400 85% 2385 / 51,000 17 149 (300) 10 11.0 (1600) % FPD-100 80% 2385 / 81,000 17 149 (301) 10 11.0 (1600) % FPD-100 97.5% 2385 / 12,400 28 138 (280) 10 (1780) 2.5% FPD-2300 90% 2385 / 37,300 18 151 (304) 10 (1700) % FPD-2300 80% 2385 / 165,000 14 158 (316) 0 23.4 (3400) 20% FPD-2300 65% 2385 / 205,000 10 158 (316) 0 15.2 (2200) 35% FPD-400 Def Type. tens. @ Tg (° C) H.F. pf Breaking polymer (%) (° C) (° C) (% by weight) 100% REXTAC® 55 -29 < 5 139 2385 97.5% 2385/56 -20 6.8 140.4 2. 5% FPD-400 92.5% 2385/45 -20 142.4 7.5% FPD-400 85% 2385/150 -20 12.1 140.3 % FPD-400 80% 2385/125 -19 14.3 140.1 % FPD-400 85% 2385/150 -20 12 141.2 % FPD-100 80% 2385/125 -20 14 136.5 % FPD-100 97.5% 2385/60 5.9 140.6 2.5% FPD-2300 90% 2385/87 11.2 145.6 % FPD-2300 80% 2385/120 -19 19 152.4 % FPD-2300 65% 2385/265 -18 14 145 35% FPD-400 EXAMPLES 120-127: 1-butene from LMW / propylene mixed with propylene from HMW A 1-butene copolymer from APAO from LMW / propylene was mixed with a HMW APAO propylene of low crystallinity (designation of FPD) to form certain polymer blends of the present invention. REXTAC ® 2780 is a LMW APAO of approximately 35% by weight of 1-butene and 75% by weight of propylene copolymer. The FPD- 100, -400, and -2300 have heats of fusion in accordance with what is stated above. The characteristics of a 1-butene copolymer of LMW / propylene APAO (example 120) and various mixtures of polymers of LMW APAO and HMW APAO of the invention (example 121-127) are presented in the following Table. These mixtures are useful in the compounds and additive compositions of the present invention. TABLE XV: Physical and mechanical properties of 1-butene / propylene high melt viscosity APAOs Type of MV NP R & _ SP OT Mod. Tens, polymer (cPs) (dmm) ° C (° F) (sec) Mpa (psi) (% by weight) mPa x s 100% REXTAC® 8,000 25 107 (225) 240 3.5 (500) 2780 97.5% 2780 / 11,200 33 111 (232) 210 (1200) 2.5% FPD-400 92.5% 2780 / 16,000 32 123 (254) 160 6.2 (900) 7. 5% FPD-400 90% 2780 / 28,500 25 139 (282) 140 6.9 (1000) % FPD-400 80% 2780 / 70,000 17 144 (291) 100 (1700) % FPD-400 90% 2780 / 37,000 23 154 (310) 60 (1900; 10% FPD-2300 85% 2780 / 70,000 17 144 (291) 120 11.7 (1700) 150% FPD-2300 80% 2780 / 145,000 15 158 (316) 20 17.2 (2500) 20% FPD-2300 Def Type. tens. @ Tg (° C) H.F p.f Polymer breakage (%) (° C) (° C) (% by weight) 100% REXTAC® 130 -23 < 2 83 2780 97.5% 2780/106 -19 < 2 89.8 2.5% FPD-4C0 92.5% 2780/81 -19 < 2 98, 7.5% FPD-400 146.9 90% 2780/315 -18 4.3 104.5, 10% FPD-400 146.2 80% 2780 / N.B. -17 6.3 101.4 20% FPD-400 90% 2780/142 - 2. 2 152 i 10% FPD-2300 85% 2780 / N.B. -17 6.3 153 15% FPD-2300 80% 2780 / N.B. -16 8 153.3 20% FPD-2300 N.B. = Absence of rupture at an elongation of 311% EXAMPLES 128-34: 1-butene of LMW / propylene mixed with propylene of HMW A copolymer of 1-butene of APAO of LMW / propylene was mixed with a propylene of APAO of HMW of low crystallinity (designation FPD) to form certain polymer blends of the present invention. The E21 polymer is a LMW APAO of about 65% by weight of 1-butene and 35% by weight of propylene. The FPD-100, -400, and -2300 have heats of fusion in accordance with the comments above. The characteristics of a 1-butene copolymer of LMW / propylene APAO (Example 128) and various mixtures of LMW APAO polymer and HMW APAO of the present invention (Example 129-134) are set forth in Table XVI below . These mixtures are useful in the compounds and adhesive compositions of the present invention. Table XVI: physical and mechanical properties of 1-butene / propylene high melt viscosity APAOs MV Type NP R & B SP OT Mod. Tens. polymer (cPs) (dmm) ° C (° F) (sec) -Mpa (psi) (% by weight) mPa x 100% E21 LMW 3,750 7 90 (195) 300 82.7 (12,000) APAO 95% E21 / 11,100 9 113 (235¡ 240 83.4 (12,100) % FPD-400 90% E21 / 15, 500 9 123 (253) 180 123 (17,900) % FPD-400 85% E21 / 22, 500 8 135 (275) 150 84.1 (12,200) % FPD-400 80% E21 / 37,500 8 152 (305) 60 93.1 (13,500) % FPD-100 85% E21 / 53,500 8 156 (313) 60 110 (16,000) 15% FPD-2300 80% E21 / 103,000 8,157 (315) 40,138 (20,000) % FPD-2300 Def Type tens. @ Tg (° C) H.F. p.f Breaking polymer (%) (° C) (° C) (% by weight) 100% E21 / LMW 20 -28 < 2 APAO 95% E21 / 305 -25 9 76 5% FPD-400 90% E21 271 -25 27 72.2 10% FPD-400 85% E21 N.B. -25 13 70.9 15% FPD-400 80% E21 N.B. -25 70.9, 20% FPD-100 150.5 85% E21 / N.B. -25 21 71.5, 15% FPD-2300 153.2 80% E21 / N.B. -23 23 71.4, 20% FPD-2300 153.4 N.B. = absence of breaking at an elongation of 311% EXAMPLE 135: LMW Ethylene / Propylene Blended with HMW Propylene A copolymer of ethylene and LMW / propylene APAO was mixed with various amounts of propylene of low crystallinity HMW APAO (designation FPD) to form certain polymer blends of the present invention. REXTAC ® 2585, is an LMW APAO of approximately 15% by weight of ethylene and 85% by weight of propylene. The APAO portion of LMW of REXTAC® 2585 was mixed with various amounts of polymers of APAO from HMW. The FPD-100-400, and 2300 have heats and fusion in accordance with the above. The characteristics of their mixtures were examined, and even though they generally have a strain to the minor breakage, they were generally found to be softer, had a higher NP, and had a longer open time than the corresponding amount of APAO of HMW of examples 109-119. These mixtures are useful in the compounds and compositions of the invention. Although preferred embodiments of the present invention were described in the foregoing description, it will be understood that the invention is not limited to the specific embodiments presented herein but that a person with certain knowledge in the art can modify said modalities. It will be understood that the materials employed and the chemical details may be slightly different or modified from the descriptions without leaving either the methods or the compositions presented in this invention.

Claims (9)

1. CLAIMS 1. A method for preparing a fiber, strand or yarn, comprising: preparing a polymer blend by combining a predominantly atactic flexible polyolefin polymer having a high weight average molecular weight of at least about 100, 300 and a heat of fusion of about 0.4 J / g to 75 J / g with an isotactic polypropylene polymer; and forming the polymer blend, into a fiber, strand or yarn, wherein the flexible polymer is present in an amount sufficient to increase the elasticity of the fiber, strand or yarn to inhibit substantial breakage thereof. The method of claim 1, wherein the flexible polyolefin polymer is prepared by the polymerization of propylene with at least one second monomer comprising a C2-C20 polyalphaolefin. 3. The method of claim 2, wherein the second moi -omer is selected to comprise ethylene. The method of claim 2, wherein the second monomer is provided in the polymer blend in an amount of about 1.5 to 20% by weight of the weight of the flexible polyolefin polymer. The method of claim 3, wherein the second monomer is provided in the polymer blend in an amount of about 2 to 12% by weight of the weight of flexible polyolefin polymer. The method of claim 1, wherein the isotactic polypropylene polymer is prepared by the polymerization of propylene with at least one second monomer comprising a polyalphaolefin C; -C2o. The method of claim 6, wherein the second monomer is selected to comprise ethylene. The method of claim 6, wherein the second monomer is provided in the polymer blend in an amount of about 1.5 to 20% by weight of the weight of the isotactic polypropylene polymer. The method of claim 1, wherein at least one of the flexible polyolefin polymer or the isotactic polypropylene polymer is a propylene homopolymer. The method of claim 1, wherein the flexible polyolefin polymer is provided in an amount of about 3 to 80% by weight of the weight of the polymer blend. The method of claim 1, wherein the polymer blend has an elongation at break between 300 and 669%. The method of claim 1, wherein the fibers, strands or yarns are formed by spinning, meltblowing, melt spraying, or carding. The method of claim 1, further comprising the configuration of the fiber, strand, or yarn in a non-woven product. The method of claim 13, wherein the nonwoven product is selected to comprise at least one fabric, film, foam or laminated structure. 15. The method of claim 15, wherein the fibers, strands or yarns are formed in a repeating pattern. 16. A fiber, strand, or yarn comprising a polymer blend of: a predominantly atactic flexible polyolefin polymer having a high average molecular weight of about 100,000, a melt flow rate of between about 0.3 g / 10 min and 30 g / 10 min at a temperature of 230 ° C, a polydispersity index of less than about 10, and a heat of fusion of about 0.4 J / g to 75 J / g; and an isotactic polypropylene polymer. 17. A non-woven product comprising the fiber, strand or thread of claim 16. 18. The non-woven product of claim 17, wherein the fibers are arranged in a repeating pattern. The fiber, strand or yarn of claim 16, wherein at least one of the flexible polyolefin polymer or isotactic polypropylene polymer is a propylene homopolymer. . The fiber, strand, or yarn of claim 16, wherein the flexible polyolefin polymer comprises propylene polymerized with at least one second monomer comprising a C2-C20 polyalphaolefin. . A composite article comprising a plurality of the fibers of claim 16 in contact with an adhesive comprising a blend of adhesive polymers of: a predominantly atactic flexible polyolefin polymer having a high weight average molecular weight of about 100,000 and a heat of fusion of approximately 0.4 J / g to 75 J / g; and an atactic polyolefin polymer having a number average low molecular weight of less than about 25,000 and a heat of fusion of about 0.1 to 20 J / g, where the high molecular weight polymer and the low molecular weight polymer are sufficiently miscible to provide a single glass transition temperature and an open time to the polymer blend, and the low molecular weight polymer is present in an amount sufficient to provide a melt viscosity greater than about 8,000 cPs at room temperature and a crystallinity below about 28 J / g to the adhesive polymer mixture. . A composite article comprising: fibers, strands, or yarn arranged in a nonwoven pattern; and an adhesive component comprising a predominantly atactic flexible polyolefin polymer having a high weight average molecular weight of at least about 100,000 and a heat of fusion of about 0.4 J / g to 75 J / g and an atactic polyolefin polymer having a high molecular weight. average molecular weight low in number of less than about 25,000 and a heat of fusion of about 0.1 J / g to 20 J / g, where the high molecular weight polymer and the low molecular weight polymer are sufficiently miscible to provide a transition temperature to single glass and an open time to the polymer blend, and the low molecular weight polymer is present in an amount sufficient to provide a melt viscosity greater than about 8,000 cPs at room temperature and a crystallinity of less than about 28 J / ga the polymer mixture. A polymer blend comprising: a predominantly atactic flexible polyolefin polymer including propylene copolymerized with ethylene present in an amount of about 1 to 40% by weight of the polymer, wherein the polymer has a high average weight-average molecular weight of at least about 100,000 and a heat of fusion of approximately 0.4 J / g to 75 J / g; and an atactic polyolefin polymer having an average molecular weight low in number of less than about 25,000 and a heat of fusion of about 0.1 to 20 J / g, where the high molecular weight polymer and the low molecular weight polymer are sufficiently miscible to provide a single glass transition temperature and an open time to the polymer blend, and the low molecular weight polymer is present in an amount sufficient to provide a melt viscosity greater than about 8,000 cPs at room temperature and a crystallinity below about 28 J / ga the polymer mixture. The polymer blend of claim 23, wherein the ethylene comprises from about 1.5 to 20% by weight of the flexible polymer. The polymer blend of claim 24, wherein the ethylene comprises from about 2 to 12% by weight of the flexible polymer. The polymer blend of claim 23, wherein the atactic polyolefin polymer comprises propylene polymerized with at least one second monomer comprising a C2-C20 polyalphaolefin. The polymer blend of claim 26, wherein the second monomer comprises from about 2 to 70% by weight of the atactic polyolefin polymer. An adhesive comprising the polymer mixture of the reiyindication 23.