TW200900545A - Colorfast fabrics and garments of olefin block compositions - Google Patents

Abstract

Dyed fabric compositions have now been discovered that often have a balanced combination of desirable properties. The dyed fabric comprises one or more elastic fibers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent. Often the fabrics are characterized by a color change of greater than or equal to about 3. 0 according to AATCC evaluation after a first wash by AATCC61-2003-2A.

Description

200900545 IX. INSTRUCTIONS: The reference material for the relevant application is hereby incorporated by reference for the purpose of the U.S. Patent Application No. 60/885,202 (Application of January 16, 2007). . 5 [Brief of the Invention] Field of the Invention 10 The present invention relates to a dyed fabric that does not fade. BACKGROUND AND SUMMARY OF THE INVENTION Various materials have been used to make dyed fabrics for use, for example, in clothing. It is generally desirable for such fabrics to have a combination of properties comprising one or more of the following: dimensional stability, heat set properties, in one or two size systems 15

20 Ability to stretch, chemical resistance, heat and friction, reduction, etc. In addition, it is generally also important that such (four) color fabrics can maintain a longer color (for example, a dye) and more when the fabric is received without a more or less of the foregoing properties. For example, when knit fabrics, the added disadvantages (e.g., fiber breakage) are sometimes desirable. [When the content of the 1st, 1 ^ fabric has been broken, it is generally included to make the color more ice and wash the color to make the color. The fabrics of such compositions can also be included in the fabric of the coffee which is not faded. The knit fabric of the present invention comprises a knitted or woven fabric of partial fibers. These are included to + 〇 ‘ such as microfiber condensed vinegar. Elastomeric fiber - 3 to 1 ethylene block polymer and at least - cross-linking reaction production 5 200900545. The fibers are characterized by a cross-linking amount of the desired properties of the fabric. The vinylidene 1-stage polymer is generally (A) an ethylene/α-olefin heteropolymer, wherein the ethylene/α-olefin heteropolymer has one or more of the following characteristics: 5 〇) greater than 〇 and up to about 1. The average block index of 〇, and the molecular weight distribution greater than about 丨3, Mw/Mn; or (2) one fraction of the fraction eluted between 4 ° C and 130 ° C when TREF is used, characteristic Here, the fraction has a block index of at least 〇5 and up to about 1; or 10 (3) Mw/Mn of about 丨7 to about 3.5, at least one melting point (Tm, in terms of C), And density (d 'in grams per cubic centimeter), where the values of Tm and d correspond to the relationship:

Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or (4) about 1.7 to about 3.52 MW/Mn ' and characterized by a heat of fusion (Δ!!, 15 J/g), and The Δ amount (ΛΤ, °C) defined by the temperature difference between the highest DSC peak and the highest CRYSTAF peak, wherein the values of ΛΤ and ΛΗ have the following relationship: ΔΤ for ΔΗ greater than 0 and up to 130 J/g; -0.1299(ΔΗ)+62.81 » 20 For ΛΗ greater than 130 J/g, ΔTgASt:, where CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer is identifiable CRTSTAF peak, CRYSTAF temperature is 30 ° C; or (5) measured by ethylene/α-olefin heteropolymer compression molding film at 6 200900545 300% strain and 1 cycle of elastic recovery (Re, %), and Having a density (d, g/cm 3 ), wherein when the ethylene/α-olefin heteropolymer has substantially no cross-linking phase, the values of Re and d satisfy the following relationship: Re >1481-1629(d); Or 5 (6) molecular fractions eluted between 40 ° C and 130 ° C using TREF fractionation, characterized in that the fractions are comparable to those eluted at the same temperature. The ethylene heteropolymer copolymer grader has a molar comonomer content of at least 5%, wherein the comparable random ethylene heteropolymer has the same comonomer and has an ethylene/α-olefin heteropolymer. 10% of the melting index, density and molar commonomer content (based on the entire polymer); (7) storage modulus at 25 ° C, G, (25 ° C), and 10 (stored modulus at TC, G' (100 ° C), wherein the ratio of G' (25 ° C) to G' (100 ° C) is in the range of about 1:1 to about 9:1. (1) to (Ό) an ethylene/α-olefin heteropolymer characterized by 15 ethylene/α-olefin heteropolymers before any significant crosslinking (ie, before 'crosslinking). Ethylene/α used in the present invention - Olefin heteropolymers are generally crosslinked to the extent that the desired properties are obtained. The use of features (1) to (7) measured prior to crosslinking is not intended to imply that the heteropolymers need not be crosslinked - only this feature is Crosslinking of heterogeneous copolymers. Crosslinking may or may not alter each of these properties, depending on the particular polymer and degree of crosslinking. The colored fabric may generally be characterized by a color change of greater than or equal to about 3 Å as assessed by AATCC after the first cleaning by AATCC 61-2003-2. The dyed fabric of the present invention may generally be characterized by a spectrophotometer. A dyed color intensity greater than or equal to about 600. 200900545 Brief Description of the Drawings Figure 1 shows the polymer of the present invention (indicated by 羡) when compared to a conventional random copolymer (represented by a circle) and a Zieglereta copolymer (expressed in %) The relationship between melting point/density. Figure 2 shows a plot of Δ DSC-CRYSTAF for various polymers as a function of DSC melting: ^. The diamonds represent random ethylene/octene copolymers; the moment triangles represent polymers Examples 5-9; and the circles represent polymer examples 10-19. The symbol Τ indicates the polymer comparative example ·*·ρ* 〇ίο 帛3 off 7^ density is expressed from the heterogeneous copolymer of the present invention (in the form of a rectangle and a circle) and the conventional U(1) triangle, which is a variety of AFs 顺ιτγ9 | The effect of the elastic recovery of the unoriented film produced by the mouth (available from The Dow Chemical Company). (4) An ethylene/tau-diene copolymer of the invention of the table; and a circle represents the ethylene/octene copolymer of the invention. 15 帛 4 is a polymer of Example 5 (represented by a circle) and a comparative polymer Ε* and F* (indicated by the TREF) of the TREF graded ethylene/i-simple hydrone fraction The olefin content is plotted against the sizing temperature of this fraction. The diamond represents a conventional random ethylene/octarene copolymer. Figure 5 is a polymer of Example 5 (curve enthalpy) and polymer Comparative Example 20 F* (curve 2) TREF graded ethylene/1-octene copolymer fraction octene content TREF of this fraction Drawing of the elution temperature. The rectangle represents the comparative example F*; and the triangle represents the embodiment 5. Figure 6 is a comparison of the ethylene/1-octene copolymer (curve 2) and the propylene/ethylene copolymer (curve 3) and the different amounts of the chain shuttling agent. The second invention of the invention 8 200900545 ene / 1- The octene block copolymer (curve 1) is a plot of the logarithm of the storage modulus as a function of temperature. Figure 7 shows a plot of TMA (1 mm) versus flexural modulus for certain inventive polymers (indicated by diamonds) when compared to certain known polymers. Triangle 5 represents various Dow VERSIFY® polymers (available from The Dow Chemical Company); circles represent various random ethylene/styrene copolymers; and rectangles represent various Dow AFFINITY® polymers (available from The Dow Chemical Company) ). Figure 8 shows a photograph of a laboratory dyeing machine. Figure 9 shows the dyeing and reduction cleaning methods. [Embodiment] DETAILED DESCRIPTION OF THE INVENTION General Definition "Fiber" means a material in which the ratio of length to diameter is greater than about 10. Fibers are typically classified according to their diameter. Filament fibers are generally defined as 15 individual fiber diameters having greater than about 15 denier per filament, typically greater than about 30 denier. Fine denier fibers generally refer to fibers having a diameter of less than about 15 denier per filament. Microdenier fibers are generally defined as fibers having a diameter of less than about 100 microns per filament. "Monofilament fiber" or "single filament fiber" means a continuous strand of material having an indefinite (ie, unscheduled) length of 20, as opposed to "short fiber", which is a discrete strand of defined length. Material (ie, strands that are cut or otherwise divided into sections of a predetermined length). ''elasticity' means that the fiber will recover at least about 50% of its stretched length after the first stretch and after the fourth to 100% strain (two times the length). Elasticity can also be 9 permanent change of the fiber "Description", the dimension is fixed by the stretching material, and the opposite is true. After the fiber, it is stretched again. The fiber starts negative = the original position before stretching, and the percentage. "Elastic material,, at, #点点Designated as permanent, . Elastomeric materials (sometimes referred to as "elastics", also known as "elastomers," and "elastomers, films, strips, strips H" contain the copolymer itself and the filaments, but are not limited to this coating, (four) The same type of copolymerization, two uncrosslinked. Do not know how to shoot shame, and / or couplet or dimension). Non-elastic) ± material means a material that is not elastic as defined above (eg, fiber, fiber, and fiber) means a polymer region having a single polymer region or range and having no different properties (eg, bicomponent fibers) Fibers. Two-component fibers, meaning fibers having two or more different polymer regions or 15 turns. Two-component fibers are also known as co- or multi-component fibers. These polymers are generally The two are different from each other, even though two or more components may comprise the same polymer. The polymer is disposed in a substantially different region of the wear surface of the bicomponent fibers 'and generally extends continuously along the length of the bicomponent fibers. The structure of the bicomponent fibers can be 'for example, a sheath-core configuration (where one polymer is surrounded by another 20), a side-by-side configuration, a pie configuration, or an "island" configuration. The fibers are further described in U.S. Patent Nos. 6,225,243, 6,140,442, 5,382,400, 5,336,552, and 5,108,820. The 'meltblown fibers' are formed by squeezing the molten thermoplastic polymer composition through a plurality of fine, generally circular molds. The tube is extruded to form a dazzling line or the 200900545 filament enters the collected high velocity gas (eg, air) stream to make the filaments or filaments thinner to reduce the diameter of the fibers. Filament or wire by high speed The gas stream is carried and deposited on the collecting surface to form a web of randomly dispersed fibers having an average diameter of generally less than 10 microns. 5 "Melt-spun fibers" are obtained by melting at least one polymer and then drawing the fibers in the melt. a fiber formed at least at the diameter of the mold (or other cross-sectional shape). "Spunbond" consists of a molten thermoplastic polymer formed by several fine (generally round) mold pores through a spinneret. A fiber formed by extruding 10 filaments. The diameter of the extruded filament is rapidly reduced, and then the filament is deposited on the collecting surface to form any dispersed fibers having an average diameter generally between about 7 and about 30 microns. "Non-woven" means a net or fabric of individual fibers or threads that are sandwiched (but not woven as in the case of knitted fabrics). According to the present invention, the embodiment 15 Elastic fibers can be used to prepare non-woven structures and composite structures in which elastic non-woven fabrics are mixed with non-elastic materials. "Yarn" means continuous length twisted or otherwise entangled filaments which can be used to make woven or knitted fabrics. Fabrics and other articles. The yarn may or may not be coated. The coated yarn is at least partially wrapped around another fiber or material 20 (typically natural fibers such as cotton or wool). The outer coated yarn. "Polymer" means a polymeric compound obtained by polymerizing monomers (the same or different types). The general "polymer" contains "homopolymer", "copolymer" "Diolefin" and "heteropoly copolymer" and the like. "Heteropolymer" means a polymer of 11 200900545 produced by polymerizing at least two different monomers. "Different copolymers" generally include the term "copolymer" (which is generally used to refer to polymers made from two different monomers) and the term "terpolymer" (which is generally used to refer to a polymer made from three different monomers). It also comprises a polymer produced by polymerizing four or more monomers. The phrase "ethylene/oxime:-olefin heteropolymer" generally means a polymer comprising ethylene and an ?-olefin having 3 or more carbon atoms. Preferably, ethylene comprises the primary molar fraction of the entire polymer, i.e., ethylene comprises at least about 50 mole percent of the total polymer. More preferably, the ethylene comprises at least about 60 mole%, at least about 70 mole%, or at least about 80 mole%, and the remainder of the entire polymer has at least one other comonomer, preferably An olefin having 3 or more carbon atoms. For many ethylene/octene copolymers, preferred compositions comprise an ethylene content greater than about 80 mole percent of the total polymer, and from about 10 to about 15 (preferably from about 15 to about 20) moles of the total polymer. % octene content. In certain embodiments, the ethylene/niobene-olefin heteropolymer does not comprise a low yield of 15 or a minor or chemical by-product. Although the ethylene/α-olefin heteropolymer can be blended with one or more polymers, the ethylene/α-olefin heteropolymer thus produced is substantially pure and generally comprises the major components of the reaction product of the polymerization process. . The ethylene/α-olefin heteropolymer comprises ethylene in a polymerized form and one or more copolymerizable α-olefin comonomers characterized by a plurality of polymerizations having two or more chemical or physical properties. A block or section of a monomer unit. Namely, the ethylene/α-dilute hydrocarbon heteropolymer is a block heteropolymer, and is preferably a heteroblock copolymer or copolymer of a multi-block. The terms "hetero-copolymer" and "copolymer" are used interchangeably herein. In certain embodiments, the multi-block copolymer 12 200900545 can be represented by the following chemical formula: (AB)n wherein η is at least 1, preferably greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70 '80, 90, 100, or 5 are higher. "Α" means a hard block or section, and "Β" means a soft block or section. Preferably, the lanthanum and lanthanide are connected in a substantially linear manner, as opposed to being substantially branched or substantially star shaped. In other embodiments, the A block and the B block are randomly distributed along the polymer chain. In other words, the block copolymer generally does not have the following structure.

10 AAA-AA-BBB-BB In other embodiments, block copolymers generally do not have a third block comprising different co-monomers. In other embodiments, each of the A block and the B block has a monomer or comonomer that is substantially randomly distributed within the block. In other words, neither the A block nor the B block contains two or more sub-sections 15 (or sub-blocks) of different composition, such as a tip segment, which has a composition that is substantially different from the remainder of the block. . Multi-block polymers typically contain various levels of "hard" and "soft" segments. By "hard" segment is meant a block of poly 20-inorganic units in which the ethylene is present in an amount greater than about 5% by weight and preferably greater than about 98% by weight based on the weight of the polymer. . In other words, the comonomer content (content of non-ethylene monomer) of the hard segment is less than about 5% by weight, and preferably less than about 2% by weight based on the weight of the polymer. In certain embodiments, the hard section comprises all or substantially all of the ethylene. In another aspect, a "soft" segment means that the comonomer content (content of non-ethylene monomer) is greater than about 5% by weight, preferably greater than 13% by weight of 200900545, greater than about 10% by weight, Or a block of polymerized units greater than about 15% by weight based on the weight of the polymer. In certain embodiments, the soft segment may have a comonomer content of greater than about 20% by weight, greater than about 25% by weight, and greater than about 30% by weight. /. , greater than about 35 weight percent, greater than about 40 weight percent per ounce, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent. The soft segment may generally be present in the block heteropolymer, preferably from about 5% by weight to about 95% by weight based on the total weight of the block heteropolymer, from about 1 weight to about 99% by weight based on the total weight of the block heteropolymer. % by weight, from about 1% by weight to about 90% by weight, from about 15% by weight to about 85% by weight, from about 2% by weight to about 8% by weight of 10%, from about 25% by weight to about 75% by weight, about 3〇 From about 70% by weight, from about 35% by weight to about 65% by weight, from about 40% by weight to about 6% by weight, or from about 45% by weight to about 55% by weight. Conversely, hard segments can exist in similar ranges. The weight percentage of the soft section and the weight percentage of the hard section can be calculated based on data obtained by DSC or NMR. These methods and calculations are disclosed in the co-pending U.S. Patent Application Serial No. 11/376,835, filed at 385, 063, 999, 558, entitled "Ethylene/α-Olefin Block Heteropolymers" March 15, 2006曰Application, in the name of c〇lin LP Shan, Lonnie Hazlitt, and the transfer to Dow Global Technologies Inc., the disclosure of which is hereby incorporated by reference in its entirety. Means a polymer that has a first-stage transfer or crystalline melt (Tm) that is determined by differential scanning calorimetry (DSC) or an equalization technique. This term can be used interchangeably with ''semi-crystalline'). . , "Amorphous," refers to a polymer that lacks the crystalline melting point as determined by differential scanning calorimetry (DSC) or an equalization technique. 14 200900545 "Multi-block copolymer" or "segment copolymer" is used to mean a chemically distinct region or segment (referred to as "block") containing two or more preferred linkages in a linear fashion. The polymer, i.e., the polymer comprising units 5 that are chemically different for the polymerized ethylene functionality in a tail-to-tail linkage (rather than lateral or grafting). In a preferred embodiment, the block is attached to the inner comonomer or in the form, the degree, the crystal, and the crystal size and tacticity caused by the polymer of the composition (all the same) The type or degree of stereo or syndiotacticity, regional regularity or regional irregularity, branching (including long-chain branches or hyperbranches), homogeneity, or any other chemical or physical property. The multi-block copolymer is characterized by a unique distribution of polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique method of making the copolymer. More specifically, when manufactured in a continuous process, the polymer desirably has a PDI of from 1.7 to 2.9, preferably from 1 to 8 to 2.5, more preferably from 8 to 2.2' and most preferably from h8 to. When manufactured in a batch or semi-batch process, the 15 polymer has a PDI of from 1 Torr to 2.9, preferably from 1.3 to 2.5, more preferably from 14 to 2.0, and most preferably from 1.4 to 1.8. In the following description, regardless of whether the words "about,, or,,,,,, etc., are used in conjunction with the words, all values disclosed herein are approximate. It may be 1%, 2%, 5 〇/., or sometimes, 10 Any change to the range of the numerical value range of the lower limit rl and the upper limit ruler 11 is disclosed, and any numerical value falling within the range is specifically disclosed. In particular, the following numerical values in this range are specifically disclosed: R =RL+k*(RU_RL), where k is a variable ranging from 1% to 100〇/〇, and is incremented by 1%, ie, 1%, 2〇/〇, 3%, 4%, 5%····5〇%, 51%, 52%·95%, he, 97%, 98%, 99%, or %. In addition, any numerical range defined by the above-mentioned two performances, 200900545 Specifically disclosed. Ethylene/α-olefin heteropolymers are used in the olefin block polymers of the examples of the present invention, for example, ethylene Ζα-dilute hydrocarbon heteropolymers (also, the heterogeneous copolymers of the present invention, or , the present invention, a compound comprising, in a polymerized form, and one or more copolymerizable alpha smoky comonomers, characterized by different chemical or physical properties a block or segment (block heteropolymer) having two or more polymerized monomer units, preferably a multi-block copolymer. The ethylene/α-olefin heteropolymer is characterized by one or more of the following In one aspect, the ethylene/α-olefin heteropolymer used in the embodiment of the present invention has a Mw/Mn of about 1.7 to about 3.5, and at least one thawing (Tm, and density (d, gram). /cubic centimeters), where the values of these variables correspond to the following relationship:

Tm>-2002.9 + 4538.5(d) - 2422.2(d)2, and preferably 15 Tmg-6288.1 + 13141(d)-6720.3(d)2, and more preferably

Tmg 858.91 - 1825.3(d) + 1112.8(d)2. The relationship between these melting points/densities is illustrated in Figure 1. Unlike conventional ethylene/α-olefin random copolymers whose melting point decreases with decreasing density, the heteropolymer of the present invention (indicated by diamonds) exhibits a melting point substantially independent of density, especially When the density is between about 0.87 g/cc to about 0.95 g/cc. For example, when the density ranges from 0.875 g/cc to about 0.945 g/cc, the melting point of such polymers is in the range of from about 110 °C to about 130 °C. In certain embodiments, the melting point of such polymers ranges from about 115 ° C to about 125 ° C when the density ranges from 0.875 g/cc to about 0.945 g/cc. 16 200900545 In another aspect, the ethylene/α-olefin heteropolymer comprises a polymerized version of ethylene and one or more alpha-olefins, and is characterized by a temperature difference of the highest difference broom calorimetry ("DSC" peak) Subtract 去:), and heat of fusion, j/g, 5 ΔΗ), and ΛΤ and ΔΗ satisfy the following relationship: For ΛΗ up to 130 J/g When, Δ Τ > -0_1299 (ΛΗ) + 62.81, and preferably Δ Τ 2-0.1299 (ΔΗ) + 64 · 38, and more preferably Δ Τ 0.1 2-0.1299 (ΔΗ) + 65.95. Further, for ΑΗ greater than At 130 J/g, the ratio is equal to or greater than 48 t: The CRYSTAF peak is determined using at least 5% of the cumulative polymer (ie, the peak needs to represent at least 5% of the cumulative polymer)' and if less than 5% of the polymer has The identifiable CRYSTAF peak' then has a CrySTAF temperature of 3 〇t: and is the value of the heat of fusion 'J/g. More preferably, the highest CRYSTAF peak contains a cumulative polymer of at least 1 〇〇/〇15. Figure 2 The graph data of the polymer of the present invention and the comparative example are shown. The integrated peak area and peak temperature are provided by the instrument manufacturer. The calculation of the drawing program. The diagonal line shown for the random ethylene octene comparative polymer corresponds to the equation + 62.81. On the other hand, when using the temperature rise elution fractionation ("TREF") classification 2 ,, ethylene / The α-olefinic heterogeneous copolymer has a molecular fraction eluted between the peach and the crucible, characterized in that the fraction has a higher ratio than that of the pseudo-ethylene heteropolymer copolymer grade eluted at the same temperature. Preferably, the height is at least 5%, more preferably at least 1%, and the molar comonomer content, wherein the random ethylene heteropolymer has the same comonomer and has 17 200900545 embedded The melt index, density, and molar comonomer content (based on the entire polymer) of the fractional heteropolymer, preferably Mw/Mn of the heterogeneous copolymer is also Within 10% of the block heteropolymer, and/or the total monomer content within 105% by weight of the heteropolymer having a block heteropolymer. "" a dilute/α-olefin heteropolymer characterized by ethylene • The molded film of the - / α -olefin heteropolymer is measured at 300% strain and 1 cycle of elastic recovery (Re, %), and has a density (d, g / cm ^ 3 ), where When the ethylene/α-olefin heteropolymer has substantially no cross-linking phase, the values of Re 10 and d satisfy the following relationship:

Re>1481-1629(d); and preferably Re2 1491-1629(d); and more preferably Re2 1501-1629(d); and more preferably Reg 1511-1629(d). 15 Figure 3 shows the effect of density on the elastic recovery of non-oriented films made from certain heterogeneous copolymers of the invention and conventional random copolymers. The heterogeneous copolymers of the present invention have substantially higher elastic recovery for the same degree of density. In certain embodiments, the ethylene/α-olefin heteropolymer has a tensile strength greater than 10 MPa, preferably a tensile strength of 2 11 MPa, more preferably a tensile strength of 2 20 13 MPa, and/or At a crosshead separation rate of 11 cm/min, the elongation at break is at least 600%, more preferably at least 700%, preferably at least 800%, and most preferably at least 900%. In other embodiments, the acetamidine/α-olefin heteropolymer has a storage modulus ratio of (1) 1 to 50, G′ (25° C.)/G′ (100° C.), preferably 1 to 20, Further 18 200900545 preferably 1 to 10; and/or (2) less than 80% of the 70 ° C compression set, preferably less than 70% 'especially less than 60%, less than 50%, or less than 40%, down to 0% compression set. In still other embodiments, the ethylene/α-olefin heteropolymer has less than 580%, less than 70%, less than 60%, or less than 5% (TC compression set. Preferably, heterogeneous copolymerization 7: (: The compression set is less than 40%, less than 30%, less than 2%, and can be reduced to about 〇%. In certain embodiments, ethylene/α-olefin heterogeneous copolymerization The material has a heat of fusion of less than 85 J/g, and/or a breaking strength of 10 or less (1800 Pa) of pellets, preferably 50 lbs/min or less.呎2 (24〇〇Pa), especially equal to or less than 5 psig (240 Pa), and as low as 〇Pound/mile 2 (〇Pa). In other embodiments, ethylene/α-olefin The heterogeneous copolymer comprises at least 50 mole % ethylene in a polymerized version and has less than 8% (preferably less than 70% or less than 60% 'best less than 4% to 5%) , and reduced to close to 〇%) 15 of 70 ° C compression set.

In certain embodiments, the multi-block copolymer possesses a PDI that fits the SchuUz-Fi〇ry distribution (rather than the Pois surface distribution). The copolymer $-step is characterized by a polydisperse block distribution and a cross-sectional size distribution with the most probable block length distribution. Preferably, the multi-block filament system contains 4 or more rice segments or segments (including terminal butterflies. More preferably, the copolymer comprises at least 5, 10 or 20 blocks or segments (including terminal blocks). 'And the NMR co-monomer content can be used in any suitable technique ("NMm spectroscopy-based technology is preferred. Furthermore, for polymers or polymer blends with relatively wide TREF curves. The desired polymer system 19 200900545 is first classified into several fractions using TREF, each having a elution temperature range of 10 ° C or less. That is, each elution fraction has 10 ° C or less. The temperature window is collected. Using this technique, the block heterogeneous copolymer has at least one such fraction having a higher molar comonomer 5 content than the corresponding fraction of the comparable heterogeneous copolymer. The inventive polymer is an olefin heteropolymer, preferably comprising a polymerized version of ethylene and one or more copolymerizable co-monomers, characterized by two or more polymerized monomer units having different chemical or physical properties. Multiple blocks (ie, at least two Block) or segment (block heteropolymer 10), preferably a multi-block copolymer having a peak eluted between 4 〇 t and 130 ° C (but not only one) Molecular fractionation) (but not collecting and/or isolating individual fractions), characterized in that the peak has a comonomer content estimated by infrared spectroscopy when expanded using a full width/half maximum (FWHM) area calculation, It can be compared with the same elution temperature and using the full width/half maximum 15 (FWHM) area. It can be compared with the peak of the random ethylene heteropolymer, preferably at least 5% higher, and better at least higher. 1〇%, the average molar commonomer content, wherein the comparable random ethylene heteropolymer has the same comonomer' and has a melt index, density within 1% of the block heteropolymer And the molar comonomer content (based on the entire polymer based on 20). Preferably, the Mw/Mn of the heterogeneous copolymer is within 10% of the block heteropolymer, and/or A comparable total of 10% by weight of the block heteropolymer Body content. The full width/half maximum (FWHM) calculation is based on the ratio of the base of the ATREF infrared detector to the response area of the base [CIVCH2], where the highest peak is identified from the baseline of 20 200900545, then FWHM The area is determined. From the distribution measured using the ATR £F peak, the FWHM area is defined as the area under the curve of several, where the D2 is around the ATREF peak by dividing the peak height by 2 Then, draw a line that is horizontal with the baseline and the left and right parts of the ATREF curve. The calibration curve for the comonomer content is determined by using random ethylene/α thin; The ratio of the total monomer content to the FWHM area ratio of the tref peak is obtained. For this infrared method, the calibration curve is generated for the same comonomer pattern of interest. The comonomer content of the TREF peak of the polymer of the present invention can be determined by referring to this calibration curve using its 10 FWHM methyl:methyl group area ratio [CH3:CH2] of the TREF peak. The comonomer content can be measured using any suitable technique, and a technique based on nuclear magnetic resonance (NMR) spectroscopy is preferred. Using this technique, the block heteropolymer has a higher molar co-monomer content than the corresponding comparable heteropolymer. Preferably, for the heteropolymer of ethylene and ruthenium-octane, the block heteropolymer has a comonomer content of the TREF fraction eluted between 40 and 130 ° C is greater than or equal to (-0_2013) The amount of T+20.07, more preferably greater than or equal to (-0.2013) Τ + 21.07 amount 'where the lanthanide is compared to the peak elution temperature of the TREF fraction, measured in ° C. 20 Figure 4 is a diagram illustrating an example of a block heteropolymer of ethylene and 1-octene, in which a plurality of comonomers of ethylene/1-octene heteropolymer (random copolymer) are compared The plot of the content on the TREF elution temperature is fitted to the line representing the (-0.2013) T+20.07 (solid line). The line of the equation (_〇.2〇i3) T+21.〇7 is depicted by a dashed line. The comonomer content of the fractions of the heteroblock copolymers (multi-block copolymers) of the various block ethylene/1_Xinthene 21 200900545 of the present invention is also described. All of the block heterogeneous copolymer fractions have a significantly higher 1-octene content than either line of equal elution temperature. This result is characteristic of the heteropolymer of the present invention and is believed to have 5 crystalline and amorphous properties as a result of the presence of different segments within the polymer chain. Figure 5 is a diagram showing the polymer of Example 5 and Comparative Example F as discussed below.

The TREF curve and comonomer content of the fraction. The peak of the elution of the two polymers from 4 Torr to i3 〇 ° C (preferably 60 to 95 ° C) is classified into three fractions, each fraction being eluted at a temperature range of less than 10 °C. The actual data of Example 5 is indicated by a triangle 10. Those skilled in the art will appreciate that a suitable calibration curve can be constructed for heterogeneous copolymers containing different comonomers, and a comparative heterogeneous copolymer prepared from a metallocene or other homogeneous catalyst composition from the same monomer. The TREF value obtained is obtained (preferably a random copolymer). The heterogeneous copolymer of the present invention is characterized by a molar monomer content greater than the value of the self-calibration curve at the same TREF elution temperature decision 15, preferably at least 5% greater, more preferably at least 10% greater. In addition to the above aspects and properties described herein, the polymeric features of the present invention may be characterized by one or more additional characteristics. In one aspect, the polymer of the present invention is an enefe heteropolymer, preferably comprising a polymerized version of ethylene oxime and one or more copolymerizable comonomers, characterized by chemical or physical properties. Multi-block or segment of two or more polymerized monomer units (block heteropolymer), preferably multi-block copolymer, when the TREF incremental fractionation is used, the 'edge block heteropolymer has 4 (Molecular fractionation eluted between TC and 130 ° C is characterized in that the fraction is higher than that of the 22 200900545 pseudo-random ethylene heteropolymer grade, which is higher than that of the mixture of the same temperature. At least 5%, more preferably at least 1 〇, 15, 20 or 25%, of the molar comonomer content, wherein the comparable random ethylene heteropolymer comprises the same comonomer, preferably It is the same comonomer, and the melt index, density, and molar comonomer content of the mole copolymer in 1% of the block heteropolymer (based on the entire polymer). Preferably, it can be compared The Mw/Mn of the heteropolymer is also within 10% of the block heteropolymer, and/or The comparative heterogeneous copolymer has a total monomer content within 1% by weight of the segmented heteropolymer. Preferably, the above heterogeneous copolymer is a copolymer of ethylene and at least one-olefin, particularly having 10 copolymers. a heteropolymer of about 0.855 to about 0.935 g/cm 3 of overall polymer density' and more particularly a polymer having more than about 1 mol% comonomer, the block heteropolymer having 40 and 13 ( The comonomer content of the TREF fraction eluted by TC is greater than or equal to (-0.1356)T+13.89, more preferably greater than or equal to (_〇.l356)T+14.93 15 and the optimum is greater than or Equivalent to (-0.2013) T + 21.07, wherein T is the peak ATREF elution temperature value of the TREF fraction compared to C. Preferably, for the above-mentioned acetamidine and at least one hydrazine: - olefin a heterogeneous copolymer, particularly a heterogeneous copolymer having an overall polymer density of from about 0.855 to about 0.935 grams per cubic centimeter, and more particularly a polymer having more than about 1 mole percent comonomer, block The heterogeneous copolymer has a comonomer content greater than that of the TREF fraction eluted between 40 and 130 ° C. Equivalent to (_〇.2013) Τ+20·07 quantity, more preferably greater than or equal to (-0.2013) Τ+21.07, where the lanthanide is compared with the peak elution temperature value of the TREF fraction, measured by .c. 23 200900545 In another aspect, the polymer of the present invention is an olefin heteropolymer, preferably comprising a polymerized ethylene and/or a plurality of copolymerizable co-monomers, characterized by different chemical or physical properties. a multi-block or segment (block heteropolymer) having two or more polymerized monomer units, preferably a multi-blocked 5-stage copolymer, which has a heterogeneous copolymer when fractionally graded using TREF Molecular fractions of 4 (TC and 13 (TC) eluted, characterized by each fraction having a comonomer content of at least about 6 mole percent, having a melting point greater than about 100 °C. For each of the fractions having a comonomer content of from about 3 mole % to about 6 mole %, each fraction has a DSC melting point of about 11 (TC or higher. More preferably 10 grounds, having at least 1 mole These polymer fractions of % co-monomers have a DSC melting point corresponding to the following equation:

Tmg (-5.5926) (% co-monomer in the fraction) + 135.90. In another aspect, the polymer of the present invention is an olefin heteropolymer, preferably comprising a polymerized version of ethylene and one or more copolymerizable 15 comonomers characterized by chemical or physical properties. Or more multi-block or segment of the polymerized monomer unit (block heteropolymer), preferably a multi-year copolymer, which has a molecular weight of 40 when graded by TREF. (: molecular fraction eluted with l3〇t, characterized in that each fraction having an AT RE F elution temperature of greater than or equal to about 7 61 has a melting enthalpy measured by DSC corresponding to the following equation ( Heat of smelting): Hyun heat (J/gm) $(3.1718) (ATREF elution temperature, 〇·136.58. The block heteropolymer of the present invention has a fraction of TREF when used, and 4 〇° A molecular fraction eluted between C and 130 ° C, characterized in that each fraction having an AREFET elution temperature between 4 Torr and less than about 76 ° C has a phase of 24 200900545 corresponding to the following equation Melting enthalpy (heat of fusion) measured by DSC: Heat of fusion (J/gm) $ (1.1312) (ATREF elution temperature, .c) + 22.97. Measurement of ATREF peak comonomer composition TREF peak comonomer by infrared detector The composition can be measured using an IR4 infrared detector available from P〇lymer Char, 5 Valencia, Spanfhttp.V/www.polvmerchar.cnm/'t. The “composition mode” of the detector is equipped with a measuring sensor (CH2) and Forming the sensor (CH3) 'It is a fixed narrow-band infrared filter with a range of 2800-3000 cm -1 zone. The measuring sensor detects the carbon of the methylene group on the polymer (which is directly related to the polymer concentration in the 10 solution), and the detector detects the methyl group (CH3) of the polymer. The composition signal (CH3) is divided by the measurement signal ( The mathematical ratio of CH2) is sensitive to the comonomer content of the polymer measured in solution, and the response is corrected by a known ethylene alpha-olefin copolymer standard. The detector provides the TREF method when used with an ATREF instrument. The concentration of the polymer (CH2) and the composition (CH3) signal are echoed during the wash. The specific correction of the polymer can be determined by the CH3 to CH2 area of the polymer having a known comonomer content (preferably measured by NMR). The ratio of the comonomer content of the ATREF peak of the polymer can be estimated by applying a reference correction of the ratio of the area of the individual CH3 and CH2 responses (ie, CH3/CH2 area ratio versus comonomer content). The full-width/half-maximum (FWHM) is used to calculate the individual signal response of the integrated TREF chromatogram after applying the appropriate baseline. The full-width/half-maximum calculation is based on the ratio of the methyl-methylene-based response area of the ATREF infrared detector [ C Based on H3/CH2], the highest peak is identified from the baseline, and then the FWHM area is determined. For the distribution using the ATREF peak 25 200900545, the FWHM area is defined as the area under the curve between T1 and T2, where Τ1 and Τ2 are around the ATREF peak, by dividing the peak height by 2, and then plotting a line that is horizontal to the baseline and intersecting the left and right parts of the ATREF curve. 5 The use of infrared spectroscopy to measure the comonomer content of a polymer in this ATREF infrared method is in principle similar to the GPC/FTIR system described in the following references. Markovich, Ronald P.; Hazlitt, Lonnie G.;

Smith, Linley; "Cell Permeation Chromatography for the Derivation of Ethylene-Based Polyolefin Copolymers - Development of Fourier Transform Infrared Spectroscopy", p〇lymer 10 Materials Science and Engineering (1991), 65, 98-100 And Deslauriers, PJ·; Rohlfing, D_C.: Shieh, Ε.Τ.;” Quantification of short-chain branched microstructures in ethylene olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC_FTIR), P〇lymer (2〇〇2), 43, 59-170, both of which are hereby incorporated by reference in their entirety in each of the the the the the the the the the It is an average block index (ABI) greater than 0 and up to about 1.0, and a molecular weight distribution (Mw/Mn) greater than about 1.3. The average block index (ABI) is between 201 and 110 C (5 C increments). The weight average of the block index ("BI") of each polymer fraction obtained by the preparation of TREF: 20 ABI = E (wiBIi) wherein 'Bli is the ethylene/oxime of the invention obtained by preparing TREE; The block index of the first fraction of the copolymer, and the weight percentage of the Wi-based i-th grade. For each polymer fraction, the BI system is defined by one of the following two equations (both 26 200900545 yielding the same BI value): ΒΙ-λΙΤχ ~l/Tx〇 戍 LnPx -LnPX0

l/TA-\/TAB ^ LnPA -LnPAB wherein the Tx is the ith fraction of the preparation of the ATREF elution temperature (preferably represented by K (Kelvin)), and the ethylene molar fraction of the Px ith fraction It can be measured by NMR or IR as described above. PAB is the ethylene molar fraction of the entire ethylene/α-olefin heteropolymer (before classification), which can also be measured by NMR or IR. What? The eight-phase pure "hard segment" (which refers to the crystalline segment of the heteropolymer) has an ATREF elution temperature and a vinyl mole fraction. As a first-order approximation, if the actual value of the hard segment is not available, the TA&PA value is set to a high-density poly(10-ene homopolymer). For the calculations performed here, the TA system is 372°K, PA. Line 1. TAB is the ATREF temperature of a random copolymer of the same composition and having a PAB ethylene molar fraction. TAB can be calculated from the following equation:

Ln PAB = a / TAB + yS where 'α and /3 can be determined by using several known random ethylene copolymers. Note that α and /3 can vary with the instrument. Furthermore, it is desirable to have an appropriate calibration curve for the polymer composition of interest and for a molecular weight range similar to the fraction. Has some micro molecular weight effect. If the calibration curve is obtained from a similar molecular weight range, this effect is essentially ignored. In some embodiments, the random ethylene copolymer satisfies the following relationship: 20 Ln P = -237.83 / Tatref + 0.639 The ATREF temperature of the random copolymer of the same composition and having a Px ethylene molar fraction. Txo can be calculated from the LnPx=α /Txo+ point. Conversely, the ethylene fraction of the random copolymer of the same composition and having the ATREF temperature of Tx is calculated as the ear fraction, which can be calculated from Ι^Ρχο=α:/Τχ+6. Once the block index (ΒΙ) of each of the prepared TREF fractions is obtained, the weight average block index (ΑΒΙ) of the entire polymer can be calculated. In certain embodiments, the lanthanide is greater than zero but less than about 0.3, or from about 0.1 to 0.3. In other examples, the lanthanide system was greater than about 0.3 and up to about 1.0. Preferably, it is desirably in the range of from about 0.4 to about 0-7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In certain embodiments, the lanthanide is in the range of from about 0 to about 3.5 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, the lanthanide is in the range of from about 0.4 to about 1.0, from about 0.5 to about 10 1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, from about 0.8 to about 1 to 0, or from about 0.9 to about 1.0. . Another feature of the ethylene/α-olefin heteropolymer of the present invention is that the ethylene/α-olefin heteropolymer of the present invention comprises at least one polymer fraction obtainable by preparing TREF, wherein the fraction has greater than about 0.1 and Up to a block index of about 1.0 and a molecular weight distribution (Mw/Mn) of greater than about 1.3. In certain embodiments, the polymer fraction has greater than about 0.6 and up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0. Block index. In other embodiments, the polymer fraction has greater than about 0.1 and up to about 1.0, greater than about 0.220, and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4, and up to about 1.0, or greater than A block index of about 0.4 and up to about 1.0. In other embodiments, the polymer fraction has greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0.5, or greater than about 0.4 and up to about 0.5. Segment index. In other embodiments, 28 200900545 the polymer fraction has greater than about 0.2 and up to about 0.9' greater than about 〇·3 and up to about 0.8, greater than about 〇.4 and up to about 0.7, or greater than about 〇·5. And up to about 0.6, block index. For copolymers of ethylene and an alpha-olefin, the polymer of the invention preferably has (1) at least 1.3 (more preferably, less than 1.5, at least 1-7, or at least 2_0, and most preferably at least 2.6), up to PDI of a maximum of 5.0 (better of a maximum of 3.5), especially a maximum of up to 2.7; (2) heat of fusion of 80 J/g or less; (3) of at least 50% by weight of ethylene Content; (4) glass transition temperature (Tg) of less than -25 ° C (more preferably less than -30 ° C); and / or (5) only one Tm. Further, the polymer of the present invention may, alone or in combination with any of the other properties disclosed herein, have a storage modulus (G,) of TC such that 丨og(G,) is greater than or equal to 400 kPa. Preferably, the polymer is greater than or equal to 1.0 MPa. Furthermore, the polymer of the invention has a relatively flat storage modulus as a function of temperature in the range of TC (illustrated in Figure 6). a segment copolymer characterized by a 15 series olefin copolymer (particularly a copolymer of ethylene and one or more C3-8 aliphatic alpha-anthracene hydrocarbons). (In this context, relatively straight , the phrase means that between 5 〇 and 100 ° C (between 〇 and 〇〇 °c) i 〇 gG, (Basca) is reduced by less than one level. The heterogeneous copolymer of the present invention The article is further characterized by at least 9 Å. (: a thermomechanical analysis penetration depth of 1 mm at a temperature of 20, and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa). In addition, the heterogeneous copolymer of the present invention The material may have an imm thermomechanical analysis penetration depth at a temperature of at least 104 C and a flexural modulus of at least 3 kpsi (20 MPa). Has a wear resistance of less than 9 mm3. Figure 7 shows the TMA (1 mm) versus flexural modulus of the polymer of the invention compared to other known polymers 29 200900545. The polymer of the invention has a higher specific polymer than the other polymers Significantly better flexibility - heat resistance balance. In addition, the ethylene riding heterogeneous copolymer may have a 〇〇1 to 2 gram / 1 〇 minute, preferably read to 诵 / 10 minutes, better system 〇〇1 to lion/m〇 5 minutes, and especially 0. 01 to 100 g/10 minutes, (iv) index (6). In certain embodiments, the ethylene/"olefin heteropolymer has a read of 1 gram / 1 minute, 〇·5 to 50 g/10 min, 1 to 30 g/10 min, (1) g/. bell, or 〇 _3 to 10 g/10 min, smelting index (12). In the embodiment, the spectroscopy index of the ethylene/«-olefinic heteropolymer is gram/chuan minutes, 3 g/10 minutes 10 minutes, or 5 g/10 minutes. The polymer may have 1, gram/ Molar to 5, gram / moule, preferably 1000 g / mol to 丨 '000,000 g / Moule, better 1 gram / mol to 500,000 g / Mo Ear, and especially 10,000 g / mol to 3 〇〇 Mack/mole, molecular weight (Mw). The density of the polymer of the present invention may be from 8 〇 to 99 15 g/cm 3 ' and for ethylene-containing polymers is preferably 0.85 g/cm 3 to 〇_97 g/cm 3. In certain embodiments, the ethylene/α-olefin polymer has a density in the range of 0.860 to 0.925 g/cm 3 ' or 0.867 to 0.910 g/cm 3. The method of making these polymers has been Described in the following patent applications: US Provisional Application No. 60/553,906, March 17, 2004 application; US 20 Provisional Application No. 60/662,937, March 17, 2005; US Provisional Application Case No. 60/662,939, Application on March 17, 2005; US Provisional Application No. 60,5662938, 'Application on March 17, 2005; PCT Case No. PCT/US2005/008916, 2005 Application on March 17; PCT Application No. PCT/US2005/008915, March 2005, 17 曰申30 200900545, and PCT Application No. PCT/US2005/008917, 2, 5, March, P曰Applications, all of which are hereby fully incorporated herein by reference. For example, one such method comprises contacting ethylene and one or more non-ethylene addition polymerizable monomers with an addition catalyst composition comprising the following under additive polymerization conditions: a mixture or reaction product: (A) a first thin-smoke polymerization catalyst having a high comonomer and a nano-index, (B) a comonomer having a catalyst (A) having a neat index of less than 9% by weight, preferably The 10 series is less than 50%, preferably less than 5% of the co-monomer of the second olefin polymerization catalyst, and (C) the chain shuttling agent. Representative catalysts and shuttling agents are as follows. Catalyst (A1) is [N-(2,6-bis(1-mercaptoethyl)phenyl)decylamino](2-15 isopropyl base) (α-naphthalene-2-diyl (6-&quot ; 〇 -2- 二 二 二 二 曱 ] ] ] ] ] ] , , 依据 依据 依据 依据 依据 依据 依据 WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO according to WO 03/40195 ' 2003 US0204017, USSN 10/429, 024 Teaching manufacturing.

Catalyst (Α2) is [Ν-(2,6-bis(1-methylethyl)phenyl)-branyl](2·methylphenyl)(1,2-phenylene-(6-pyridine) -2-diyl)methyl) to dimethyl, its 31 200900545

Manufactured according to the teachings of WO 03/40195, 2003 US0204017, USSN 10/429, 〇24 (filed on May 2, 2003) and WO 04/24740

The catalyst (human 3) is a double [>^"'-(2,4,6-tris(nonylphenyl)nonylamino)phenylenediamine]decyldiphenylmethyl group.

Catalyst (A4) is bis(2-decyloxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane -u-diyl zirconium (IV) bis 10 benzyl, which is essentially prepared in accordance with the teachings of US-A-2004/0010103.

The catalyst (B1) is 1,2-bis-(3,5-di-t-butylphenylene 32 200900545-based) (1-(N-(1-methylethyl)imino)methyl) ( 2-decyloxy)nonhenyl C(CH3)3

Catalyst (B2) is 1,2-bis-(3,5-di-t-butylphenylene) (1-(indolyl-(2-methylcyclohexyl)-imino)methyl) (2) -nonyloxy)zirconium-2-yl

Catalyst (C1) is a (t-butylammonium)difluorenyl (3-N-pyrrolyl-1,2,3,33,73-;?-indol-1-yl)nonane titanium dimercapto group, It is manufactured in substantial accordance with the teachings of Case No. 118,268,444.

(H3Lj2M\ /Ti(CH3)2 NI c(ch3)3 Catalyst (C2) is a (t-butylammonium) bis(4-methylphenyl)(2-methyl-1,2,3, 3a,7a-indol-1-yl)nonane titanium dimethyl, which is essentially made according to the teachings of US-A-2003/004286. 33 200900545

Catalyst (C3) is a (t-butylammonium) bis(4-methylphenyl)(2-methyl-1,2,3,3&,8&-77-8-imida-1- The base is pulverized in a dimethyl group, which is manufactured in accordance with the teachings of US-A-2003/004286.

Catalyst (D1) is bis(dimethyldioxane)(茚-1-yl)zirconium di-gas, available from Sigma-Aldrich:

The shuttle agent used in the shuttle comprises diethyl zinc, di(isobutyl), 10 bis(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, isobutylammonium double ( Dimethyl (t-butyl) decane, isobutyl aluminum bis(di(tridecyl decyl) decylamine), n-octyl aluminum di(pyridine-2-oxide), double (positive) Octadecane 34 200900545 base)isobutyl sulphate, isobutyl bis (di(n-pentyl) decylamine), n-octyl bis (2,6-di-t-butyl phenoxide, n-octyl succinyl (ethyl) (1Qinyl), amine, bis (tert-butyl dimethyl fluorene oxide), ethyl succinium (8) trimethyl sulphate), ethyl shuang AW stupid and small nitrogen Heterocyclic heptane 5 oxime), n-octyl bis (2,3,6,7-dibenzothiazepine), n-octyl bis (dimethyl (tert-butyl) weide, Ethyl zinc (2,6 diphenyl oxide), and ethyl (third butoxide). Preferably, the foregoing method uses a continuous solution method to form blocks using several catalysts that cannot be converted to each other. Copolymer, especially multi-block Preferably, the linear multi-block copolymer of two or more monomers (particularly ethylene and olefinic or cyclic: hydrocarbons, and most particularly ethylene and CVmqi-olefins), ie, the catalysts are chemically different. Under continuous solution polymerization conditions, the process is ideally suited for polymerizing a monomer mixture at a high monomer conversion. Under these polymerization conditions, the shuttle from the bond (4) to the charge of the agent is compared to the chain growth. Advantageous and multi-back copolymers (especially linear multi-blocks) are formed with high efficiency. The heteropolymers of the invention can be produced by sequential monomer addition, flow catalyst, anionic or cationic living polymerization techniques. The random copolymer, the physical blend of the polymer, and the block copolymer are different, in particular, the same monomer and monomer containing random copolymers of equal crystallinity or modulus are reduced. The heterogeneous copolymer of the present invention has a good (higher) ratio (in terms of melting point), a higher TMA penetration temperature, a higher high temperature resistance, a degree, and/or a higher high temperature torque. Storage modulus (by dynamic mechanical = fixed) Compared with the random copolymer of the same monomer and monomer content, the present invention has a lower degree of shrinkage and is distinguished by high temperature, lower stress gas, relaxation, and higher resistance. Creep, higher tear strength, higher resistance to adhesion, due to temperature change due to two crystallization (10), faster recovery (especially when enthalpy) Preferred for abrasiveness, higher retraction force, and better oil and filler acceptance. The heteropolymer of the present invention also exhibits a unique relationship of crystallization and branching distribution. That is, the heterogeneous copolymer of the present invention has a relatively large difference between the peak temperature measured by cRYSTAF and DSc (which is a function of the heat of fusion), especially with the same monomer and monomer content at an equal overall density. A random copolymer of 10 or a physical blend of a polymer, such as a blend of a high density polymer and a lower density copolymer. The unique characteristics of the heterogeneous copolymers of the present invention are believed to be due to the unique knives of the comonomers in the inner block of the polymer backbone. In particular, the heteropolymer of the present invention may comprise interlaced blocks (including homopolymer blocks) having different levels of co-monomers. The heteropolymer of the present invention may also comprise a distribution of the number and/or block size of polymer blocks having different densities or comonomer contents, which is a Schultz-Flory type distribution. In addition, the heteropolymer of the present invention also has a unique peak melting point and crystallization temperature distribution, which is substantially independent of polymer density, modulus and morphology. In a preferred embodiment, the microcrystalline sequence of the polymer demonstrates 20 characteristic spherulites and flakes distinguishable from random or block copolymers, even at less than 1.7 or at least 丨.5, at least At a PDI value of 13. Further, the heteropolymer of the present invention can be produced using techniques that affect the extent or amount of the block. That is, the amount and length of the comonomer of each polymer segment or segment can be varied by controlling the ratio and type of catalyst and shuttling agent to the polymerization temperature 36 200900545 and other polymerization variables. One of the surprising benefits of this phenomenon is the discovery that as the degree of blockiness increases, the optical properties, tear strength, and south temperature recovery properties of the formed polymer are improved. In particular, when the average number of blocks of the polymer is increased, the 'turbidity is reduced' and the clarity, tear strength and high temperature recovery property are increased by 5 times. Other types of polymer terminations can be effectively inhibited by selecting a combination of a shuttling agent and a catalyst having the desired bond transfer capability (two shuttle rates with low chain end chain). Thus, very little, if any, of the hydride-hydrogen removal is observed in the polymerization of the ethylene/α-olefin comonomer mixture in accordance with embodiments of the present invention, and the crystalline block system formed is highly (or substantially The complete line ίο sex 'has little or no long chain branching. The polymer having the end of the crystalline chain can be selectively produced in accordance with embodiments of the present invention. For elastomer applications, lowering the poly- & This result can be obtained by selecting a chain shuttling agent and a 15 catalyst which respond appropriately to hydrogen or other chain terminators. In particular, if the catalyst ratio resulting in a highly crystalline polymer results in a lower crystalline polymer segment (such as via a higher comonomer and a regional error, or the formation of an atactic polymer) The polymer is more susceptible to chain termination (such as by the use of hydrogen), and the highly crystalline polymer segments are preferentially located at the terminal end of the polymer. Not only the end groups are formed, but also the crystalline phase is formed. The polymer catalyst position is again available for re-starter formation. Thus, the initially formed polymer is another high polymer segment. Therefore, the two-block copolymer formed is preferred. Highly crystalline. The ethylene "-olefin heteropolymer" used in the examples of the present invention is preferably 37 200900545. A heteropolymer of ethylene and at least _r, a minus-hydrocarbon. Ethyl and c3-c2 (c C : The copolymer is particularly preferred. The heteropolymer can be further included: not::: and/or alkenyl. Suitable for the polymerization of ethylene with a suitable unsaturated monoterpene & human 7, cardamom 3, For example, ethylenically unsaturated monomers, conjugated or non-common vehicles Diene, ¥, π # β-decene, alkenyl, etc. Examples of such comonomers include c3-c20 a-olefins, such as & propylene, isobutylene, 1-butene, u Hexene, decene, 10 15 20 mesopentene, heptene, 1-octene, 1-decene, 1-decene, etc. 1_butylene and 1-octene are particularly difficult. Other suitable singles The body comprises styrene, styrene substituted with a halogen group or a burnt group, vinyl benzocyclobutane, 14 hexadiene, 1,7-octadiene, and a cycloalkane (for example, cyclopentene, ring) Hexene, and cyclooctene. Although an ethylene/α-olefin heteropolymer is a preferred polymer, other ethylene/olefin polymers may also be used. The olefin used herein refers to having at least one carbon-carbon double. The bond is a family of unsaturated hydrocarbon-based compounds. Depending on the choice of catalyst, any olefin can be used in the examples of the present invention. Preferably, the suitable olefin is a CVCzo aliphatic and aromatic character containing ethylenic unsaturation. 'With cyclic compounds such as 'cyclobutene, cyclopentene, dicyclopentadiene and norbornene, unrestrictedly contained in positions 5 and 6 with CVC2 JS _ group-substituted norbornene. Also included is a mixture of such olefins, and a mixture of olefins such as hydrazine and a C4-C2o diolefin compound. Examples of olefin monomers include, without limitation, propylene and isobutylene. , 丨_丁归卜戊稀, 1-hexaped, 1-heptene, 1-octene, 1-decene, u癸, and 1, twelve carbon, 1-tetrafluorocarbon, 1_ Hexadecene, 1-eighteen Jun, 1 _ carbene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl+pentene, 4 6 dimethyl 1-heptene, 4-ethylenecyclohexene, vinyl ring burned, water drop 38 200900545 diene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene , cyclooctene, C4-C40 diene, including, without limitation, 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1, 7-octadiene, 1,9-decadiene, other C4-C20 hydrazine; - olefin, and the like. In certain embodiments, the alpha-olefin is a mixture of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or the like. While any vinyl containing hydrocarbon can be used in embodiments of the invention, practical problems (such as monomer availability, cost, and the ability to readily remove unreacted monomers from forming a polymer) are When the molecular weight becomes too high, it becomes more problematic. 10 The polymerization process described herein is suitable for the manufacture of a monovinylidene aromatic monomer (including styrene, o-methyl styrene, p-methyl styrene, t-butyl phenyl hydrazine, etc.). Olefin polymer. In particular, heteropolymers comprising ethylene and styrene can be made according to the techniques herein. Alternatively, a copolymer comprising ethylene, styrene and C3-C2()a; an olefin, optionally 15 comprising C4-C2Q dilute, may be made. Suitable non-conjugated diene monomers can be linear, branched or cyclic hydrocarbon dienes having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include, without limitation, linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1, 9-decadiene, a branched chain acyclic diene, such as 20 5-mercapto-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7 - dimethyl-1,7-octadiene, and a mixed isomer of dihydromyricene and dihydrocarbene, a monocyclic alicyclic diene such as 1,3-cyclopentadiene; 1,4 - cyclohexadiene; 1,5-cyclooctadiene, and 1,5-cyclododecadiene, and polycyclic alicyclic fused and bridged cyclic dienes, such as tetrahydroanthracene, methyltetrahydrogen Anthracene, dicyclopentadiene, bicyclo-(2,2,1)- 39 200900545 heptane-2,5-diene; alkenyl, alkylene, cycloalkenyl and cycloalkylene norbornene, For example, 5-methylene-2-norbornene (MNB); 5_propenyl_2_norborn, 5-isopropylidene-2-norbornene, 5-(4,cyclopentenyl )norbornene, 5-cyclohexylene-2_norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the diene typically used in the manufacture of EPDM, particularly preferred are diene 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), and 5-vinylidene-2-nor Borbornene (VNB), 5_mercapto-2_norbornene (MNB), and dipentarene (DCPD). Particularly preferred is a diene 5-ethylidene-2-norborn (ENB), and l,4-hexadiene (Hd). 10 15 A class of elastomeric heteropolymers which may be prepared according to embodiments of the invention are ethylene, C3_C2〇a-olefins (particularly propylene) and optionally one or more diene monomers. Preferred α-olefins for use in the examples of the present invention are indicated by the formula CHfCHR* wherein R* is a linear or branched alkyl group of 1 to 12 carbon atoms. Examples of suitable alpha-olefins include, without limitation, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-mercapto-indenyl pentane, and 1-octene. A particularly preferred α-olefin is propylene. Polymers based on propylene are generally referred to in the art as hydrazine or EPDM polymers. Suitable dienes for use in the manufacture of such polyconjugates (especially multi-block EPDM-type polymers) comprise linear or branched chains, rings or multiples containing co-conducting or non-co-rolling rolls of up to 20 carbon atoms A cyclic diene. Preferred dienes include 1,4-pentadiene, 14-hexane dipenta-5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylene-2-nor The borneol is thin. A particularly preferred diene 5-ethylene-2_norborn is thin. Because the dilute-containing polymer contains alternating sections or blocks containing larger or smaller amounts of dienes (including none) and alpha-olefins (including none), and two are included in 200900545 α-smoke The total amount can be reduced without losing the properties of the polymer thereafter. That is, because a dilute and a-ene mono-system is preferentially incorporated into one of the polymers, rather than uniformly or randomly within the entire polymer, T is more utilized by AM. 'And thereafter, the crosslink density of the polymer can be controlled better than 5. These crosslinkable elastomers and cured products have advantageous properties, including more tensile strength and better elastic recovery. The heterogeneous copolymers of the present invention, which are manufactured by a two catalyst in a different amount of comonomer, have a block weight ratio formed thereby from 95j to 5:95. The elastomeric polymer desirably has a matte content of from 2% to 9%, a diene content of from ί to 1%, and an "-olefin content of from 1% to 8% by weight based on the total weight of the polymer. Benchmark. Further preferably, the multi-block elastomeric polymer has an ethylene content of from 60 to 90%, a diene content of from 01 to 10%, and an olefin content of from 10 to 40%, based on the total weight of the polymer. Preferably, the mono-compound is a high molecular weight polymer having from 1 Torr, from about 15 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000 by weight average molecular weight (Mw), and less than 3.5. More preferably less than 3.0 dispersity' and 1 to 250 Mooney viscosity (ML (1+4) 125. 更. More preferably, these polymers have an ethylene content of 65 to 75%, 〇 to 6% of the diene content, and 20 to 35% of the α-olefin content. 20 The ethylene/α-olefin heteropolymer can be functionalized by the incorporation of at least one functional group in its polymer structure. The base may include, for example, ethylenically unsaturated mono- and di-functional carboxylic acids, ethylenically unsaturated mono- and di-functional carboxylic anhydrides, salts thereof and esters thereof. These functional groups may be bonded to ethylene/α-olefin heterogeneous copolymerization. ' or may be copolymerized with ethylene and optional additional comonomers. 41 200900545 A heteropolymer of ethylene, a functional comonomer, and optionally other comonomers. Used to graft functional groups to polyethylene. The above is described in, for example, U.S. Patent Nos. 4,762,890, 4,927,888 and 4,950,541. The disclosures of these patents are hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety the the the the the the the the the the the the the the the The base may typically be present in the copolymerized functionalized heterogeneous copolymer in an amount of at least about 1.0% by weight, preferably at least about 5% by weight, and more preferably at least about 7% by weight. The functional groups are typically less than A functionalized heterogeneous copolymer present in the copolymer form in an amount of about 40% by weight, preferably less than 10% by weight, and more preferably less than about 25% by weight. Test Methods In the following examples, the following analytical techniques Used: GPC method for samples 1-4 and AC 15 Robotic arm for automating the treatment of a heated needle set at 160 °C is used to add enough 1,300, Ionol to stabilize the 1,2,4 - Trichlorobenzene to each dried polymer sample yielding a final concentration of 30 mg/ml. A small glass stir bar is placed into each tube and the sample is heated to a heated orbital shaker rotating at 250 tpm to 160 ° C for 2 hours. Then, 20 The polymer solution was reduced using the automated liquid-handling robot and the dilution was heated needle set to 160 ° C to the 1 mg / ml of.

The Symyx Rapid GPC system was used to determine the molecular weight data for each sample. A Gilson 350 pump set to a flow rate of 2.0 ml/min was used to deliver three Plgel 10 micron (//m) mixes 42 200900545 combined B 300mm x 7.5mm columns in a series placed and heated to 160 ° C, pump Take as a mobile phase with 3 〇〇ppm Ionol 疋 之 以 以 以 以 ι ι ι ι ι ι ι ι ι ι. The p〇iymer Labs ELS 1000 detector was set to 165 with an evaporator set at 250 °C. (:sprayer' and nitrogen flow rate of 60-80 psi (400-600 kPa) is set to ι·8 SLM. The polymer sample is heated to 160 ° C, and each sample uses a treatment liquid. The robotic arm and the heated needle were injected into the 250 β 1 loop. Polymer samples were analyzed using a series of two switched loops and overlapping injections. Sample data was collected and analyzed using Symyx EpochTM software. Peaks were manually integrated and molecular weight information The calibration curve for the polystyrene standards is uncorrected. The standard CRYSTAF method is distributed by CRYSTAF using CRYSTAF 200 units available from PolymerChar, Valencia, Spain. 1,2,4 trichlorobenzene (0-66 mg/ml) at 160 ° C for 15 hours, 15 and stabilized at 95 ° C for 45 minutes. At a cooling rate of 0 2 t / minute, the sampling temperature range is 9 5 to 3 0 C. Infrared detector is used to measure the concentration of polymer solution. The cumulative soluble concentration is measured when the polymer is crystallized at a temperature drop. The analysis of the cumulative distribution reflects the short-chain branching distribution of the polymer. CRYSTAF Odd temperature And the area is identified by a peak analysis module included in the crystaF software 20 (2001 _b_ version 'PolyChar, Valencia, Spain). The CRYSTAF peak finding routine is either the maximum of the dW/dT curve and the identification peak of the derivative curve. The area between the maximum positive bends on the side and the peak temperature. To calculate the CRYSTAF curve, the preferred processing parameters are the temperature limit of 7 〇 ° c and the number of smooth 43 43 200900545 above the temperature limit of 0.1 and below the temperature limit of 0.3. DSC Standard Method (Excluding Samples 1-4 and AC) Differential broom calorimetry results were determined using a TAI Ql〇〇〇 type DSC equipped with an RCS cooling accessory and an autosampler. 50 mL/min of nitrogen purge gas A flow of 5 was used. The sample was placed in a press at about 175. (: pressed into a film and melted, and then cooled to room temperature with air (25. 〇. Then, 3-10 mg of the material was cut into a 6 mm diameter dish). Accurately weighed, placed in a light aluminum pan (about 5 〇 mg), and then curled off. The thermal behavior of the sample was studied with the following temperature profile. The sample was rapidly heated to 180 ° C and maintained isothermal for 3 minutes to move Except for any previous ίο History. The sample was then cooled to _4 〇 ° C at a cooling rate of 10 ° C / min and maintained at -40 ° C for 3 minutes. Then, the sample was heated to 150 C at a heating rate of urc / min. Cooling and second The secondary heating curve was recorded. The DSC molten bee was measured at a maximum thermal flow rate (W/g) relative to the linear baseline drawn between -30 °C and the end of the smelting. The heat of fusion was measured using the linear basis I5 line at -30 C and the area under the melting curve between the ends of the graft. GPC Method (Excluding Samples 1-4 and A-C) The gel permeation chromatography system consisted of either P〇lymer Laboratories PL-210 or Polymer Laboratories PL-220. The column and the rotating cell were operated at 140 °C. Three P〇iymer LaWat〇ries % 20 micron hybrid _B column was used. The solvent is 1,2,4-trichlorobenzene. The sample was prepared at a concentration of 50 ml of a solvent containing 200 ppm of butylated hydroxytoluene (BHT) in a solvent. The sample was prepared by slightly mixing for 2 hours at 16 °C. The injection volume used was 100 microliters and the flow rate was 1 milliliter per minute. The GPC column calibration was performed with 21 narrow molecular weight distribution polystyrene 44 200900545 standards (molecular weight range 580 to 8, 4 〇〇, 〇〇〇, and in a 6 "cocktail" mixture configuration' and Implementation with at least 10 separations between individual molecular weights. Standards were purchased from p〇lymer Laboratories (Shropshire, UK). Polystyrene standards are equal to or greater than! The molecular weight of ruthenium, osmium was prepared in 0.025 g of 5 〇 5 ml of solvent, and was prepared at 0.05 g for less than 1, 〇〇〇,000 molecular weight in 50 ml of solvent. The polystyrene standards were dissolved at 80 ° C and gently stirred for 3 minutes. The narrow standard mixture is operated first and the highest molecular weight component is reduced to minimize degradation. The peak molecular weight of the polystyrene standards was converted to polyethylene molecular weight using the following equation (as described by Williams and Ward, J. Polvm. 10 Sci, Polym. Let) 6, 621 (1968): Μ Polyethylene = 0.431 (Μ Polystyrene) Polyethylene molecular weight calculations were performed using Viscotek TriSEC software version 3.0. Compression set 15 Compression set was measured according to ASTM D 395. Samples were stacked by 3.2 mm, 2_0 mm and 0.25 mm thick 25.4 mm diameter The round dish was prepared to achieve a total thickness of 12.7 mm. The dish was cut by a press molding of 12.7 cm X 12.7 cm molded by a hot press under the following conditions: at 0 °C at 190 ° C After 3 minutes, it was continued at 860 ° C for 86 minutes at 86 MPa for 2 20 minutes, after which the inside of the press was cooled with a cold running water of 86 MPa. The density was used to measure the density of the sample according to ASTM D 1928. The measurement was performed using ASTM D792. Method B was pressed into the sample within 1 hour. Flexure / secant modulus / storage modulus 45 200900545 The sample was compression molded using ASTM D 1928. Flexure and 2% secant modulus were measured according to ASTM D-790. The quantity is based on ASTM D 5 026- 01 or equalization technique measurement Optical properties 5 〇 _ 4 mm thick film was compression molded using a hot press (Carver #4095-4PR1001R). The pellets were placed between Teflon sheets at 55 psi ( 380 kPa) was heated at 190 ° C for 3 minutes, then at 1.3 MPa for 3 minutes, and then at 2.6 MPa for 3 minutes. Then, the film was cooled in a press machine with a flow of cold water of 1.3 MPa for 1 minute. Membranes were used for optical measurements, tensile ten behavior, recovery, and stress relaxation. Transparency was measured using BYK Gardner Haze-gard as specified by ASTM D 1746. The 45 ° gloss was BYK Gardner Glossmeter Microgloss 45 as specified by ASTM D-2457. measuring.

15 Internal turbidity is based on BYK based on ASTM D 1003 Procedure A

Gardner Haze-gard measurement. Mineral oil is applied to the surface of the membrane to remove surface scratches. Mechanical Properties - Tensile, Hysteresis, Tear The stress-strain behavior of uniaxial tension was measured using ASTM D 1708 micro-resistance 20 samples. The samples were stretched with Instron at 21 ° C at 500% min-1. Tensile strength and elongation at break were reported as an average of 5 samples. The 100% and 300% lag images were determined using ASTM D 1708 micro-tensile samples with periodic loading from InstronTM instruments to 1% and 300% strain. The sample was loaded at 21 C with a load of 267% min 1 and unloaded for 3 cycles. At 46 200900545 300% and 8 (Tc periodic experiments were carried out using an environmental chamber. In the 8 叱 experiment, the sample was equilibrated at the test temperature for 45 minutes before the test. The periodic experiment at 2 rc, 3 〇〇% should be , The initial unloading period is 15〇0/. The strain shrinkage should be recorded. The percentage of recovery from all experiments is calculated from the strain at the first unloading cycle using the cut-back to the baseline. The percentage of recovery is defined as: Complex % ^-f ^ X too £f where ' ef is the strain obtained by the critical load' and the strain when the load is returned to the baseline during the first unloading cycle. 10 Stress relaxation is performed using the Instr〇 The nTM instrument was measured at 5 〇 % strain and 37 ° C for 12 hours. The metrology geometry 76 _ χ 25 χ 〇 4 mm. After equilibrating for 45 minutes at 37 t in the environmental chamber, the sample was stretched to 50% strain at 333% minutes. Stress is recorded as a function of time for 12 hours. The percent stress relaxation after 12 hours is calculated using the following equation: Stress relaxation % = hr X|0q L ❶ 15 where L〇 is 0 when 50% strain is applied and L12 is at 50% strain load after 12 hours. The test was performed on a sample with a density of 〇88 g/cc* less using an instronTM instrument. The geometry consisted of a metering section of 76 mm χ丨3 mm X 〇_4 mm with cut-in at half the length of the sample A 2 mm cut in sample 20. The sample was stretched to break at 508 mm min-1 on page 21. The tear energy was calculated as the area under the strain at which the stress-extension curve was up to the maximum load. The average of at least 3 samples was reported. 47 200900545 ΤΜΑ Thermomechanical analysis (through temperature) is carried out on a 30 mm diameter χ 3.3 mm thick compression molded disc (formed at 180 ° and 1 MPa molding pressure for 5 minutes and then quenched by air) The instrument used was TMA 7, which is a brand of 5 Perkin-E1mer. For this test, a probe with an i.5 mm radius tip (P/NN519-0416) was applied to the surface of the sample dish with a force of 1 N. The temperature rises from 25 ° C at 5 ° C / min. The probe penetration distance is measured as a function of temperature. The test ends when the probe has penetrated into the sample by 1 mm.

DMA 10 Dynamic Mechanical Analysis (D ΜΑ) is a compression molded disc (which is placed in a hot press at 18 Torr. Torr and 10 MPa for 5 minutes, then cooled in a press at 90 C / min water) The upper measurement ◦ test was performed using an Ares controlled strain rheometer (TA Instruments) equipped with a double cantilever beam device for torque testing. 15 1.5mm sheet is pressed and cut into 32 χ 12mm strips. The two ends of the sample were placed between devices with a spacing of 1 mm (clamping interval Δ[) and subjected to a continuous temperature phase of -1 〇〇 ° C to 200 ° C (5 每 per stage). At each temperature, the torsion modulus G is measured at an angular frequency of 10 rad/s. The strain amplitude is maintained between (U% and 4%) to ensure that the torque system is sufficient and the measurement dimension is maintained. In a linear system, the initial static force of 10 grams is maintained (automatic tension mode) to avoid slack in the sample when thermal expansion occurs. Therefore, the clamping interval AL increases with temperature, especially above the melting point or softening point of the polymer sample. The test is stopped at the maximum temperature or when the gap between the devices reaches 65 mm. 48 200900545 Melt index blush index ' or 12, measured according to ASTM D 1238, condition 190 ° C / 2.16 kg. Melt index, or I1Q, It is also measured in accordance with ASTM D 1238, condition 190 ° C / l 〇 kg.

5 ATREF Analytical Temperature Rising and Stripping Fractionation (AT R EF) analysis is based on US Patent No. 4,798,081 and Wilde, L.; Ryle, TR; 1〇Knobeloch, branching from , and polyethylene and ethylene copolymers The distribution is determined by the method described in J. Polym. Sci., 20, 441-455 (1982), which is hereby incorporated by reference in its entirety. The composition to be analyzed was dissolved in trichlorobenzene and crystallized in a column containing an inert support (stainless steel pellet) by slowly dropping the temperature to 2 ° C at a cooling rate of 〇1 cC / /min. The column is equipped with an infrared detector. Then, the ATREF chromatographic curve was generated by slowly increasing the temperature of the elution solvent (tri-benzene) from 20 ° C to 120 t at a rate of 1.5 X: / minute: 15 The crystallized polymer sample was eluted from the column. 13C NMR analysis The sample was prepared by adding about 3 grams of a 50/50 mixture of tetrachloroethane-d2/o-dichlorobenzene to a 0.4 gram sample in a 10 mm NMR tube. The sample is heated to 150 by heating the tube and its contents. (: dissolve and homogenize. The data is collected using a JEOL EclipseTM 400MHz spectrometer or a Varian Unity PlusTM 400MHz spectrometer (corresponding to a 13c resonance frequency of 100.5 MHz). The data uses 4000 transients per data file and Obtained with a 6-second pulse repetition delay. To achieve the minimum signal-to-noise ratio for quantitative analysis, several data files are added together. The spectral width is 25,000 Hz, and 49 200900545 The minimum weight size is 32 K data points. The probe was analyzed by a l〇mm wide band probe at 130 C. The comon monomer was used in the Randall triad method (Randall, J_C.; JMS-Rev. Macromol. Chem. 30 Phys., C29, 201-317 ( 1989), which is hereby incorporated by reference in its entirety in its entirety. 5 The TREE fractionation of the polymer by TREF is achieved by dissolving 15-20 grams of polymer in 2 liters by stirring at 160 °C for 4 hours. 1,2,4-trichlorobenzene (TCB) was carried out. The polymer solution was forced to a spherical quality of 30-40 mesh (600-425 // m) by 15 psig (100 kPa) of nitrogen. Glass beads (available from potters 10 Industries, HC 30 Box 20, Brownwood, TX, 7680) 1) and non-recorded steel, 0.028" (0.7 mm) diameter tangential pellets (available from peuets, Inc. 63 Industrial Drive, North Tonawanda, NY, 14120) 60:40 (v:v) mixture filled 3吋 x 4 inches (7.6 cm x 12 cm) steel pipe column. The pipe string is immersed at the initial setting of 160. (: Thermal control oil casing. The pipe column is first ballistic 15 cooled to 125 ° C ' Then, 〇 〇 4 ° C / min slowly cooled to 20 ° C, and maintained for 1 hour. The new TCB was introduced at about 65 ml / min, while the temperature was increased by 0.167 C / min. From the preparation of TREF column about 2000 Multiple fractions of the extract were collected in 16 stations (hot fraction collector) and the polymer was concentrated in each fraction using a 20 rotary evaporator to a polymer solution of about 50 to 100 ml. The concentrated solution was allowed to stand overnight before adding excess methanol, filtering and rinsing (about 3 〇〇 5 mM methanol) containing the final rinse. The filtration step was carried out at a 3-position vacuum-assisted filtration station using 5 〇 to m. Fluoroethylene coated filter paper (available from Osmonics Inc., Cat# Z50WP04750) was implemented. Filtered 50 200900 The 545 grades were dried overnight in a 60 ° C vacuum oven and weighed on an analytical scale before further testing. Melt Strength The melt strength (MS) was measured by using a capillary rheometer equipped with a 2 〇:1 mold having a diameter of about 2.5 degrees. After the sample is balanced at i9〇°c for 10 minutes, the piston is! Speed operation of 吋 / min Hong 54 cm / min). The standard test temperature is 19 〇 ° c. The sample was axially stretched at an acceleration of 2.4 mm/sec 2 to a set of acceleration clamps located 1 mm below the mold. The required tensile resistance is recorded as a function of the exit speed of the nip rolls. The maximum tensile strength reached during the test was defined as the melt strength. In the case of a polymer melt exhibiting tensile resonance, the tensile strength before the start of tensile resonance is obtained as the melting strength. The melt strength is recorded in centiNewtons (cN). Catalyst "overnight" is used when it is used for about 16-18 hours, and room temperature" 15 refers to the temperature of 20-25 °C, and, mixed alkane, the term refers to available from ExxonMobil A mixture of commercially available C6-9 aliphatic hydrocarbons is available from Chemical Company under the tradename Isopar E(g). Where the compound name is not in conformity with its structural representation, the structural representation will be controlled. The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using a 2 dry oven technique. All solvents used were HPLC grade and dried prior to use. MMAO refers to a modified methyl ester, which is commercially available from Akz〇_N〇bie Corporation, modified with triisobutylaluminum methylaluminoxane. The preparation of catalyst (B1) is carried out as follows. 51 200900545 必尔(1-methyl 匕 练 ) )) methyl imino 3,5-di-t-butyl salicylaldehyde (3 gram) added to 1 liter of isopropylamine The solution quickly turned bright yellow. After the ambient temperature _3 hours, the 5th substance was removed under vacuum to produce a bright yellow crystalline solid (97% yield). Although 1,2-etc. (Imino)methyl)(2-indole) is a (1-methylethyl) group (2_yl)- 3,5-di (t-butyl) A solution of phenyl)imine (605 mg, 2.2 mmol) was slowly added to a solution of Zr(CH2Ph)4 (500 mg, U mmol) in 5 mL of toluene. The yellow solution was stirred for 30 minutes. The solution was removed under reduced pressure to give the desired product as a reddish brown solid. The preparation of the catalyst (B2) was carried out as follows: (1-(2-methylcyclohexyl)) Base) (2_醯氧其j 5·二(第芏15 butyl) 笨) The amine 2-mercaptocyclohexylamine (8.44 ml, 64.0 mmol) was dissolved in methanol (9 mL), and di-tert-butyl-salicylic acid (10-00 g, 42 67 mmol) was added. The mixture was stirred for 3 hours, then cooled to _25 for 12 hours. The formed yellow solid precipitate was collected by filtration and washed with cold methanol (2 χ 15 20 ml) and then dried under reduced pressure. 1U7g of a yellow solid. 1H NMR and the desired product as a mixture of isomers. _..?.)-.U dance bis-(1-(2-methylcyclohexyl)ethyl) (2 y y early _ ^_Bis(tributyl)phenyl)imido) is more than 200 ml of toluene (1_(2-methylcyclohexyl)ethyl (2 methoxy 52 200900545 -3, A solution of 5-bis(t-butyl)phenyl)imide (7 63 g, 23 2 mmol) was slowly added to 6 mL of Zr(CH2Ph)4 (5 28 g, u 6) A solution of millimolar. The dark yellow solution formed was at 25. (: stirring for 1 hour. The solution was further diluted with 680 ml of toluene to give a solution having a concentration of 〇〇〇 783 M. 5 cocatalyst 1 tetrakis(pentafluorophenyl) Borate methyl dichloride (Cm a mixture of an octaalkyl)ammonium salt (hereinafter referred to as an aliphatic primary amine decanoate) substantially as disclosed in Example 2 of U.S. Patent No. 5,919,988, by a long chain trialkyl group. It is prepared by reacting an amine (ArmeenTM M2HT, available from Akzo-Nobel, Inc.), HC1 and Li[B(C6F5)4]. 10 Co-catalyst 2 bis(tris(pentafluorophenyl)-alkane)-2-10 A mixture of monoalkylimidazolidines c^i8 alkyldimethylaluminum salts was prepared according to Example 16 of U.S. Patent No. 6,395,671. The shuttling agent used for the shuttle contains diethyl zinc (DEZ, SA1), di(isobutyl) (SA2), di(n-hexyl)zinc (Sa3), triethylaluminum (TEA, 15 δΑ4), three Octyl aluminum (SA5), triethylgallium (SA6), isobutyl aluminum bis(dimethyl(t-butyl)oxyl) (SA, isobutyl aluminum bis(bis(trimethyldecane) Base) decylamine (SA8), n-octyl aluminum di(pyridine-2-oxide) (SA9), bis(n-octadecyl)isobutylaluminum (SA10), isobutylaluminum bis (two) (n-pentyl) decylamine) (SA11), n-octyl aluminum bis(2,6-di-t-butylbenzene oxide 20) (SA12), n-octyl aluminum di(ethyl (1-naphthyl)醯amine)0Λ13), ethylaluminum bis(second butyl bisfluorene oxime oxide) (SA14), ethyl dimethyl (bis(trimethyldecyl) decylamine) (SA15), ethyl aluminum Bis(2,3,6,7-dibenzo-1-azepine) (SA16), n-octyl aluminum bis(2,3,6,7-dibenzo-indole-aza Cycloheptane decylamine (SA17), n-octyl aluminum bis(dimethyl(t-butyl)phosphonium oxide 53 200900545 (recognition 18), ethyl zinc (2,6-diphenyl phenoxide) (3, 8 19), and ethyl zinc (third butoxide) (SA20).

1-4, bh#You 丨AC generally high throughput throughput parallel polymerization conditions 5 polymerization using a high throughput throughput parallel polymerization reactor available from Symyx technologies, Inc., and Substantially operating in accordance with U.S. Patent Nos. 6,248,540, 6,030,917, 6,362,309, 6,306,658, and 6,316,663. The ethylene copolymerization is carried out at 13 〇 (: and at 200 psi (1.4 MPa) with ethylene as needed and using 1.2 equivalents of cocatalyst 10 1 (based on the total catalyst used) (when MMA0 is present, equivalent) The series of polymerizations were carried out in a parallel pressure reactor (PPR) containing 48 individual reactor units in a 6 x 8 array equipped with pre-weighed glass tubes. The operating volume is 6 〇〇 / / m. Each unit controls the temperature and pressure, and provides agitation by individual stirring paddles. 15 monomer gas and quenching gas are directly sent into the PPR unit by pipeline, and by Automatic valve control. The liquid reagent is added to each reaction unit by a robot arm by a syringe, and the solvent of the reservoir is mixed and burned. The order of addition is a mixed combustion solvent (4 ml), ethylene, 1-octene comon (1) ML), co-catalyst or co-catalyst 1/MMA0 mixture, shuttling agent, and catalyst or catalyst mixture. 20 When a mixture of cocatalyst 1 and MMA0 or a mixture of two catalysts is used, the reagent is added immediately before the addition to the reactor. Yu Xiao Premixed in the glass bottle. When the reagent is omitted in the experiment, the above addition sequence is maintained for about 1-2 minutes until the predetermined ethylene consumption is reached. After the C0 quenching, the reactor is cooled, and The glass tube was removed. The tube was transferred 54 to 200900545 to a centrifugal/vacuum drying unit and dried for u u hours. The tube containing the dry polymer was weighed and the difference between this weight and the weight of the container produced a net polymer yield. The formula is included in the Table!. In the table and elsewhere in this application, the comparative compounds are indicated by an asterisk (*). 5 Examples 1-4 demonstrate the synthesis of linear block copolymers by the present invention, which are formed by extremely narrow formation The MWD confirmed that when DEZ is present, it is essentially a monomodal copolymer, and in the absence of DEZ, it is a product of a bimodal broad molecular weight distribution (a mixture of individually prepared polymers). Since the catalyst (A1) is known as a nanocomposite catalyst ( B1) Table 1*氺氺AB c 1 06 6 6 6 6 6 ο ο ο ο ο 0·0·0·0·0· More octene, different blocks or zones of the copolymer of the invention Segment system 10 based on branch or density The difference is catalyzed by catalyzed by Λ 1Λ 1Λ II 1 H f0·0·0·0·0·0· Cocatalyzed MMAO penetrant A* Mn Mw/Mn hexvls1 & iumol, iumoH iumol) 0.066 0.3 - 0.1363 300502 3.32 0.110 0.5 - 0.1581 36957 1.22 2.5 0.176 0.8 - 0.2038 45526 5.302 5.5 0.192 - DEZ(8.0) 0.1974 28715 1.19 4.8 0.192 - DEZ(80.0) 0.1468 2161 1.12 14.4 0.192 - TEA(8.0) 0.208 22675 1.71 4.6 0.192 - TEA(80.0) 0.1879 3338 1.54 9.4 Content of <:6 or higher chain per 1000 carbons 2 Bimodal molecular weight distribution 15 It was found that the polymers produced according to the present invention have relatively comparative properties compared to polymers prepared in the absence of a shuttling agent. Narrow polydispersity (Mw/Mn), and large block copolymer content (trimer, tetramer, or greater). Further characteristic data of the polymer of Table 1 is determined with reference to the drawings. More specifically, the DSC and ATREF results show the following: 20 The DSC curve of the polymer of Example 1 shows a melting point (Tm) of 115·7 ° C and a heat of fusion of 158 J/g. The corresponding CRYSTAF curve shows a high number of bees at 34.5 °C with a peak area of 52.9%. The difference between DSC Tm and Tcrystaf is 81.2 °C. 55 200900545 The DSC curve for the polymer of Example 2 shows a peak with a melting point (Tm) of 1 〇 9.7 ° C with a heat of fusion of 214.0 J/g. The corresponding CRYSTAF curve shows a peak at 46.2 ° C and has a peak area of 57.0 %. The difference between DSC Tm and Tcrystaf is 63.5 °C. 5 The D S C curve of the polymer of Example 3 shows a peak with a melting point (T m ) of 12 0.71 and a heat of fusion of 160.1 J/g. The corresponding CRYSTAF curve shows a peak at 66_1 ° C and has a peak area of 71-8%. The difference between DSC Tm and Tcrystaf is 54.6 °C. The D S C curve of the polymer of Example 4 was shown to have a 〇 4.5. (: melting point (T m) 10 peak with a heat of fusion of 170.7 J/g. The corresponding CRYSTAF curve shows a peak at 30 ° C and has a peak area of 18.2%. The difference between DSC Tm and Tcrystaf 74.5 ° C. Comparative Example 03 (: The curve shows 90_0 ° (: the melting point (Ding 111), and has a heat of fusion of 86.7 J / g. The corresponding CRYSTAF curve shows a peak of 15 peaks at 48.5 ° C, And having a peak area of 29.4%. These values are all consistent with the low density resin. The difference between DSC Tm and Tcrystaf is 41.8 ° C. The DSC curve of Comparative Example B shows the melting point (Tm) of 129.8 ° C, with 237.0 The heat of fusion of J/g. The corresponding CRYSTAF curve is at 82.4. (: shows several peaks and has a peak area of 83.7%. These values are consistent with high-density tree 20 lipid. The difference between DSC Tm and Tcrystaf 47.4 ° C. The DSC curve of Comparative Example C shows 125.3. (: melting point (Tm), with a heat of fusion of 143.0 J / g. The corresponding CRYSTAF curve is at 81.8. (: shows the peak number ' and has 34.7% The peak area and a lower crystallization peak at 52.4t. The interval between the two peaks is related to the presence of highly crystalline and low crystalline polymers - 56 200900 545. The difference between DSCTm and Tcrystaf is 43.5 °C.

The A1/B2+DEZ continuous solution polymerization is carried out by a computer controlled 5 疋 da da reactor equipped with an internal stirrer. Purified mixed burning solution (IsoparTM E, available from

ExxonMobil Chemical Company), 2.70 lbs/hr (1.22 kg/hr) of ethylene, 1-octene and hydrazine (if used) were supplied to a 3.8 liter reactor equipped with a jacket for temperature control and an internal thermocouple. The solvent supply to the reactor is measured by a mass flow controller. The variable speed diaphragm pump controls the solvent flow to the reactor at 10 speeds and pressure. When the pump is discharged, a side stream is taken to provide a flushing stream for the catalyst and cocatalyst 1 injection line and reactor agitator. These flows are measured by a Micro-Motion mass flow meter and are measured by a control valve or by manually adjusting the needle valve. The remaining solvent is mixed with 1-octene, ethyl hydrazine, and hydrogen (if used) and supplied to the reactor. The mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled by the use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst component solution was metered using a pump and mass flow meter' and mixed with the catalyst rinse solvent and introduced into the bottom of the reactor. The reactor was run at 500 psig (3_45 Mpa) with full liquid gymnastics and stirred vigorously. The product is removed via an outlet line at the top of the reactor. 2〇 All outlet lines of the reactor are traced and isolated by water vapor. The polymerization reaction is stopped by adding a small amount of water to the outlet line with any stabilizer or other additive and passing the mixture through the static mixture. The product stream is then heated by a heat exchanger prior to devolatilization. The polymer product was recovered by extrusion using a devolatilizing extruder and a water-cooled granulator. Method Details and Conclusions 57 200900545 The results are included in Table 2. The polymer properties selected are provided in Table 3. 58 200900545 9% si·# ΟΟΓ^ΓΠΓ^·»—'»—'ON·—'V〇〇〇N^Hf^C^.S〇〇^^ii^P5S5sSPiS2:?5?5ii38 Q> (* \J r— *« f'vj (Sj C*Nj ·—* th »—< «-Η 1-^ l—( c^CSO *»4 vm w ^aa *«· 〇Q 〇〇«- ^ΌΟ^^ΓΊΓΛ^ΟΟ fO inch ooasw^^OfnriocNmv'iONOTrr^^-oosr^ odcisodoso^ONCicScjO'sciasOsoxo'o^aso oooooooooqooCnOnOsooOsdqoocoOsoooo^ £.t -Ί -Ί SZ/I 0-1 itn 69.1 on 89· I 5.1 5.1 Ζ9Ί 09Ί 59.1 SI -, 1 卜寸.1 18.1 When, ''/七令5许¥荽<0铋5£ Is 90S i 0 § 9-6 inch Z-inch I -- -i 0 Bu s 61 inch-inch IJZHa] /PH"' ^-έ^sdd s- 举咪- 涑i 0·0 -T SO 60Ό 0ΙΌ i so 0ΙΌ 慧^- -.0 es -Ό 9Γ0 ΠΌ i -.0 9-mi 9- εκι 9-§1 I €?l §ϊ?? Box zaa so 60Ό iro §Ό i -.0. 05 SO 60Ό -,0 6Γ0 s'o OS -.0 ii 6v 〇o 〇oossoo Is iH [,) ooooo 寸 r^ 卜 soovr-f^^·?^ »—· 〇〇fvj ψ^* *-* fv| OOOOOCiOOd: S 〇〇〇〇〇〇〇n Cui 2〇« ooooo o = 5=Ρ3Λ r— mmcocna sr^> _ s 0Γ0 0-0 inch Γ0 i "Ό -Ό 9S ΖΙ 5 i so 01Ό i i '-Ό ϊ / s 1VI # - For 3 · - 37'-uidd -V s- give

F—< i—^ ^ _ — · · I 9—4 I 4 I ", l· P. seven p_e8s-4"々/ 1 £ 瑟 sKa3 z-,, Is Ii s Ϊ 33 0- 5 3- 5 1- Ϊ 0-3 £-i 3 iysi „ 06,9£ „ 0卜_-3 36.inch 5 丨3 9-magic „ g-0-06,3⁄4 s3 •ll ,, •6 3 Bu· -3- -0 69Ό 』zM+Jas=s*s^/#♦ △ age 々 々, - spider negative order s-^^OWMg^^g 资^碉爿龚令铋 a M>q1K-裨4«:| |鹄^# ^^-^'^^(^^^(^^(fh-H-gJ-^-loM-f^li-csK^toc^Qlf'ts--cl-I)-^^ ^ ®-4Ί?(ΐίΒ-(硪-=--ίΝ·^ψ--9)(Ί·Μ-ζ-_ _5(硪蚪硝tswlc-z)I 锲 ls(fi4(^tol-®- -I)u-9tvr)-N;r 娥令/令&&;; distinctive _ 冢镩驷驭洳+铢二锑qr 59 200900545 teiiIJ.卑φϊ#ί!ί5Γ>^εϊ*

CR - l IS Ϊ Ι Ι Ι Ι & & & & & & Οο 5" ? 沄r< M wear p C strict « H § r"HS! fn Os s Dad O\ •>C o Ό <J\ rj § 1/1 s 苎η νζ Gan rj fN Vj^ &gt ;»S6 R gg民? μ -D ίΐ s O pan <P st 1 s CO flS s ΓΝ r: rs! Os «e 〇\ 3 o ΓΝ o r4 〇> Os £Ρ Ιδ C ο «# *; 〇r«"» i ϊ ϊ Ο ο Η 〇Ρ Π ο Β< Π V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V 1 ik 30 1—ii—1 1 ΓΝ •–^ g η Ο ΓΛ 1 t 8 fN W VO § £ § mg o. g Ch 14S,500 1 s if 1 £" co r. wi X f«-| S Ι/-Ι so I-- οί «Λ '•ό •n vc 't in <3 3 Uv •<C Kr <ϊ S 2 S cn 1^1 nd οσ Λ «η f- n* 3 S ι<-| ri o ri V5 vS vq only 3 t\ A ι^ι CT\ vj -; C'J ΙΛ I—· 1-4 O\ H ·*; ><£? r4 § 1 /: I-*. 5 y *s ύ S 〇uO sd iri 〇Λ CCr OU W 1XJ dw ου VI CN iXj Xl S3 tXi «C <η uC 芸uC. SO 'ύ I ώ 00 ¢0 VO 5s α> ac ci | in e: § Bodhidé I U: Id-i Bu· 3β «* |_J cj (Π 2 2 QO »-H 60 200900545 The polymer formed was tested by DSC and ATREF as in the previous examples. The results are as follows: The DSC curve of the polymer of Example 5 shows a peak with a melting point (Tm) of 119.6 ° C and a heat of fusion of 60.0 J/g. The corresponding CRYSTAF curve shows a peak at 5 47.6 ° C and has a peak area of 59.5%. DSC Tm and

The difference between Tcrystaf is 72.0 °C. The D S C curve of the polymer of Example 6 shows a peak with a melting point (T m ) of 115.2 ° C and a heat of fusion of 60.4 J/g. The corresponding CRYSTAF curve is at 44.2° (: shows the peak of the number and has a peak area of 62.7%. 03 (the difference between D and 111 Tcrystaf is 71.0 ° C. The DSC curve of the polymer of Example 7 shows 121.3 The peak of °C melting point (Tm) with a heat of fusion of 69.1 J/g. The corresponding CRYSTAF curve shows a peak at 49.2 ° C with a peak area of 29.4%. The difference between DSC Tm and Tcrystaf is 72.1 ° C. 15 The DSC curve for the polymer of Example 8 shows a peak with a 123.5 ° C melting point (Tm) with a heat of fusion of 67.9 J/g. The corresponding CRYSTAF curve shows a peak at 80.1 ° C with a peak of 12.7. The peak area of %. The difference between DSC Tm and Tcrystaf is 43.4 ° C. The DSC curve of the polymer of Example 9 shows a peak with a melting point (Tm) of 124.6 ° C and a heat of fusion of 73.5 J/g. The corresponding CRYSTAF curve shows a peak at 80.8 ° C and has a peak area of 16.0%. The difference between DSC Tm and Tcrystaf is 43.8 ° C. The DSC curve of the polymer of Example 10 shows a melting point of 115.6 ° C (T m a peak with a heat of fusion of 60.7 J/g. The corresponding CRYSTAF curve shows a peak at 61 200900545 40.9 ° C, and There is a peak area of 52.4%. The difference between DSC Tm and Tcrystaf is 74.7 ° C. The Dsc curve of the polymer of Example 11 shows a peak with a melting point (Tm) of 丨丨3 6 °c, and has a peak of 70.4 J/g. Heat of fusion. Corresponding cRYSTAf curve shows a peak at 5 39.6 ° C and has a peak area of 25.2%. DSC Tm and

The difference between Tcrystaf is 74. The dsc curve of the polymer of Example 12 shows a peak with a melting point (Tm) of 113.2 ° C and a heat of fusion of 48.9 J/g. The corresponding crystaF curve shows no peaks specific to or south of 30 C. (Tcrystaf 10 for further calculation purposes is therefore set to 3 °C). The difference between DSC Tm and Tcrystaf is 83.2 °C. The DSC curve for the polymer of Example 13 was shown to have 114.4. (: melting point (Tm) peak with 49.4 J/g heat of fusion. The corresponding crystAF curve is at 33_8° (: shows the peak number and has a peak area of 7.7%. 03 (: between Ding 111 and Tcrystaf) The difference was 84.4 ° C. 15 The DSC curve of the polymer of Example 14 was shown to have a peak of 120.8. (: melting point (Tm) with a heat of fusion of 127.9 J/g. The corresponding CRYSTAF curve shows the number at 72.9 ° C. Peak, and having a peak area of 92.2%. The difference between DSC Tm and Tcrystaf is 47.9 ° C. The DSC curve of the polymer of Example 15 shows a peak with a melting point (Tm) of 114.3 ° C and a 36.2 J/g The heat of fusion is corresponding to the CRYSTAF curve at 32.3° (: shows a peak number and has a peak area of 9.8%. 〇 8 (the difference between D 111 and Tcrystaf is 82.0 ° C. The DSC of the polymer of Example 16 The curve shows a peak with a melting point (T m) of 116 · 6 ° C and a heat of fusion of 44.9 J/g. The corresponding CRYSTAF curve shows a peak at 62 200900545 48.0 ° C, and has an ancient μ Λ〇 / and has 65.0% peak area. DSC Tm and

The difference between Tcrystaf is 68.63⁄4. The Dsc curve of the polymer of Example 17 shows the heat of fusion with a peak U.OJ/g of the depleted point (iv). The corresponding curve shows a peak at 5 43.1 ° C, and has a peak area of 5.6 〇 / and has a peak area of 56 · 8 / 〇. DSC Tm and

The difference between Tcrystaf is 72.93⁄4. The Dsc curve for the compound of Example 18 showed a peak with a melting point and a heat of fusion of eight 141.8 J/g. The corresponding CRYSTAF curve shows a peak at 70.0 ° C and is right-like. / Α and has a peak area of 94.0%. The difference between DSC Tm and 10 Tcrystaf is 5〇.5°c. The Dsc curve of the polymer of Example 19 showed a melting point (peak of Ding' and a heat of fusion of 174.8 J/g. The corresponding crystaf curve showed a number of peaks at 79.9 C and had a peak area of 87 9%. The difference between DSC Tm and Tcrystaf is 45.〇°c. 15 The DSC curve of the polymer of Comparative Example 0 shows a peak with a melting point (Tm) of 37.3 °C and a heat of fusion of 31 _6 J/g. Corresponding CRYSTAF curves show that there is no peak equal to or above 30c. These values are consistent with low density resins. The difference between DSCTm and Tcrystaf is 7.3 ° C. The DSC curve of the polymer of Comparative Example E shows 124.0 X: melting point (Tm) peak of 2〇 and has a heat of fusion of 179.3 J/g. The corresponding crystAF curve shows a peak at '79.3 ° C and has a peak area of 94.6%. These values are high density. The resin was consistent. The difference between DSCTm and Tcrystaf was 44.6 ° C. The DSC curve of the polymer of Comparative Example F showed a melting point (Tm) of 124.8 ° C and a heat of fusion of 90.4 J/g. The corresponding CRYSTAF curve was 63. 200900545 77.6 ° C shows the peak number, and has a peak area of 19.5%. The interval between the two peaks is related to local crystallization and low crystal aggregation. The presence of the compound. The difference between DSC Tm and Tcrystaf is 47.2 ° C. Physical property test 5 Polymer samples are evaluated such as high temperature resistance (confirmed by Τ 温度 A temperature test), pellet adhesion strength, high temperature recovery , high temperature compression set and storage modulus ratio (〇' (25 ° 〇 / 〇 ' (100 ° 〇) physical properties. Several commercially available products are included in this test: Comparative Example G* is substantially linear Ethylene/1-octene copolymer (AFFINITY®, available from The Dow Chemical Company), a substantially linear ethylene/1-octene copolymer of the comparative H* 10 elastomer (AFFINITY® EG8100, available from Dow Chemical Company), Comparative Example I is a substantially linear ethylene/1-octene copolymer (AFFINITY® PL1840, available from The Dow Chemical Company), Comparative Example J is a styrene/butadiene/benzene A triblock copolymer of ethylene (KRATONTM G1652, available from KRATON 15 Polymers), which is a K-based thermoplastic vulcanizate (TPV, a polyolefin blend containing a crosslinked elastomer dispersed therein). The system is presented in Table 4. 64 200900545 Table 4 Example of high temperature mechanical properties TMA-lmm Permeable eight rc) Pellet adhesion strength pounds / mile 2 (kPa) G ' (25 ° Cy G, (100 ° C) 300% strain recovery (80 ° 〇 (%) compression set (70 ° 〇 (%) D* 51 - 9 Failure - E* 130 - 18 - - p* 70 141(6.8) 9 Failure 100 5 104 〇(〇) 6 81 49 6 110 - 5 - 52 7 113 - 4 84 43 8 111 - 4 Failure 41 9 97 - 4 - 66 10 108 - 5 81 55 11 100 - 8 — 68 12 88 - 8 _ 79 13 95 - 6 84 71 14 125 - 7 - - 15 96 - 5 _ 58 16 113 - 4 _ 42 17 108 0(0) 4 82 47 18 125 - 10 _ _ 19 133 - 9 _ - G* 75 463(22.2) 89 Failure 100 H* 70 213(10.2) 29 Failure 100 I* 111 - 11 _ J* 107 - 5 failure 100 K* 152 - 3 40 in the fourth table 'Comparative Example F (which is a physical blend of the two polymers formed by the polymerization of the catalyst and the ruthenium) has about 1 〇 °c 〇1111 penetrates into temperature' and Examples 5-9 have 1〇〇. The im or higher imm penetrates into the temperature of 5 degrees. Furthermore, Examples 10-19 all have greater than 85. (: 1mm penetration temperature, and most of them have a temperature greater than 9〇 °c or even greater than 1〇〇^21ηπη tmA. This is not comparable to the physical blend, the novel polymer has a higher temperature The preferred dimensional stability. Comparative Example j (commercial SEBS) has a good 1 mm TMA temperature of about 1 〇 7 C, but it has a very poor (high temperature 7 〇 1 〇 C) compression change of about 1 〇〇 %, and At high temperatures (10), the 3% strain recovery of the crucible cannot be recovered. Therefore, the polymer of this example has a unique combination of properties that is not available even in some high performance thermoplastic elastomers that can be said. Table 4 shows a low (good) storage modulus ratio of 6 or less for the polymer of the invention, G, (25t) / G, (1 〇 (rc), and physical blending 65 200900545 (Comparative Example F A random ethylene/olefinic residue having a similar storage modulus ratio of 9 (Comparative Example G) has a storage modulus ratio greater than (89) numerical grade and a desired storage modulus ratio of the polymer As close as possible to 1. These $composites are relatively unaffected by temperature and are made from such polymers. It can be used usefully in a wide temperature range. This low volatility ratio and characteristics irrespective of /ironity are particularly useful in elastomer applications, such as in pressure sensitive adhesive compositions. The data in Table 4 also proves The polymer of the invention has improved pellets = strength. In particular, Example 5 has the adhesion strength of the pellets, which is compared to Comparative Examples F and G which show considerable adhesion, in the test conditions; By flow. Adhesive strength is important, (iv) Bulk transport of aggregates with large adhesive strength can cause agglomeration or knotting of the product during storage or transport, resulting in poor handling properties. High temperature (7 ° C) compression set is generally good, less than about 80%, preferably less than about 70%, and especially 4. 4 about 0. Conversely, Comparative Examples F, G, HAj has 1% of 7

Change ' Γ I (Dare to be a big value, indicating no reply). Good high temperature compression set values) Special requirements for applications such as gaskets, window frames, 〇-rings, etc. 66 200900545 _ Λ 1 1 t ΓΛ PO 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 21'C's calendar change (%) 1 1 2 2 R fS (N in (N (N port 1 2 m 1 1 CN fO CS 1 ΙΛ s 〇 〇 v〇1 O o 790 IS oo 1810 I 1760 1 1 〇00 o •noo 1 ) 1770 1 11040 I Ch 1 1 〇o 00 cn 1 〇2 1 phase CsS m 00 1 in o P ? to <〇V% 1 1 m 00 oo fO OO 1 1 m ir ^ S 1 v〇5S 1 F320 S 1 00 ss 1 tN 0〇CN OO 1 o 00 〇\ 00 st 〇\ oo 00 oo m 1 1 Ό oo £ 1 m 1 _ $ want to record! • l ON cn r〇 1 tt lH inch 1 l Q\ cs 0\ 1 inch R 1 δ 1 1 word r- ON u-> 1 1 1 ijsyr· ft l 1 ΓΟ σ\ wear 1 n 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 S inch g σ\ o inch (N OO 12 DO m σ\ S OO ο oo m (N oo s S o ae<) as 00 OO in oc VO a\ (N m cs g 00 sg 〇〇\ cs 00 ON 〇SO 1 »degree 〇s S 2] u 2 CN 2 rn 2 〇\ CN o rj 2 沄om r- in a (N cn 1 % 1 1 1 rH in ON 1 os ΙΟ CO t 1 macro 1 f5 1 1 1 1 1 1 1 1 m>> t 1 2 1 in rn 1 1 1 1 I 1 1 1 1 r 1 1 1 w If m 1589 ___I 妄OS tN P; *T) m 00 ΓΛ m CN (N 2 2 〇 2 s 00 ON C^> CN 3 JO 2 1 [曲模童(MPa) cs Ό 〇\ oo iri r*% 5 m rs SM PM <N oo s S [323 1 〇12 lH o > 1 X- Q m L· ID Oo 〇\ o rH JN PO s in s DO Os * o * ffi * ^ff-^KSE-?l^ 67 200900545 Table 5 shows the mechanical properties of the novel polymer and various comparative polymers at ambient temperature. It can be seen that the polymers of the present invention have good abrasion resistance when tested in accordance with 岱〇 4649 and generally exhibit a volume loss of less than about 90 mm 3 , preferably less than about 80 mm 3 , and especially less than about 50 mm 3 . For the 5 test, higher values indicate higher volume loss and thus lower wear resistance. The tear strength measured by the tensile tear strength of the polymer of the present invention is generally 100 mJ or more as shown in Table 5. The tear strength of the polymers of the present invention can be as high as 3000 mJ, or even as high as 500 mJ. The comparative polymer generally has a tear strength of not more than 750 mJ. 10 Table 5 also shows that the polymer of the present invention has a retractive stress better than that of some comparative samples at 150% strain (as evidenced by higher retraction stress values). Comparative Examples F, G, and Η have a retraction stress value of 400 kPa or less at 150% strain' while the polymer of the present invention has 5 kPa (Example 11) up to about 1100 kPa (Example 17) The value of the retraction stress at 150% strain. Polymers having a value of 15 to 150% retraction stress are quite useful for elastic applications such as elastic fibers and fabrics, especially non-woven fabrics. Other applications include diapers 'hygiene items, and belts for medical clothing, such as hanging straps and elastic bands. Table 5 also shows that, for example, in Comparative Example g, the stress relaxation (at 50% strain) of the polymer 20 of the present invention was also improved (less). Lower stress relaxation means that the application of the polymer at a body temperature for a long period of time, such as diapers and other garments, preferably maintains its elasticity. Optical Measurement 200900545 Table 6 Polymer Optical Properties Example Internal Turbidity (%) Cleanliness (%) 45° Gloss (%) P* 84 22 49 G* 5 73 56 5 13 72 60 6 33 69 53 7 28 57 59 8 20 65 62 9 61 38 49 10 15 73 67 11 13 69 67 12 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 61 22 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59 The optical properties reported in Table 6 are based on a compression molded film that is substantially lacking in orientation. The optical properties of the polymer can be varied over a wide range due to changes in crystal size due to changes in the chain shuttle dose used in the polymerization. Extraction of multi-block copolymers Extraction studies of the polymers of Examples 5, 7 and Comparative Example E were carried out. In the experiment, the polymer sample was weighed into a porous glass extraction cannula and fitted into a Kumagawa type extractor. The sample extractor was purged with nitrogen and the 10 and 500 mL round bottom flask was charged with 350 ml of diethyl ether. The flask is then assembled to the extractor. The ether is heated while stirring. The time was recorded as the ether began to condense in the cannula and the extraction was carried out under nitrogen for 24 hours. At this point, stop 69 200900545 heating, let the solution cool. Leave any shy in the extractor back to the flask. The bond in the flask was evaporated under vacuum at ambient temperature, and the formed body was blown dry with nitrogen. Any residue is continuously washed using hexane and transferred to a weighed bottle. Then, the mixture was purged and purged with a nitrogen purge to evaporate, and the residue was dried under vacuum at 40 ° C overnight. Any remaining shouts in the extractor are blown dry with nitrogen. Then, / main is connected to the extractor with a second clean round bottom flask of 350 ml of burnt. The hexane was heated to reflux and stirred, and was maintained at reflux for 24 hours after being condensed into the cannula for the first time. Then, the heating was stopped, 10 and the flask was allowed to cool. Any hexane remaining in the extractor is transferred back to the flask. The hexane was removed by evaporation under vacuum at ambient temperature, and any remaining residue in the flask was transferred to the weighed bottle using a continuous cleaning. The hexane in the flask was evaporated by a nitrogen purge, and the residue was vacuum dried overnight at 4 CTC. 15 The polymer sample remaining in the cannula after extraction was transferred from the cannula to the weighed bottle and vacuum dried overnight at 4 ° C. The results are included in Table 7. Sample No. 7 Sample Weight (g) Ether Soluble (g) Ether Soluble (%) Molar %1 Hexane Soluble (g) Hexane Soluble (%y Heart Moll%1 Residual C8 Mo Ear V Comparative Example F* 1.097 0.063 5.69 12.2 0.245 2235 13.6 6.5 Example 5 1.006 1 0.041 4.08 - 0.040 3.98 "14.2 11.6 Example 7 1.092 0.017 1.59 13.3 0.012 1.10 1Ϊ.7 9.9 Determination of additional polymer by 13C NMR Example 19 AF, hydrazine solution polymerization, catalyst

20 A1/B2+DEZ For the implementation of your Π9Α-Τ continuous solution polymerization in a computer-controlled, fully mixed reactor 70 200900545

get on. The purified mixed alkane solvent (IsoparTM E, available from ExxonMobil Chemical Company), ethylene, 1-octene, and hydrogen (if used) were mixed and supplied to a 27 gallon reactor. The feed to the reactor is measured by a mass flow controller. Prior to entering the reactor, the temperature of the feed stream was controlled by using a heat exchanger cooled with ethylene glycol. The catalyst component solution was metered using a pump and a mass flow meter. The reactor was operated at about 550 psig with full liquid. Water and additives are injected into the polymer solution as it leaves the reactor. Water hydrolyzes the catalyst and terminates the polymerization. The post reactor solution is then heated in a two stage devolatilization process. The solvent and unreacted monomer are removed by 10 during the devolatilization treatment. The polymer melt is pumped to a mold for underwater pellet cutting. The continuous solution polymerization of Example 19J was carried out in a computer controlled high pressure dad reactor equipped with an internal stirrer. Purified mixed combustion solvent (ISOparTME, available from ExxonMobil Chemical Company), 2.70 hr/hr (1.22 kg / 15 hr) of ethylene, hydrazine-octene, and hydrogen (if used) are supplied to the installation for temperature Controlled casing and internal thermocouple 3.8 liter reactor. The solvent supply to the reactor is measured by a mass flow controller. The variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. When the pump is discharged, a side stream is taken to provide a flushing stream for the catalyst and co-catalyst injection line and reactor agitator. This 20-way flow is measured by a Micro-Motion mass flow meter and is measured by a control valve or by manually adjusting the needle valve. The remaining solvent is mixed with 1-octane, ethylene, and hydrogen (if used) and supplied to the reactor. The mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled by the use of a heat exchanger prior to entering the reactor. This stream enters the bottom of the reactor. Catalyst 71 200900545 5 10 The component solution is metered using a pump and a mass flow meter and mixed with the catalyst rinse solvent and introduced into the bottom of the reactor. The reactor was operated in full liquid at 500 psig (3.45 Mpa) with vigorous stirring. The product is removed via the outlet line at the top of the reactor. All outlet lines of the reactor were traced and isolated by water vapor. The polymerization reaction is stopped by adding a small amount of water to the outlet line with any stabilizer or other additive and passing the mixture through the static mixture. The product stream is then heated by a heat exchanger prior to devolatilization. The polymer product was recovered by extrusion using a devolatilizing extruder and a water-cooled granulator. Method details and results are included in Table 8. The polymer properties selected are provided in Tables 9A-C. In Table 9B, Examples 19F and 19G of the present invention showed an immediate change of about 65-70% strain after 500% elongation. 72 200900545 ^as ito'3#<nr$* %p 9.U 0,8s -ε ^<p 0.MM ε££ 寸·-s 2ε s·-ss8 ss ^<p sw OSZ Bp "- -, -6, ss 563 p-0000 β1-.1-0·'°°'°° room, / poor f good "5f f*~i Ό " ^ {S ^~· rO Ovp' — i〇-^f〇Kc*JV〇fiSo^j-fvi^fuSfnco'id 60 00 00600000 00 00 00 009 S9- β OS 哀一9ΙΌ sws 89ε I 16 inch 99Ό § es UO s inch z es —5ld2T33 „ §"$ vs 泰命铋-举咪 edd ψ^φ i 0^s ss ^ Target change ϊ3αϊ〖ζ3α sqvqO^vewjiotot^. —*〇c>ooc5ooo S8S8SS8SS ν"»^τ»ιηΐΛ»Λ»Λΐη« 〇ιη inch inch inch inch inch inch inch Tf 52l2§l2|B|

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H SI 6e sd 6.0 I °°-0 6.0 S8 0 ¢98.0 s-0 p-0 °°AS_o H61 061 &I S1 V61 , 羿甶 羿甶 踅 -±-4*冷铋长【4 S6»· Η Q Q ) ) ) ) \ \ \ ϊ Φ Τ) » φ § — i φ 5 i Φ 怃 怃. ooourAVSW 袈^/(^-ft^o^^-Ir^^^o^J/^pwdz/OOOOOOI/^^uz^c^fF^^GZYOOOU'^z- SM3 Ipi^i3i .s^s^ Bs Fff3 75 200900545 Examples 20 and 21 The ethylene/α-olefin heteropolymers of Examples 20 and 21 were produced in a manner substantially similar to the above-described Example 19Α-Ι and the polymerization conditions shown in Table 11 below. The polymer exhibits the properties shown in Table 10. Table 10 also shows any additives for the polymer. Table 10 - Properties of Examples 20-21 and Additive Density (g/cc) Example 20 Example 21 0.8800 0.8800 MI 1.3 1.3 Additive Deionized Water 100 Irgafos 168 1000 Irganox 1076 250 Irganox 1010 200 Chimmasorb 2020 100 Deionized Water 75 Irgafos 168 1000 Irganox 1076 250 Irganox 1010 200 Chimmasorb 2020 100 Hard Segment Split (% by Weight) 35% 35%

Irganox 1010 is a tetracycline (3,5-di-t-butyl-4-transhydrocinnamate) methane. Irganox 1076 is an octadecyl-3-(3',5-ditridecyl-4'-hydroxyphenyl)propionate. Irgafos 168 is a tris(2,4-di-t-butylphenyl 10 -yl) hypothermite. 〇1丨〇^8〇 2020 is 1,6-hexanediamine with 2,3,6-trichloro-1,3,5-triazine, N,N'-bis (2,2,6, 6-Tetramethyl-4-piperidinyl)-polymer, with N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction product. 76 200900545

252W 188.11 鑫* s type 1694 1752 SI ^ 8925 8923 poly money rate 5 mins / hour £ g Zn4 PPm^ g § htn 0478 136 Cocat2 黯__PP5_ mm 289.14 Cocatl treatment hours 3 S ΟχΛΙ _VP^ 563436 57064 DEZ Breaking/hour 11 DEZ ίΜ Weight% 480&C3 4999847 cam Ship broken/hour § C^B^ 航. ppm 29&S9 298.89 CatAl crushed/hour when 5 C^tAl2 __E2D_ 49958 462.4 § § Ridge 1767 15Ώ Solvent Obstacle J, time 71268 70823 QH, 6 mins/hour 196l17 19922 » 13a7 13213 1^ R CN - e\0^w .-.- Η^ΙΝΓΐ 铋v:t- bully WE^^欢蜞* sdd Vu--奴^-9)^4-2:-3⁄4.33⁄444^^3⁄4^)3⁄4^s'f^cf^-WOM----Ml .J ^φ^$$ - - i ^ * 77 200900545 Suitable for The present invention relates to dyed fabrics suitable for textile articles such as shirts, pants, swimwear, and the like. The fabric can be made in any manner, and the stretch is typically woven or knitted. The woven fabric of the present invention is typically characterized by at least a stretch based on ASTM D window measurements, while the woven fabric of the present invention is typically characterized by a stretch of up to 30% as measured by ASM. V. The dyed fabric generally comprises - or more elastic fibers, wherein the elastic fibers comprise at least one ethylene olefin block polymer and at least one reaction product suitable for the crosslinking agent. As used herein, "crosslinking agent," is any means of crosslinking the fibers of one or more of the best. Thus, the crosslinking agent can be a compound, but need not be. Also used herein are electron beam irradiation, /3 irradiation, r irradiation, corona irradiation, sinter, peroxide, propyl propyl compound, and uv radiation, with or without a crosslinking catalyst. Electron beam irradiation methods useful in embodiments of the present invention are disclosed in U.S. Patent Nos. 6,803,014 and 6,667, 351. Typically, sufficient fibers are crosslinked to allow the fabric to be dyed in an amount that is tailored to the particular polymer used. Depending on the nature, however, in certain embodiments, the percentage of crosslinked polymer is at least about 5% (preferably at least about 1 Torr, more preferably at least about 15% by weight) to about 2 Torr to at most 75 (preferably Up to 65, preferably up to about 50%, more preferably up to about 40%) 'It is measured by the weight percentage of the gel formed according to the method described in Example 25. The fiber is typically based on ASTM D2653- 01 (the elongation of the first-filament break test) is greater than about 200 %, preferably greater than about 210%, preferably 78 200900545 is greater than about 220%, preferably greater than about 23%, preferably greater than about 24%, and more preferably greater than about 250%, preferably More than about 260%, preferably greater than about 270%, preferably greater than about 28% by weight, and up to _% filament elongation at break. The fibers of the present invention are further characterized by having (1) greater than or equal to about one. 5, preferably greater than or equal to about 16, preferably greater than or equal to about I?, preferably greater than or equal to about 1-8, preferably greater than or equal to about ,9, preferably greater than or equal to about 2.0, more preferably Preferably, the system is greater than or equal to about 2, preferably greater than or equal to about 2-2', preferably greater than or equal to about 2, preferably greater than or equal to about 2.4' and can be as high as 200% elongation of the load/1〇 〇% elongation of the load ratio of 1〇, based on ASTM D2731-〇l (in the form of finished fiber type at a specific elongation). The polyolefin may be selected from any suitable ethylene olefin block polymer. A preferred olefin block polymer is an ethylene/α-olefin heterogeneous copolymer in which an ethylene/α-olefin heteropolymer is blended The former has one or more of the following characteristics: (1) an average block index greater than 0 and up to about 1.0, and a molecular weight distribution greater than about 13, Mw/Mn; or (2) at 40 when using TREF classification (: at least one knife fraction eluted at 130 ° C is characterized by a block index of at least 〇·5 and up to about 1 20 in this fraction; (3) Mw/ of about 1 _7 to about 3_5 Mn 'at least one melting point (Tm, in terms of C), and twist (d, in grams per cubic centimeter) 'where the values of Tm and d correspond to the relationship:

Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or 79 200900545 (4) Mw/Mn of from about 1.7 to about 3.5, and characterized by a heat of fusion (ah, J/g) 'and one The Δ amount (ΛΤ, °C) defined by the temperature difference between the highest DSC peak and the highest CRYSTAF peak, wherein the values of ΛΤ and ΛΗ have the following relationship: 5 For AH greater than 0 and up to 130 J/g Τ>-0.1299(ΔΗ)+62.81, when /\11 is greater than 130 1/8, it is octagonal 2 48. (:,

Wherein, the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRTSTAF peak, the CRYSTAF 10 temperature is 30 ° C; or (5) is ethylene/a-olefin The compression molded film of the heterogeneous copolymer measures the elastic recovery (Re, %) at 300% strain and 1 cycle, and has a density (d, g/cm 3 ) where the ethylene/α-olefin heteropolymer is When there is substantially no cross-linking phase, the values of Re and d satisfy the following relationship: 15 Re>1481-1629(d); or (6) at 40 when using TREF classification. (: with 130. (: inter-eluting molecular fraction, characterized in that the fraction has at least 5% higher than the random ethylene heteropolymer grades compared to the same temperature elution) a monomer content, wherein the comparable random ethylene heteropolymer has a phase bismuth co-monomer and has a melt index, density, and mole within 10% of the ethylene/α-olefin heteropolymer Co-monomer content (based on the entire polymer); (7) at 25: storage modulus at room time, G, (25t > C), and storage modulus at 10 CTC, G, (100° C), wherein, the ratio of g, (25 ° C) to G, (100 ° C) is in the range of about 1:1 to about 9: 1. 200900545 The fiber can be made into a shape depending on the intended application. Application, about the size and cross section of the round can be used as desired. However, other shapes (such as - due to its reduced friction) shape can also be used. Danny number system leaves open or even ( That is, "band,,,, weaving words, A fixed or metric fiber length of the fiber grams. Compared with ', ·,,, mother 000 wonderful place m A soil Danny size system Depending on the shape of the fabric and the desired application, typically the needle 3 material s , ^ 包含 contains at least about 1 (# preferably at least about 20, preferably at least about s (the season is about 150, preferably Up to about 18 inches from Danny to Eve (preferably the main fiber of the Danny number at most. The other side 'T-to-multi-touch Danny number) 10 15 20 face, woven fabric can contain more than knitting Danny has a maximum number of fibers up to the Danny's number. The other aspect of the machine can contain most of the fibers with a Danny number greater than knitting and up to 3000 denier. The fibers may be in any suitable form, including staple fibers or binder fibers. Typical examples may include single component _, bicomponent fibers, solvent spray fibers, miscellaneous _, or __. , may have a sheath-core structure; an island-in-the-sea structure; a side-by-side structure; a matrix fibril structure; or a segmental structure. Advantageously, the conventional method can be used to manufacture the aforementioned fibers. For example, it is described in the US special case. Depending on its composition, the fiber can be Made to the same or better as other fibers to facilitate processing and unwinding from the reel. Generally, fibers that have a circular cross-section often fail to provide satisfactory unwinding performance due to excessive stress relaxation of their base polymer. This stress relaxation is proportional to the degree of aging of the reel 81 and causes the filaments on the surface of the reel to lose their surface and become loose filament strands. Thereafter, when this volume contains conventional fibers The cartridge is placed on the positive feed coil (ie, Memminger_IR〇) and begins to rotate to the industrial speed (ie '100 to 300 rpm), the loose fibers are thrown to the side of the roll surface, 5 and finally from the reel The edge is falling. This failure is referred to as derailment, which is a tendency for conventional fibers to slip off the shoulder or end edge of the package, which interrupts the unwinding procedure and ultimately causes a mechanical stop. The above fibers may exhibit the same or a significant degree of derailment. This can have a larger production volume. Another advantage of this fiber is that fabric defects or elastic filaments or the loss of fiber 10 breaks are equal or reduced compared to conventional fabrics. Namely, the use of the above-mentioned fibers can reduce the aggregation of the fiber fragments on the needle bed - a problem that often occurs in a circular knitting machine when the polymer residue adheres to the surface of the needle. Therefore, when such fibers are formed into, for example, a fabric on a circular knitting machine, the fibers can reduce the rupture of the corresponding fabric caused by the residue. Another advantage is that the fibers can be knitted in a circular machine with the elastic yarn guides that tend to move the filaments from the reel all the way to the needle, such as ceramic or metal fusiforms. Conversely, 'some conventional elastic olefin fibers need to be made such that the yarn guides are made of rotating elements (such as pulleys) to minimize friction when the machine parts (such as the shuttle eye) are heated, thus making the machine Stopping or filament breakage 20 can be avoided during the circular knitting process. That is, the frictional force with the yarn guiding members of the machine is reduced by using the fibers of the present invention. Further circumstance for circular knitting is found in, for example, Bamberg Meisenbach, "Circular Knitting: Technology Process, Structures, Yarns, Quality 5, 1995 (herein incorporated by reference in its entirety). 200900545 Additive antioxidants (eg IRGAFOS® 168, IRGANOX® 1010, IRGANOX® 3790, and CHIMASSORB® 944, manufactured by Ciba Geigy Corp.) can be added to ethylene polymers to protect against degradation and/or degradation during molding or manufacturing operations. It is preferred to control the degree of grafting or crosslinking (ie, inhibit excessive gelation). Processing additives (eg, calcium stearate, water, fluoropolymer, etc.) can also be used to passivate residual catalysts and/or improve processability. For this purpose, TINUVIN® 770 (available from Ciba-Geigy) can be used as a light stabilizer. Copolymers may or may not have fillers. If filled, the amount of filler 10 should not exceed the adverse heat that would adversely affect high temperatures. Or an amount of elasticity. If present, the amount of filler typically is between 0.01 and 80% by weight based on the total weight of the copolymer (or if the copolymer and one or more other polymerizations) The blend is based on the total weight of the blend. Representative fillers include kaolin clay, magnesium hydroxide, zinc oxide, vermiculite, and calcium carbonate. For example, the filler is a material coating that avoids or slows the tendency of the filler to interfere with the crosslinking reaction. Stearic acid is an example of such a filler coating. To reduce the coefficient of friction of the fibers, various spinning finishing compositions can be used. , for example, 'metal soaps dispersed in textile oils (see, for example, U.S. Patent No. 3,039,895 or U.S. Patent No. 6,652,599), 20 surfactants in base oils (see, for example, 'US Bulletin 2003/0024052 No.) and a polyalkylene oxide (see, for example, U.S. Patent No. 3,296,063 or U.S. Patent No. 4,999,120), the disclosure of which is incorporated herein by reference. Spinning finishing composition. Fabric 83 200900545 The present invention relates to a textile article comprising an olefin inlaid p. For the purposes of the present invention, an improved dyed article of the article (ie, since then) (including, for example, the object contains fabrics and fabrics made of clothing). Knitwear means that by hand, a fabric of one color and other items, a series of connecting coils are wound around each other. Or a knitting of any type on the machine, including, for example, the present invention can be applied to any knitting. Particularly preferably, the knitting comprises + weaving, and a circle (mschel), and the preferred weft knitting comprises a circle, ' ((10)) and raschel The invention is used in the case where the circular needle is made flat and seamless. However, a circular knitting of 10 15 20 ^ (i.e., circular knitting) is particularly advantageous. The invention can also be applied to 'y, any type of woven fabric. Preferably, the dyed fabric of the present invention comprises one or more elastic fibers, wherein the elastic fibers comprise at least an ethylene olefin block polymer and at least a reaction product of a crosslinking agent, wherein t, a hydrocarbon is embedded The segment polymer is an ethylene olefin copolymer, and the towel, the acetylene copolymer has one or more of the following characteristics before crosslinking: (1) an average of more than 0 and up to about 1 〇 a segment index, and a molecular weight distribution greater than about 13,] VIw/Mn; or (2) at least one molecular fraction eluted between 4 ° C and 130 ° C when TREF fractionation is used. a block index of at least 且5 and up to about 1; (3) Mw/Mn of from about 1.7 to about 3_5, at least one melting point (Tm, in C), and density (d, in grams per cubic centimeter) , where the values of Tm and d correspond to the relationship:

Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or 84 200900545 (4) from about 1.7 to about 3.5iMw/Mn, and characterized by a heat of fusion (ΔΗ, J/g)' and one of the highest The amount of Δ (ΔΤ, °C) defined by the temperature difference between the DSC peak and the highest CRYSTAF peak, wherein the values of ΛΤ and Δ!! have the following relationship: 5 For ΔΗ greater than 0 and up to 130 J/g ΔΤ>-0.1299(ΔΗ)+62.81 > For ΔΗ greater than 130 J/g,

Wherein, the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRTSTAF ♦, the CRYSTAF 10 temperature is 30 ° C; or (5) is ethylene/α- The compression molded film of the olefin heteropolymer is measured at 300% strain and one cycle of elastic recovery (Re, %) and has a density (d, g/cm 3 ), where 'when ethylene/〇:-olefin heterogeneous When the copolymer has substantially no cross-linking phase, the values of Re and d satisfy the following relationship: 15 Re>1481-1629(d); or (6) elution between 40 ° C and 130 ° C when fractionated using TREF a molecular fraction characterized in that the fraction has a molar comonomer content that is at least 5% higher than a comparable random acetylated heteropolymer copolymer fraction eluted between the same temperature, wherein the fraction is comparable The random ethylene heterogeneous copolymer has a phase 20 comonomer, and has a melt index, a density, and a molar comonomer content within 10% of the ethylene/α-olefin heteropolymer (based on the entire polymer) (7) Storage modulus at 25 ° C, G' (25 ° C), and storage modulus at 100 ° C, G' (l 〇〇 ° C Wherein, the ratio of G' (25 ° C) to G' (100 ° C) is in the range of about 1:1 to about 9:1. 85 200900545 The amount of polymer in the dyed fabric depends on the polymer, the application and the desired properties. The dyed fabric typically comprises at least about 1 (preferably at least about 2, preferably at least about 5, preferably at least about 7) weight percent of the ethylene Ax-olefin heteropolymer. The fabric typically comprises less than about 50 (preferably less than about 5 40, preferably less than about 30, preferably less than about 20, more preferably less than about 10) by weight of ethylene/α-olefin. Heterogeneous copolymer. The ethylene/α-olefin heteropolymer may be of a fiber type and may be blended with another suitable polymer (for example, polyolefin' such as random ethylene copolymer, HDPE, LLDPE, LDPE, ULDPE, polypropylene homopolymer, copolymerization Blending of materials, plastomers and elastomers, lastol, 10 polyamines, etc.). The ethylene/α-olefin heteropolymer of the fabric can have any density, but is generally at least about 0.85, and preferably at least about 0.865 g/cm3 (ASTM D 792). Correspondingly, the density is generally less than about 0.93, preferably less than about 0.92 g/cm3 (ASTM D 792). The ethylene/α-olefin heteropolymer of the fabric is characterized by an uncrosslinked melt index of from 15 to about 1 gram per minute. The percentage of crosslinked polymer is generally at least 1% (preferably at least about 20, more preferably at least about 25% by weight) up to 90 (preferably up to about 75), if desired. It is measured by the weight percentage of the gel formed. The fabric generally comprises a material selected from the group consisting of rayon, nylon's viscose, polyester (such as 20 microfiber polyester), polyamide, polypropylene, cellulose, cotton, linen, ramie, hemp, wool, silk, linen. An additional material of the group consisting of bamboo, Tencel, Maohai, other natural fibers, other synthetic fibers, and mixtures thereof. Generally, other materials include a major portion of the fabric. In this case, it is generally preferred that the other material comprises at least about 5 Å of the fabric (preferably at least about 6 Å, preferably 200900 545 is preferably at least about -, ethylene / «- ene smog ^ 49 〇. 95 ) t type. Preferred dimensions include i other materials, or both may be at least about 5. The Danny number is up to about: preferably one is about 1 〇 0, preferably more than about (10), preferably m is particularly preferred. And the ten-woven fabric comprises a fiber-type polymer, the content of which is about 5% of the vinyl-olefin of the fabric. The preferred knitted fabric comprises the fiber type (by weight). Special 10 15 20 polymer, the content of which is about 1G to the fabric of the fabric (to the fabric of the homogenized knit and circular knit fabric also contains polyester or micro-^). Generally, this fabric (especially needles) is as cool as horizontal. The two have less than about 5 (preferably less than 4, more than perpendicular, or less than 2, preferably less than i, preferably less than the father = 3, preferably after the cleaning shrinkage Rate (based on (3) 5). Less than 0 but / after setting) generally in the length direction, width direction or both = (thermal change + 7%, preferably -5% to about +5%, preferably It is about _3% to about ‧ / = about ==: ·; better, about +1% of the size stability; 'e Al). In addition, the fabric-like system has a lower cleaning AATCC 135 IVAi than the comparable elastic fiber fabric with higher cross-linking. According to the knit fabric, if necessary, it can be stretched in two directions by controlling the type and amount of ethylene/α-olefin heteropolymerization and other materials. Knitted woven;: Secondly characterized by at least about 30% stretch (measured according to ASTM D2594). Similarly, the fabric can be made to have a length in the length and width directions of less than about 87 200900545, preferably less than about 5, preferably less than about 4, preferably less than about 3, preferably less than about 2. Preferably, it is less than about 1) to as little as 0.5% (according to ASTM D 2594). Using the same test (ASTM D 2594), the 60 second length growth can be less than about 15 (preferably less than about 12, preferably less than about 1 Torr, preferably less than about 8%. Correspondingly Using the same test (ASTM D 2594), the 60 second width growth can be less than about 20 (preferably less than about is, preferably less than about 16, preferably less than about 13%). About ASTM 60 minutes of D 2594 test, 10 15 20 growth in the width direction may be less than about 10 (preferably less than about 9, preferably less than about 8, preferably less than about 6)%, and 60 minutes The lengthwise growth may be less than about 8 (preferably less than about 7 'preferably less than about 6, preferably less than about 5) percent. The lower growth described above results in fewer fabrics of the present invention. Preferably, it is less than about 170, preferably less than about 170, preferably less than about 160, preferably less than about 150. The temperature of the crucible is thermally set, while still controlling the size. Contrary to the knitted fabric, the woven fabric is particularly The stretching may be at least about Η)% (measured according to ASTM D). Advantageously, the knit fabric of the present invention can be used without a large amount of rupture and using a needle comprising a mesh feeder line, a pulley system, or the like. Loom manufacturing. Therefore, it has improved moldability and acceptable dimensional stability (length direction and width direction), the ability to pick up and increase the weight and shrinkage, the ability to change and control the size at low temperatures, and false Eight '"' -" recycled circular knit stretch fabric can be produced without significant cracking, with high production..> Derailed. "Knitting machine without dyeing. Actually any dyeing method is described in Fundamentals 〇 f The dyed fabric of the present invention can be constructed by, for example, many useful techniques.

Dyeing and Printing ’ Garry Mock, North Carolina State

University 2002, ISBN 9780000033871. The advantage of the fabric of the present invention is that the dyed fabric can be produced by contacting the dye at a temperature of at least about 130 ° C, wherein the fabric exhibits less than 〇 5, preferably less than 〇 4, preferably less than 5 Preferably, less than 0.3' is preferably less than 0.25, preferably less than 〇2, preferably less than 0.15, preferably less than 〇1, preferably less than 〇〇5. The ratio of growth to stretching. Advantageously, the dyed fabric of the present invention formed is generally characterized by a color change of greater than or equal to about 3.0, preferably greater than or equal to about 3 to 5, more preferably greater than or equal to about 4 Torr (by 10 AATCC 61- After the first cleaning of 2003-2A, it was evaluated according to AATCC). Another advantage is that the fabric of the present invention can sometimes exhibit a color change greater than or equal to about 2.5, preferably greater than or equal to about 3.0, and more preferably greater than or equal to about 3.5. (by AATCC 61-2003-2A) After the second cleaning, it is evaluated according to AATCC). Basically, this means that the dyed fabric of the present invention exhibits less fading than the conventional dyed fabric when it is washed. The dyed fabric of the present invention is also characterized by a favorable color strength after dyeing, i.e., the fabric is deep. For example, dyed fabrics are generally characterized by a color 20 strength of greater than or equal to about 600, preferably greater than or equal to about 650, preferably greater than or equal to about 700, and preferably greater than or equal to about 75 Å. Measured with a spectrophotometer). Advantageously, the color is substantially maintained, even after the first and second cleaning. For example, the dyed fabric may be characterized by a color strength of at least about 90, preferably at least about 95, and more preferably at least about 97%, after dyeing by AATCC 61 -2003-2A to the color strength after the first cleaning. Wherein each color intensity is measured by a spectrophotometer. The dyed fabric of 200900545 may sometimes be characterized by at least about 9 〇, preferably at least about 92.5, by the color intensity of the color intensity m after the first 'month wash. It is better to have at least about 94% of the R, A, a, where each color intensity is measured by a spectrophotometer. 5 Although it is not limited to any theory, it is believed that the dyed woven # dyeing of the present invention is due to the fiber of the olefin block polymer. That is, the dilute (four) length of polymer fibers are dyed to a lesser extent to make other materials deeper. Further, when the vinylene polymer is used as a fiber, a higher dyeing temperature can be used with less fiber breakage. In a similar manner, it is believed that the dyed 10 fabrics are less interesting in cleaning the thin hydrocarbon block polymer fibers to the extent that they are as large as the fibers made with other polymers. In this way, the olefin block polymer does not discolor or bleed a lot. EXAMPLES Example 22 - Elastomeric ethylene/α-olefin heteropolymer fiber 15 The elastomeric vinyl hydrazine-olefin heteropolymer (olefin block polymer) of Example 20 was used to make 40 Danny having an approximately circular footprint. A number of single filament fibers. Prior to the fiber being manufactured, the following additives were added to the polymer: 7000 ppm PDMSO (polydidecyloxane), 3 pprn of CYANOX 1790 (1,3,5-tri-(4-third) Butyl _3_hydroxy-2,6-dimethylphenylhydrazine 20 yl)-1,3,5-tri-qin-2,4,6-(1Η,3Η,5Η)-trione, and 3000 ppm CHIMASORB 944 poly-[[6-(1,1,3,3-tetradecylbutyl)amino]-s-triazine-2,4-diyl][2,2,6,6-tetra Methyl-4-piperidinyl]imino)hexamethylene [(2,2,6,6-tetramethyl-4-piperidinyl)imido]] and 0.5% by weight of 11〇2 . The fiber system uses a mold profile with a circular diameter of 0.8 mm, a spinning temperature of 290 ° C 90 200900545 degrees 'winding machine speed of 650 m / min ' 2% spinning finishing, 6 〇 / 〇 cold stretching , and 150g bobbin weight manufacturing. Then, the fibers were crosslinked by using a total amount of 176 4 kGy irradiation as a crosslinking agent. Example 23 - Fiber Hard Yarn 5 A hard yarn was produced comprising Example 22 and an elastic fiber and 150 denier 288 filament polyester. Microfiber filaments are finely levied to ο.] Danny/filament. Two comparative examples were also made. A comparative example of the hard yarn used was 40 denier random ethylene-octene copolymer fibers manufactured at a line speed of 45 ft./min, and the same 150 denier 288 filament polyester fibers. The random ethylene-octene copolymer 10 had an average melt index of 3. gram/10 minutes, a density of 875 g/cm3, and was crosslinked by a dose of 166.4 kGy as a crosslinking agent. The hard yarn of the second comparative example was made of (Lycra) LyCraTM 162 C polymer multifilament fiber and the same 150 Danny 288 filament polyester fiber. Example 24 - Dyeing 15 Experiments were designed to evaluate the staining of elastic fibers and the color depth of fabrics based on microfiber polyester. The experiment evaluated the color of the fibers comprising the olefin block polymer, the fibers comprising LycraTM 162C, and the disperse dye on the fibers comprising the random ethylene-octene copolymer. One of the three different fibers for producing one gram of the hard yarn and nine grams of the microfiber polyester fabric for making the hard yarn (refer to the woven fabric) were loaded in a laboratory rapid dyeing machine as shown in Fig. 8. The dyeing and reduction cleaning treatment shown in Fig. 9 is then carried out for one of the three different fibers. Clariant's dye, Foron Black S-WF, was used to dye fibers and fabrics black. The fiber based on Lycra is 125. (: dyeing, therefore 'this elastic fiber will suffer severe damage at higher temperatures. The other two 91 200900545 fiber systems are dyed at 135 ° C. After dyeing, the first reduction cleaning, and the second reduction cleaning sample are collected. For evaluation. The three different fibers after dyeing and reduction cleaning were visually evaluated. The microfiber fabric was also tested to obtain a color intensity of 5 degrees, color change, and staining value as an indication of color fading. The fiber is defined by visual evaluation in D65 standard daylight. The color intensity (K/S) is measured by a spectrophotometer (Dataco丨or model -600PLUS). The high κ/s value represents a deeper Color. The color change is measured according to AATCC 61-2003-2A, which reports the color difference between the original sample and the sample after cleaning. The evaluation range is based on the 10 AATCC evaluation procedure with gray scale system 1~5. The lower level indicates the larger color. The change is therefore less fading. After dyeing, the sample after the first reduction wash and the second reduction wash are washed by AATCC 61-2003-2A, and the color change before and after is measured. It is also based on the test of AATCC 61-2003-2A. A multi-fiber test fabric consisting of ethyl acetate, cotton, polyamide, propylene and wool fibers is attached to the sample to be cleaned. The test grade is 1~ 5, and the lower grade means heavier staining. The textile industry practice uses the classification result of polyamine as an indicator of staining. After dyeing, after the first reduction and after cleaning, and after the second reduction and cleaning 20 Color samples of different elastic fibers were carried out. For fabrics containing olefin block polymers, the results indicated good colorfastness and darker color. Table 12 shows the first reduction after cleaning and the second reduction after dyeing. The staining of the elastic fibers after washing. More dyes are absorbed on the elastic fibers themselves to produce darker colors. High dye absorption is used to obtain the dark color fronts, but it may ooze during cleaning (home 92 200900545 cleaning) Disadvantageous. Leica tm fiber shows the darkest color after dyeing, after first reduction cleaning, and after second reduction cleaning. Random ethylene-octene copolymer and olefin block polymer show lighter staining The sample is very similar after dyeing, after the first reduction cleaning, and after the second reduction cleaning. 5 The olefin block polymer shows less dye absorption, and its non-fading property on the microfiber polyester fabric helps better. Fading. Table 12 staining test item Lycra 162C random ethylene octene copolymer olefin block polymer dyed elastic fiber stained the deepest lighter and lighter than the first RC1 after the elastic fiber The lightness of the elastic fiber after the first lightening of the first RC2 is the darkest and lighter: the reduction cleaning table 13 shows the color strength (K/S) value of the microfiber polyester fabric. A higher κ/s value of 10 represents a darker color. The reference micropolyester fabric dyed with random ethylene-octene copolymer and olefin block polymer fibers showed a darker black color than Lycra. While not wishing to be bound by any theory, it is believed that this result is due to the use of higher dyeing temperatures. After the dyeing, there was no significant difference between the samples after the first reduction washing and the second reduction washing. However, the microfiber polyester of the olefin block polymer 15 cannot achieve a darker color. 93 200900545 The color strength (K/S) value of the 13th table fabric test item Lycra 162C Random ethylene-octene copolymer olefin block polymer dyed micro-PES reference fabric color strength (K/S) 423.38 755.77 774.71 Micro-PES reference fabric after first reduction and cleaning K/S 414.68 783.83 753.67 Micro-PES reference fabric after second reduction and cleaning K/S 411.75 753.00 739.86 Table 14 shows after dyeing, after first reduction cleaning, and Second, the color change value of the microfiber polyacetate after the reduction and cleaning. Higher values mean lighter color changes. All samples showed good color change results. 5 Table 14 Micro-polyester color change results Test item Lycra 162C Random ethylene-octene copolymer olefin block polymer dyed micro-PES reference fabric color change 4 4 4 After the first reduction and cleaning Color change of the reference fabric of PES 4 4 4 Color change of the reference fabric of the micro-PES after the second reduction and cleaning 4 4 4 Table 15 shows the staining property of the polyamide fabric (test fabric). Higher values mean less staining. The reduced cleaned fabric shows a better stain. There was no significant difference between the results displayed after the first and second reductions. The dyed reference fabric 10 of the random ethylene-octene copolymer and olefin block polymer is deeper than the dyed Lycra fabric, which has utility for non-fading as shown in Table 12. None of the results involved thermal deformation of the fabric. 94 200900545 15th table fabric stain test item dyed Lycra 162C random ethylene-octene copolymer olefin block polymer 3 2.5 ~ 2.5 3rd, /7Γ~ Sc: successively broken 1 fabric pair The non-fading property of the cleaning is also the second. ^ PES reference fabric cleaning. Non-fading _ , .—_ 3.5 H~~~~~ 3.5 3.5 3.5 —~ 3.5 Two-time early knit fabric was used for this test. It is a non-woven vinyl-dye copolymer of 40 Danny's Lycra 40 Danny, and a microfiber poly-gloss yarn of 4 Denny's thin smoke block V s fiber knitted. The knitting speed, elastic stretch and fabric weight of the primary color cloth are shown in Table 16. Table 16 Fabrics of fabrics containing various elastic fibers Description Sample speed (rpm) DR Primary color Braka 162C 12.4 2.6 203 g/m 2 Random ethylene-octene copolymer 12.4 2.6 170 g/m 2 Olefin block polymerization Material 20 3.2 186 g/m 2 The primary color cloth of the random ethylene-octene copolymer and the olefin block polymer was washed at 85 ° C for 20 minutes at 135. (: drying for 45 minutes, dyeing at 130C for 60 minutes without tension, at 120 ° C with 20% overfeeding for 120 seconds (15 yards / minute), 10 and finishing. For the inclusion of random ethylene-octene copolymer and The conditions for dyeing and reduction of the olefin block polymer fabric are shown in Figure 9. The Lycra virgin fabric was dyed at 125 ° C and thermally set at 185 ° C. The finished fabric was in Table 17. Description 95 200900545 Table 17 Fabric Weights of Fabrics with Various Elastic Weaves Sample ID Finished Weight Lycra 162C 269 g/m 2 Random Ethylene-Octene Copolymer 210 g/m 2 Olefin Block Polymer 190 g / m 2 Table 18 shows the results of AATCC 61-2003-2A, before and after thermal set, compared with Lycra 162, random ethylene-octene copolymer and olefin block polymer have color change Excellent performance. The reason is that random ethylene-octene co-polymers and olefin block polymer fibers are dyed at 135 ° C, and the disperse dyes have better reaction at this temperature. Batches of microfiber polyester / Lycra dyeing An unreacted disperse dye on a fabric due to a low dyeing temperature Color, and bleed out during the test to discolor the sample. Compared with Lycra, the random ethylene-octene copolymer and OBC have good colorfastness. Lycra shows poor colorfastness after heat 10 change. Disperse dyes migrated during high temperature heat set at 185 ° C. Results of color change and non-fading of fabrics of Table 18 Test item Lycra 162C Random B-bake-octene copolymer olefin block polymer RC Color change 3 4 4 Color change after heat setting 2.5 4 4 Non-fading property after cleaning after RC 3 3.5 3.5 Non-fading property after cleaning after heat setting 2 3.5 4 Three after heat setting The fabric was tested by a spectrophotometer (Datacolor Model - 600 PLUS). Table 19 shows the color intensity (κ/s) indicating the depth of the face 96 200900545. Contains randomness compared to the knitted fabric containing Lycra using the same dye composition. The microfiber polyester knitted fabric of ethylene-octene copolymer and olefin block polymer has a deeper color. The fabric width test item of the primary color cloth and the finished article of the 19th table Lycra 162C random ethylene-octene copolymerization OBC EXP 6116 Color Intensity (K/S) ^54.23 ^47.55 774.18 5 Example 25 _ Varying amount of textured crosslinked The elastomeric ethylene/α-olefin heteropolymer of Example 20 was used to make 40 dan having an approximately circular cross section. Single filament fiber of Nis. In the fiber is manufactured, the following additives are added to the polymer: 7〇〇〇卯111?〇]^0 (polydimethyl oxalate), 3000 ppm CYANOX 1790 (1,3,5-tri-(4-Tertiary 10 butyl-3-carbyl-2,6-dimethylbenzyltriazine-2,4,6-(lH,3H,5H) )-^iij , ^3〇〇〇ppm^CHIMASORB 944 ^-[[6-(1,1,3,3-h9 f ^T^)^&]-s-^»*-2,4- ^^][2,2,6,6-Tetramethyl-4-piperidinyl]imino)hexamethylene[[2,2,6,6-tetramethyl-4-Niang]-based Amino]], and 0.5% by weight of butyl hydrazine 2. The fiber system uses a mold profile with a circular diameter of 15 〇.8 mm, a spinning temperature of 299 ° C, a winder speed of 650 m/min ' 2% spinning finishing, 6% cold drawing, and i5 〇g's bobbin is manufactured in heavy weight. Then, the fiber is crosslinked by using a varying amount of irradiation from an electron beam as a crosslinking agent. The gel content versus exposure is shown in the figure. The gel content is determined by the accuracy of weighing 20 fiber samples to 4 significant figures. The sample was then mixed with 7 ml of xylene in a capped 2 _ sample vial. Bottles range from 125 C to 135. (: Heating for 90 minutes, and inverting mixing every 15 minutes (i.e., making 97 200900545 #瓦子反倒)' to extract substantially all of the uncrosslinked cooling to about 25 ° C, deuterated benzene-based gel decantation. 0. Once the bottle is filled with new xylene, rinse it into a small plate in the bottle. The gel is equipped with a plate at 125° (: vacuum #_, 胄 简 5 5) The plate with dry gel was weighed on an analytical balance. The gel content was calculated based on the weight of the extracted gel and the original fiber Fanxian" Xia Feng benchmark. Figure 11 shows cross-linking as the electron beam dose increases. The amount (gel content) is increased. Those skilled in the art will appreciate that the precise relationship between the amount of cross-linking and the electron beam dose will be affected by the specific polymer properties (eg 'molecular weight or melt index'). :> ^The melting point/density of the inventive polymer (indicated by diamonds) when the random copolymer of the age and the material (the relational table (4) and the Zieglereta copolymer (indicated by the square) are compared) Figure 2. Figure 2 shows the diagram of the eight 15 DSC-CRYSTAF of various polymers as a function of Dsc melting enthalpy. The diamonds represent random ethylene/octene copolymers; the rectangles represent polymer examples; the 4' dime represents polymer examples 5-9; and the circular forms are polymer examples 10-19. The symbol "χ" indicates polymer Comparative Example A*-F*. Figure 3 shows the density of the heteropolymer from the present invention (represented by a rectangle and a circle of 2〇) and a conventional copolymer (indicated by a dihedron, which is a variety of affinity® polymers ( The effect of the elastic recovery of the unoriented film produced by the Dow Chemical Company). The rectangle represents the ethylene/butene copolymer of the present invention; and the circle represents the ethylene/octene copolymer of the present invention. Polymer of Example 5 (represented by a circle) and comparative polymer 98 200900545 Comparative Example E* and F* (denoted by the symbol "X") The octene content of the TREF graded ethylene/octene copolymer fraction A plot of the TREF elution temperature for this fraction. The diamond represents a conventional random ethylene/octene copolymer. Figure 5 is a polymer of Example 5 (curve 1) and a polymer comparative example 5 F* (curve) 2) the octene content of the TREF graded ethylene/1-octene copolymer fraction The TREF elution temperature of the grade is plotted. The rectangle indicates Comparative Example F*; and the triangle indicates Example 5. Figure 6 is a comparison of the ethylene/1-octene copolymer (curve 2) and the propylene/ethylene copolymer ( Curve 3) and the logarithm of the storage modulus of the two 10 olefin/1-octyl block copolymers of the invention (curve 1) as a function of temperature, prepared with different amounts of chain shuttling agents. Figure 7 shows a plot of TMA (lmm) versus flexural modulus for certain inventive polymers (indicated by diamonds) when compared to certain known polymers. Triangles represent various Dow VERSIFY® polymers ( Available from Dow Chemical Company 15; Round indicates various random ethylene/styrene copolymers; and rectangular indicates various Dow AFFINITY® polymers (available from The Dow Chemical Company). Figure 8 shows a photograph of a laboratory dyeing machine. Figure 9 shows the dyeing and reduction cleaning methods. [Main component symbol description] (none) 99

Claims (1)

200900545 X. Patent application scope: ι_ A dyed fabric comprising one or more elastic fibers, wherein the elastic fiber comprises a reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent, and wherein The fabric is characterized by a color change greater than or equal to about 3. 评估 evaluated by AATCC after the first cleaning of 5 AATCC 61 - 2003-2A. 2. The dyed fabric of claim 1 wherein the fabric is characterized by a color change greater than or equal to about 35 as assessed by the AATCC after the first cleaning of AATCC 61-2003-2A. 10. The dyed fabric of claim 1, wherein the fabric is characterized by a color change of greater than or equal to about 4 Torr as assessed by AATCC after the first cleaning of AATCC 61_2 〇〇 3_2a. 4. The dyed fabric of claim 1, wherein the fabric is a woven fabric characterized by at least about 15% stretch according to ASTM D3107. The dyed fabric of claim 1, wherein the ethylene olefin mobile polymer is an ethylene/α-olefin heteropolymer characterized by one or more of the following characteristics before crosslinking: a) having a Mw/Mn of from about 1.7 to about 3.5, at least one melting point (Tm, in terms of C 2 )), and a density (d in grams per cubic centimeter), wherein the values of Tm and d are corresponding In relation to: Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or (b) having from about 1.7 to about 3.52 MW/Mn and characterized by a heat of fusion (Δ Η, J/g) and The amount of Δ defined by the difference between the highest dsc peak and the highest CRYSTAF peak temperature 100 200900545 (ΔΤ, 〇, where the at and AHi values have the following relationship: for ΛΗ greater than 0 and up to 130 J/g ΔΤ>-0.1299(ΔΗ)+62.81 > for ΛΗ greater than 130 J/g, wherein the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer is identifiable The cRTSTAF peak, the CRYSTAF temperature system is 30. (:; or (c) is characterized by compression molding of ethylene/〇;-olefin heteropolymer The film measures the elastic recovery (Re, %) at 300% strain and 1 cycle, and has a density (d, g/cm 3 ), wherein when the ethylene/α; olefin heteropolymer is substantially free of cross-linking phase The values of Re and d satisfy the following relationship: Re>1481-1629(d); or (d) having a molecular fraction at 40 ° C and 13 (extracted between TCs) when using TREF classification is characterized by The fraction has a molar comonomer content of at least 5 Å/〇 higher than that of the comparable random ethylene heteropolymer copolymer grade eluted between the same temperature, wherein the comparable random ethylene heteropolymer is comparable a melt index, a density, and a molar comonomer content (based on the entire polymer) within 10% of the same comonomer and having the ethylene/α-olefin heteropolymer; (e) Storage modulus at 25 ° C, G, (25 ° C), and 100. (: storage modulus at the time 'G, (10 (TC), where, G, (25 ° C) versus G, (100 The ratio of °C) is from about 1:1 to about 10:1; or (7) has a ratio of 4 when used with TREF (TC and 130. (: one of the elution 101 200900545 molecular grades, characterized by The fraction having a molecular weight distribution of at least 0.5 and up to about 1 and a molecular weight distribution greater than about 1.3, Mw/Mn; or (g) having an average block index greater than 〇 and up to about 1.0, and greater than about 1.3 Molecular weight distribution, Mw / Mn. 5. The dyed fabric of claim 1 wherein the fabric is a knit fabric characterized by at least about 30% stretch measured in accordance with ASTM D2594. 7. The dyed fabric of claim 1, wherein the elastic fiber comprises from about 2 to about 30% by weight of the fabric. 10. The dyed fabric of claim 1, wherein the fabric further comprises a polys, a cellulose, a cotton, a linen, a hemp, a hemp, a wool, a silk, a linen, and a bamboo. , Tencel, Maohai, other natural fibers, and mixtures thereof. 9. The dyed fabric of claim 8 wherein the polyester is a 15 microfiber polyester. 10. The dyed fabric of claim 8 wherein the polyester comprises at least about 50% by weight of the fabric. 11. The dyed fabric of claim 9, wherein the microfiber polyester comprises at least about 50% by weight of the fabric. The dyed fabric of claim 5, wherein the ethylene/α-olefin heteropolymer is blended with another polymer. The dyed fabric of claim 5, wherein the ethylene/(X-olefin heteropolymer is characterized by a density of from about 0.865 to about 0.92 g/cm3 (ASTMD 792), and from about 0.1 to about A dyed fabric of the first aspect of the invention, wherein the fabric is a knitted fabric and comprises a majority of from about 1 Danny to about 180 Dan. The fiber of the Danny's number. 15 · The dyed fabric of the first paragraph of the patent, wherein the fabric is characterized by a second cleaning by AATCC61-2003-2A and evaluated according to AATCC. A color change of greater than or equal to about 25. I6, such as the dyed fabric of claim 1, wherein the fabric is characterized by a greater than AATCC evaluation by AATCC after the second cleaning of AATCC 61-2003-2A Or a color change of about 3 。. 10 I7. The dyed fabric of claim 1, wherein the fabric is characterized by a greater than AATCC evaluation after AGBCC 61-2003-2A Or equal to a color change of about 3.5. 1 8. A dyed fabric comprising one or more elastic fibers, wherein the elastic fibers comprise a reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent, and wherein the fabric is characterized A dyed fabric having a colorimetric intensity of greater than or equal to about 600 as measured by a spectrophotometer. 19. The dyed fabric of claim 18, wherein the fabric is characterized by being greater than that measured by a spectrophotometer. Or equal to about 6 5 〇 to the color intensity after dyeing. 20 20. The dyed fabric of claim 18, wherein the fabric is characterized by a spectral photometer greater than or equal to about 7 〇〇. The dyed fabric of claim 18, wherein the fabric is characterized by a color intensity of greater than or equal to about 750 to 103 200900545 as measured by a spectrophotometer. 22. The dyed fabric of claim 18, wherein the fabric is characterized by a strong color after the first cleaning by AATCC 61-2003-2A A dyed fabric having a color intensity of at least about 90% after dyeing, wherein each of the color strengths is measured by a spectrophotometer. 23. The dyed fabric of claim 18, wherein the fabric is characterized by The color intensity after the first cleaning by AATCC 61-2003-2A is at least about 95% of the color intensity after dyeing, wherein each color intensity is measured by a spectrophotometer. The dyed fabric of item 18, wherein the fabric is characterized in that the color intensity after the first cleaning by AATCC 61-2003-2A is at least about 97% of the color intensity after dyeing, wherein each The color intensity is measured by a spectrophotometer. 25. The dyed fabric of claim 18, wherein the fabric 15 is characterized in that the color strength of the AATCC 61-2003-2A after the second cleaning is at least about the color intensity after dyeing. 90%, wherein each color intensity is measured by a spectrophotometer. 26. The dyed fabric of claim 18, wherein the fabric is characterized in that the color intensity of 20 after the second cleaning by AATCC 61-2003-2A is at least about the color intensity after dyeing. 92.5%, wherein each color intensity is measured by a spectrophotometer. 27. The dyed fabric of claim 18, wherein the fabric is characterized in that the color strength of the AATCC 61-2003-2A after the second cleaning is at least about 94 after the dyeing. %, its 104 200900545 'Each color intensity is measured by a spectrophotometer. 28. The dyed fabric of claim 18, wherein the fabric is a woven fabric and is characterized by at least about 10% stretch measured in accordance with ASTM D3107. 5. The dyed fabric of claim 18, wherein the ethylene olefin block polymer is an ethylene/α-olefin heteropolymer characterized by one or more of the following characteristics prior to crosslinking: (a) having a Mw/Mn of from about 1.7 to about 3.5, at least one melting point (Tm in terms of C) and a density (d in grams per cubic centimeter), wherein the number of Tm and d is one Corresponding to the relationship: Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or (b) having Mw/Mn of about 1.7 to about 3.5, and characterized by a heat of fusion (gossip J /g) and a Δ amount defined by the temperature difference between the highest DSC peak and the highest CRYSTAF peak (ΛΤ, 〇, where at and the value of 15 have the following relationship: for AH greater than 0 and up to 130 J /g is ΔΤ>-0.1299(ΔΗ)+62.81 * for ΔΗ greater than 130 J/g, wherein the CRYSTAF peak uses at least 5% of the cumulative polymer, and if less than 5% The polymer has an identifiable CRTSTAF peak, and the CRYSTAF temperature system 301; or (c) is characterized by a compression molded film of a ethylene/α-olefin heteropolymer. 300% strain and 1 cycle of elastic recovery (Re, %), and having - twist (d, gram / cubic centimeter), wherein when ethylene / alpha olefin heterogeneous 105 200900545 polymer substantially no cross-linking phase The values of Re and d satisfy the following relationship: Re>1481-1629(d); or (d) a molecular fraction having an elution between 40 ° C and 130 ° C when fractionated using TREF, characterized in that the classification The composition has a molar comonomer content that is at least 5% higher than a comparable random ethylene heteropolymer grade of the same temperature elution 5, wherein the comparable random ethylene heteropolymer has Melt index, density and molar comonomer content (based on the entire polymer) within 10% of the same comonomer and having the ethylene/α-olefin heteropolymer; 10 (e) having 25 Storage modulus at °C, G'(25°C), and storage modulus at l〇〇°C, G'(100°C), where G'(25°C) versus G'(100 °C) is a ratio of from about 1:1 to about 10:1; or (f) having a molecular fraction eluted between 40 ° C and 130 ° C when fractionated using TREF, characterized in that The grade has a block index of at least 0.5 and up to about 15 1 and a molecular weight distribution greater than about 1.3, Mw/Mn; or (g) has an average block index greater than 0 and up to about 1.0, and greater than about 1.3. Molecular weight distribution, Mw / Mn. The dyed fabric of claim 18, wherein the elastic fiber comprises from about 2 to about 30% by weight of the fabric. The dyed fabric of claim 18, wherein the fabric further comprises a mixture of polyester, nylon, or the like. 32. The dyed fabric of claim 18, wherein the polyester is a microfiber polyester. 33. The dyed fabric of claim 31, wherein the polyester 106 200900545 comprises at least about 80% by weight of the fabric. 34. The dyed fabric of claim 32, wherein the microfiber polyester comprises at least about 80% by weight of the fabric. 35. The dyed fabric of claim 28, wherein the ethylene 5 /α-alkenyl heteropolymer is blended with an additional polymer. The dyed fabric of claim 18, wherein the ethylene/α-olefin heteropolymer is characterized by a density of from about 0.865 to about 0.92 g/cm 3 (ASTM D 792), and from about 0.1 to about 1 gram/10 minutes of uncrosslinked melt index. 1037. The dyed fabric of claim 18, wherein the majority of the fibers have a Dani number of from about 1 denier to about 18 denier. 38. A method of making a dyed fabric, wherein the fabric comprises one or more elastic fibers comprising a reaction product of at least one ethylene dilute hydrocarbon block polymer and at least one crosslinker, wherein the method comprises The fabric is contacted with 15 of the dye at a temperature above room temperature, and then the fabric is dried, wherein the 'improvement comprises bringing the fabric to the dye at least about 13 Torr. (The temperature contact produces a dyed fabric wherein the fabric exhibits a growth-to-stretch ratio of less than 〇5. 39. The method of claim 38, wherein the fabric exhibits less than 20 〇 _25 The ratio of growth to stretching. 40. The method of claim 38, wherein the dyed fabric is characterized by a greater than AATCC evaluation after the first cleaning by AATCC 61-2003-2A. Or a color change of about 3.0. The method of claim 38, wherein the dyed fabric 107 200900545 is characterized in that the color intensity after the first cleaning by AATCC 61-2003-2A is The color intensity after dyeing is at least about 90%, wherein each color intensity is measured by a spectrophotometer. 42. The method of claim 2, wherein the method is performed in the absence of a penetrant on the substance 5 43. The method of claim 38, wherein the dyed fabric is characterized by a color intensity measured by a spectrophotometer greater than or equal to about 600 after dyeing. The method of claim 38, wherein the dyed fabric 10 is characterized in that the color intensity after the first cleaning by AATCC 61-2003-2A is at least about 90% of the color intensity after dyeing, wherein each A color intensity is measured by a spectrophotometer. The method of claim 38, wherein the ethylene olefin block polymer is an ethylene/α-olefin heteropolymer characterized by 15 or less before crosslinking. One or more of the characteristics: (4) having a Mw/Mn of from about 1.7 to about 3.5, at least one melting point (Tm, to .c § ten)' and density (d, in grams per cubic centimeter), wherein Tm and d The values are corresponding to the relationship: Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or 20(b) has a Mw/Mn of from about 1/7 to about 3.5 and is characterized by a heat of fusion (Bagua ' J / g ) and a Δ amount (AT, 〇 C) defined by the temperature difference between the most DSC peak and the highest cryistaf peak, wherein the values of at and ah have the following relationship: For ΔΗ greater than 〇 and up to 130 J/g is 108 200900545 ΔΤ>-0.1299(ΔΗ)+62.81 > for ΛΗ greater than 130 J/g Wherein the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRTSTAF 5 peak, the CRYSTAF temperature is 3 〇 ° C; or (c) The compression molded film of the ethylene/α-olefin heteropolymer was measured at 300% strain and one cycle of elastic recovery (Re, %), and had a density (d, g/cm 3 ), wherein, when ethylene/ When the α-olefin heteropolymer has substantially no cross-linking phase, the values of Re and d satisfy the following relationship: 10 Re>1481-1629(d); or (d) having a TREF classification at 40 ° C and 130 a molecular fraction eluted between °C, characterized in that the fraction has a molar comonomer content of at least 5% higher than that of a comparable random ethylene heteropolymer fraction eluted at the same temperature, wherein , the comparable random ethylene heterogeneous 15 copolymer has the same comonomer, and has a melt index, a density, and a molar commonomer content within 10% of the ethylene/germanium-olefin heteropolymer. The entire polymer is based on the basis); (e) has a storage modulus at 25 ° C, g, (2 5 ° C), and 100 Χ: the storage modulus of the time, G' (l 〇〇 ° c), where g, (25 ° C) versus G, (10 (TC) ratio of 20 cases is about 1:1 Up to about 10:1; or (f) having a rating of 40 when using TREF. (: eluting one of the molecular fractions with 13CTC, characterized in that the fraction has a block index of at least 〇5 and up to about 1 and a molecular weight distribution greater than about 丨3, Mw/Mn; or (g) An average block index of greater than about 〇 and up to about 1. 〇, and a molecular weight distribution of greater than about 109 200900545 1.3, Mw/Mn. 46. The fabric of claim 1 wherein the fabric is a woven fabric and A fabric comprising a majority of denier having a denier of less than about 3000 denier. 47. The fabric of claim 18, wherein the fabric is a knit fabric and is characterized by at least about 30 as measured according to ASTM D2594. % stretch. 110