CA2674597A1 - 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

COLORFAST FABRICS AND GARMENTS OF OLEFIN BLOCK COMPOSITIONS
CROSS-REFERE.NNCE TO RELATED AI'PLICATIONS

[00011 For purposes afC'nited States patent practice, the contents of U.S.
Provisional Application No. 60;'885,.202, tiled.lanaary 16, 2007, is herein incorporated by reference in its entirety.

FIELD OF 'l"HE INVENTION

100021 This invention relates to dyed fabrics that are colorl:ast.
BACKGROLND AND SUMMARY OF TI-IE INVENTION

[00031 Many different materials have been used in making dyed fabrics for use in, for example, barments. It is often desirable that such fabrics liave a combination of properties including one or more of the following: dimensional stability, heat-set properties, capability to be made stretchable in one or both dimensiotis, chemical, heat, and abrasion resistant, tenacity, etc. In addition, it is also often important that such dyed fabrics be able to hold color, e.-., dve, long;er aiid darker when subje.cted to laundering without significantly degrading one or more of tfle aforenientiozied properties. Fut-the.r, increased throughput with reduced defects, e.g., fiber breaka~e-, is so~.times desirable if the dyed i'abric is, for example, a knitted fabric.
[0004] Improved fabrics have now been discovercd ~khich often have a balanced combination of desirable properties including beii-ig able to be able to be c-olored darker and 11oEd color, i.e., colorfast, with laundering. These compositions may also allow for irnproved processability in some applications. The fabric of the present invention is typically a knit or woven fabric comprisirzt-, elastic fibers. Such knit fabrics include, for example, polyesters like microfiber polyesters. "I'be elastic fibers often coinprise the reaction product of at least one etliylerie block polymer and at least orre crosslitiking agent. Tbe fibers are characterized by an arnount of cross4inkirL~ such that the fabric lias the desired properties. -1.`bc ethylene block polyi7ier is usually (A1 an ethylenc=0.-olefi:j in'.',rpc?l, mer. wherein the ethv lene:'ft-olct~~al i1iierpolx yi-ie;r (1) an average block index greater than zero and up to about 1.0 and a molecular Gveiglit distribution, Mw'IV1.n., greater than aboLit 1.3; or (2) at least one molecular fraction which elutes between 40"C and 1'30"C.
when fractionated using "fREF, cliaracterized in that the fraction has a block index of at least 0.5 and up to about 1; or (3) anMwiMn frorn about 1.7 to about 3.5, at least one melting point.. Tm, in degrees Cefsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:

T, > -2002.9 + 4538.5(d) - 2422.2(d)2; or (4) an iv1w!Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, AH in J/g, and a delta quantity, AT, in degrees Celsius defined as the temperature diflerence between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of AT and Af1 have the following relationships:

AT > -0. 1299(AH) + 62.81 for dFl greater than zero and up to 130 .l/g, AT > 48 C: for A H greater than 130 J.%g , wherein the CRYSTAF peak is determined tising at least 5 percent of the curnulative polyiner, and if less than 5 percerlt of the pofymer lias an identifiable CRYSTAF peak, then the CRYSTAFtemperature is 5(3'C; or (5) an elastic rc,covery, Re, in percent at 300 percent strain and I cycle measured with a conipression-molded film of the ethylene,'a-oletim interpolyaner, aild has a clensity. d, in ~,~rams"cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene,'a-olefin interpolymer is substantially free of a cross-linkecl phase:

Re > 1.481-1629(d); or (6) a inol4cular frac.ticjn v, i-.ich e4utcw betvvt;en 40 C a1id 130 C:

_ = 9 . ... r . I.. _ . . . . . . _ . _ _ . . .. . . . ~ . .. ..

interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/u.-olefin interpolymer; or (7) a storage modulus at 25 C. G'(25 C), and a storage modulus at 1 00 C. G'(1[f0 C), wherein the ratio of Cr'(?a C) to G'( l00 C) is in the range of about I:1 to about 9:1.

(00051 The ethylene/ct-olefin interpolymer characteristics (1) through (7) above are given with respect to the ethylene/a-olefin interpolymer before any signiti.cant crosslinkino, i.e., before crosslinking. The etkrylene/a-olefin interpolymers useful in the present invention are usually crosslinked to a degree to obtain the desired properties. By using characteristics (1) through (7) as measured before crosslinking is not meant to suggest that the interpolymer is not required to be crosslinked - only that the characteristic is measured with respect to the interpolymer without significant crosstinking. Crosslinking may or may not change each of these properties depending upon the specific polymer and degree of crosslinking. The dyed fabrics of the present invention may often be characterized by a color change of greater than or equal to about 3.0 according to AAT'CC. evalLiation after a first wash by 2A. The dyed fabrics of the present invention may often be characterized by a color strength after dying of greater than or equal to about 600 as rneasured with a spectrum photometer.
BRIEF DE:SCRIP`I'ION OF Tl.-IE I)RAWING5 100061 Figure I shows the ertelting point/density relationship for the inventive polyi-ners (represented by diainonds) as compared to traditional randorn copolymers (represented by circles) and Ziegler-Natta copolymers (represeilted by triangles).
100071 Figure 2 shows plots of delta DSC-CRYSTAF as a function of DSC. Melt Enthalpy for various polymers. The dianronds represent random ethvle,ne/octene copoiyYilers:
the squares represent poly3ner examples 1-4; the triangles represent polymer examples 5-9;
and the circles represent polymer examples 10-19. The. "X" svm.bols represent polyrner examples A*-F *.
100081 Figure 3 shows the etfect of density on elastic rec;overy for unoriented films rl1ade . . , , ~:(:;r, inventiv.w ira _ Tiel from The Dow Chemical C,ompany)). The squares represent inventive ethyloueibutene copolymers; and the circles represent inventive ethvlenc;:'octene copolymers.
100091 Figure 4 is a plot of octene content of TREF fractionated ethylene/ 1-oetene copolvmer fractions versus `I`REF elution temperature of the fraction for the poEvmer of Example 5 (represented by the circles) and comparative poly-mers E and F(represented by the "X" symbols). 'T'he diamonds represent traditional random etlzylene,`octene copolymers.
100101 Figure 5 is a plot of octene content of TREF fractionated ethyleDe,` l-octene copolyrmer fractions versus yI'REF elution temperature of the fraction for the polymer of Example 5 (curve 1) and for comparative F(c-urve 2). 'I'he squares represent Exan-iple F*;
and the triangles represent Example 5.
1001.11 Figure 6 is a graph of the log ofi'storage modulus as a function of temperature for comparative ethylene/1-octene copolymer (curve 2) and propylene/ ethylene-copolymer (curve 3) and for two ethylerie/ 1-oetene block copolymers of the invention made, with differing quantities of chain shuttling agent (curves 1).
100121 Figure 7 shows a plot of TMA (I mm.) versus flex modulus for some inventive polymers (repre-sented by the diamonds), as compared to some known polymers.
The triangles represent various Dow VERSIFY `' polymers(available from The Dow Chemical Company); the circles represent various random ethylenei'styrene copolymers;
and the squares represent various Dow AFFINITYT'll polymers(available from The Dow Cliemica[
Company).
100131 Figure 8 shows photos of a lab dveing machine.
100141 Figure 9 shows a dyeing and reduction wash process.
DETAILED DESCRII'TION OF 'FHF. INVENTION, General Definitions ((I0151 "Fiber'" tneans a material in which the length to diameter ratio is greater titall about 10. Fiber is typica3ly- classified according to its diameter. Filainent fiber is generally defined as having an individual fiber diametcr ~_,reater than about 15 denier, usuafl;~ oreater tliai1 about S0 denier per filament. Fine denier tiber generally refers to a fiber b.avim.): a diaineter less tb~:n abotit 15 den:. r per fiiament. 'Micrcjdenier fiber is ~:nerally di~;Iined as y .~.-: iic,:, ], a disc:otitinuous strand of material of definite leilgth (i.e., a strand which has beeri cut or other",,-ise divided into segments ofapredeterinined length).
[00171 "Elastic" means that a fiber will recover at least about 50 percent of its stretched length after the first pull and after the fourth to 100% strain (doubled the length). Elasticity can also be described by the "permanent set" of the fiber. Permanent set is the converse of elasticity. A liber is strretched to a certain point and subsequently released to the original position before stretch, and then stretched again. 'T'he point at which the fiber begins to ptill a load is designated as the percent pern-mnent set. "Elastic materials" are also referred to in the art as "elastomcrs" and "elastameric". Elastic material (sometimes referred to as an elastic article) includes the copolymer itself as well as, but tiot limited to, the copolymer in the form of a fiber, filrn, strip, tape, ribbon, sheet, coating, molding and the like.
The preferred elastic niaterial is fiber. The elastic material can be either cured or uncured, radiated or un-radiated, andlor crosslinked or uncrosslinked.
[00181 "Nonelastic material" means a material, e.g., a fiber, that is not elastic as defined above.
100191 "Flomofil fiber" means a fiber that has a single polymer region or damain, and that does not have any other distinct polyrn.c:r regions (as do bicomponent fibers).
100201 "Bicomponent fiber" means a iiber that has two or more distinct polymer regions or domains. Bicomponent fibers are also know as conjugated or multicompon:erit fibers. The polymers are tiisually different f'roin each other altholi(vh two or more coinponents may comprise the same polyniir. "l'he polymers are arranged in substaxitially distinct zones across the cross-section of the bic<>mponent liber, aiid usually extend continuously alolag the length of the bicomponent fiber. '-1'be configuration of a bicomponezit fiber can be, for example, a sheath/core arrangement (in which one polymer is surrounded by another), a side by side arrangement, a pie arrangement or an `islands-irl-the sea" arrangement.
Biconiponeiit fibers are further described in U.S. Patents No. 6,225,243, 6,140,442, 5,382,40{), 5,336,552 and 5,1 08.820.
10021.1 -'Meltblor.~,n fibers"- are fibers formed by extruding a molten therm.op[astic potyilrer coiiipositic>n through a plurality of fine, usually circalar, die capillaries as molten threads or fiianients into converging high velociiy gas strcai-ns (e.g. air) ~.vhich liÃnction to attetiuafic the tbrG_acis or filarnents to rGducc 1 ".l'he: filaments or threads are cai-ried , ._. ,..: ... _ 4,. _I ~_ _. - _.,. . `. .1. i. .. .-.. ....
Sti.1.Ac 4 .. A41 1.~. ,. ~e1s [0022] "Meltspun fibers" are fibers formed by i-nelting at least one polyi-ner and then drawing the fiber in the melt to a diameter (or other cross-section shape) less than the diameter (or other cross-section shape) of the die.
[0023[ "Spunboncl fibers" are fibers formed by extruding a molten thermoplastic polymer composition as filaments through a plurality of fine, usually circLElar. die capillaries of a spinrreret. The diameter of the extruded filaments is rapidly reduced, and then the filaiiients are deposited onto a collecting surface to form a web of randonily dispersed fibers with avera~;e diaaneters generally between about 7 and about 30 microns.
100241 -Nonwoven" means a web or fabric having a structure of individual fibers or t.hreads which are randomly interlaid, but not in an identifiable manner as is the, case of a knitted fabric. The elastic fiber in accordance with embodiments of the invention can be employed to prepare nonwoven structures as well as composite structures of elastic nonwoven fabric in. combination with nonelastic materials.
100251 ":Yarn" means a continuous length of twisted or otherwise entangled filaments which can be used in the manufacture of woven or knitted fabrics anci other articles. Yarn can be covered or uncovered. Covered yarn is yarn at least partially wrapped within an outer covering of another fiber or material, typically a natural fiber such as cotton or wool.
[0026] "Polymer" means a polymeric cotnpound prepared by polymerizing monomers, whether of the same or a different type. The generic term "polymer" embraces the terms -homop ly mer," '-copolymer,: " .`terpolymer ' as well as "interpolymer."
[0027[ "Interpolyrn.er" means a polymer prepared by the polymerization of at least two different types of nionomers. Tl1e generic term '`interpolymer" includes the term "copolymer" (wlaich is usually employed to refer to a polymer prepared from two different monomers) as well as the term "terpolymer" (which is usually employed to refer to a poly=ner prepared from three differerit types of monomers). It also encompasses polyillers made by polymerizing four or more types of monomers.
100281 The term "ethvlene%'a-olehn interpolyrner" generally refers to polyiners comprising ethylene and an a-oletin having 3 or more carbon atoins.
Preferably, ethylene comprises the ina.jority z-ae3ie fraction of the whole polymer, i.e.. ethylene comprises at least about 50 mole perceiit of the whole polymer. More preferably ethylene comprises at least abocjt 60 mole pereent, at least about 70 mole percent. orat least about 80 niole percent. ~~=ith } .
f >}'5q = ""L- q [[t y( vi~pt13Yl3Y1J~>-. Lxs. ~ ~L.zWi~Wr+ rr>>A:A~ ..~...:.5. ~.. = e~.i. ._ ._.nl v~sl _..._i. ` a...:.1 ~ ~__~ i~.. .,.,....ta.

n'tole percent of the whole polymer and an octene content of from about 10 to about 15, preferably from about 15 to abotit 20 mole percent of the whole polymer. In some ernbodiments, the ethylene.`a-oletin interpolymers do not include those produced in. low yields or in a rninor amount or as a by-product of a chemical process. While the ethylene=a-olcfin interpolymers can be blended with one or more polymcrs, the as-produced ethylcne,'a-oletin interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
100291 The ethylene/rx-oletin interpolyniers comprise ethylene and one or more copolymerizable a-olefin comonomers in polymerized forni, characterized by multiple blocks or segnients of two or more polynierizzed monomer units difterinb in chemical or physical properties. That is, the ethylene/a-olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers. 'I`hc terms "interpolymer" and "copolyi-ner" are used interchangeably he-rein. In some embodiments, the multi-block copolymer can be represented by the following formula:
(AB)õ
where n is at least 1, preferably an integer greater than 1, such as 2, 3. 4, 5, 10, 15, 20, 30. 40, 50" 60, 70, 80, 90, 100, or higher, :-A" represents a hard block or se-gment and "B" represents a soft block or segment. Preferably, As and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chai-1. In other words, the block copolymers uscia[Iy do not have a structure as follows.
AAA-----AA-BBB-BB
[0030] In still other embodiments, the block copolyniers do not usually have a third type of block, which comprises different comonomer(s). I.n yet other en-ibodirncnts, each of block A and block B I-ias monomers or comonomers substantially randomly distributed ~vithin the block. In other worcls, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition. such as a tip se~,~ment, which has a substantialiy different composition than the rest of the block.
10031.1 -rhe multi-block polymers typically comprise various amounts of `hard a~1Ãi soft" se-ments. ` I Iard" segments refer to blocks of polymerized units in which c.thyletre is present in an aTtlouiit Lireater than about 95 ~,vei_vht per::erit. ~1nd prctcrably greater thati abotlt _'ni,- is s ,". . . ' . :a '~li.e polymer. In some, enzbodiments, the hard segmen.ts comprises all or substantially all ethylene. "Soft'' segments, on the other hand, refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about Sweight percent. greater than about 10 weight percent, or greater than about 1. 5 weight percent based oii the weil;ht of the polymer. In some embodiments, the comonona.er content in the sQft segments can be greater than about 20 weight percc nt, greater than about 25 weight percent, greater than about 30 weight percelit, greater than about 35 weight percent, greater thai-i about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weil;ht percent.
100321 The soft segments can often be present in a block interpolymer from about I
weight percent to about 99 weight percent of the total weight of'the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 90 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent., froin about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer. C,anversely, the hard segments can be present in similar ranges. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such metliods and calculations are disclosed in a concurrently filed U.S. Patent Application Serial No.
11/376,835, Attorney Docket No. 3850639Ã39558, entitled " Ethyfene!ci-C}letins Block Iiiterpolymers", tiled on March 15. 2006, in the iia.me of Co1ii7 L.P. Shan, Lonnie HazlÃtt, et. al. and assigiled to Dow Global Technologies Inc., the disclosure of which is incorporated by referen.cc; herein in its elitiretv.
100331 The term ``crystallinc." if enaployed. refers to a polymer that possesses a first order trailsitiott or crystalline aiielting point (Tm) as detertiiined by differential scainliilg calorinietry {DSC} or equivalent tecbniÃ.lue. The term rnay be used interchangeably witli the, teri1i "sernicrystalline". Tbe term " amorpbous" refers to a polymer lacking a crystalline me.ltino point as determined bv dit-f:erentia.l sÃ:Ginn..rtg calc;rinic,try-(DSC) or equivalent ~ ~ ~ ,~ ..,_. . ~= . .~
i I't=c tcr~ii `n- t, -~
C.,~ ~Jlrxsingf -_kÃ~ or rnor~
_~_ preferablyjoit-ieci in a linear manner, that is, a polymer cornprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion. In a preferred embodiment, the blocks differ in the a.moun.t or type of comonomer incorporated therein, the de.nsity, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregedarity, the amount of branching, including long chain branchiilg or hyper-branching, the homogene.ity, or anv other cbei-nical or physical property. The multi-block copolymers are characterized by uilique distributions o#'both polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique, process making of the copolymers.
More specifically, when produced in a continuous process, the polyniers desirably possess PDI
f'rom 1.7 to 2.9, preferably Froni 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. Wtien produced in a batch or semi-batch process, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most pre.ferabEy from 1.4 to 1.8.
10035] In the following description, all numbers disclosed herein are approximate values, regardless whether the word "about" or `'approxir~ate' is used in connection therewith. They may vary by I percent, 2 percent, 5 percent, or, sornetinies, 10 to 20 percent. Whenever a numerical range with a lower limit, Rl- and an upper limit, R"", is disclosed, any number falling within the range is specilically disclosLd. In particular, the i'ollowing nunibers within thc, range are specifically disclosecl: R-R'--k*(R" R1). wherein k is a variable ranging from 1 percent to 10(1 percent with a 1 percent increment, i.e., k is i percent, 2 percent, 3 percent, 4 percent, 5 perc-ent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover, any numerical range defined by two R
numbers as defined in the above is also specifically disclosed.

Ethy[ene/u-41efin Interpolymers [00361 `I'he oletin block polymers, e.g. ethylen.eicl-olelin interpol y mers, used in ctiibodimetits of the invention (also referred to as "inventive interpolymer"
or'`inve,rrtive polymer"} comprise ethylene and one or riiore copolymerizable a-olefin coinonorners in polymerized l'orr .Ã.',.--~~c1,e-ritcd by multi.ple blocks or sepncnts of Vvo or z?iore polyrricrired ~~-rabiy a ~.z i: ~r~d se Ã~r ti .t.xe o.'thi- ~.~slnek_ :., _ . ..s.

[0037] In one aspect, the ethylenc;ra-olefirl interpolymers used in embodiments of the invention have aM,:M,, from about 1.7 to about 3.5 and at least one nielting point, 'I',,, in degrees Celsius and density, d. in grainsr`ctibic ceatimeter, wherein the numerical values of the variables correspond to the relationship:
T,,, > -2002.9 + 45' ) $.5(d) - 2422.2(d)2-, and prelerably T, ?-6288.1 + 13141(d) - 6720.3(d)2, and more prel:erably .
"T? 858.91 - 1825.3(d) + 1112.8(d)2 100381 Such meiting point/density relationship is illustrated in Figure 1.
Unlike the traditional random copolymers of ethylen.e/a-olefins whose rne[ting points decrease with decreasing densities, the inventive interpolymers (represented by diamonds) exhibit melting points substantially independent of the density, particularly when density is between about 0.87 g/cc to about 0.95 g'cc. For example, the melting point of such polymers are in the range of about 110 C to about 13 W C when density ranges from 0.875 g:~cc to about 0.945 g1cc. In sozne ernbodirnents, the melting point ol'such polymers are in the range of about I 15 C to about 125 C wb.en density ranges from 0.875 g.`cc to about 0.945 Z,.`ce.
[00391 In another aspect, the etb.ylene/o.-olefin interpolymers comprise, in polyrnerized forrn, ethylene and one or more Ex-oletins and are characterized by a `h, in degree Celsius, defined as the temperature for the tallest Differe7itial Scanning Calorimetry ("DSC"') peak minus the temperature for the tallest Crystalf.i:zation Analysis Fractionation (`'CRYSJ"AF") peak and a?aeat of 1'usicin in J;'g, AH, and Al' and AIl satisfy the following relatioilships:
AT >-0. I 299(Ali) + 62.81, and preferably AT > -0.1299(AI--I) + 64.38, and more preferably AT > -0.1299(A,1-I) ~ 65.95, for Af1 up to 130 Jig. Moreover. A'I' is equal to or greater than 48 C for A1l greater than 130 J: g. "I"he C'RY STAF peak is deterniined using at least 5 percent of the cumulative polymer ( . that is, the peak must represent at least 5 percent of the cun-iulative polymer), and if less than percent ol`the polymer has an identifiable,~ CRYST,~F peak, then the CRYSTAF

tCt11 i.l? . dAll is the Yl 1 i. JF- ileat .7f i~is ? i;? '. i t.R`V StA`

~7101_ VL
~.~~.'..

examples. Integrated peak areas and peak tei-nperatures are calculated by thc computerized drawing pro8rarn supplied by the instrument maker. The diagonal line shown for the random ethylene octene comparative polymers corresponds to the equation AT =-0.1299 (AH) T
62.81.

100401 In yet another aspect, the ethylene `u-oletin interpolymers have ainolecular fraction which elutes between 40 C and 130 C when fractionated using Teniperature Rising Elution Fractionation {"TREF"), characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer fraction eluting bemven tlle same temperatures, wherein the comparable random ethylene interpolymer contains the same cotnonomer(s), and has a melt index, density, and molar comonomer content (based on the whole polymer) within 1.0 percent of that of the block interpolymer.
Preferably, the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the block interpolymer andlor the comparable interpolymer has a total comonoiner content within 10 weight percent of that of the block interpolymer.
[0041] In still another aspect, the ethylen.e,'cr-olefin interpolymers are characterized by an elastic recovery, Re, in percent at 340 percent strain and 1 cycle rlleasured on a compression-molded filin of an ethylene,'a-olelin interpolymer, and has a density, d. in grarns/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when cthylenela-olefin interpolymer is substantially free of a cross-1i:n.k.ed phase:
Re >1481-1629(d); and preferably Re ? 1491-1629(d); and more preferably Re>15f11-16''9(d) ; arid even rnore: preferably Re >1 5 11-1629(d).

,ure ; shov,,'s tiie effect of density on elastic recovery ror unoriented fifin.s niade 100421 Fig i-rom ce-rtairi inventive interpolymers and traditional randoin copolymers.
For the sainc density. the invenzize interpolymers have substantially higher elastic recoveries.
100431 1~1 some em1?odime.nts, the :.'thyiene-'(t-olei-1iFtiterpoly~-ners have a tensile strength - _ _ t= t -, ,, ..~. . 10 s 1 percent, highly preferably at least 800 percerit, and most highly preferably at least 900 percent at a crosshead separation rate of 11 cm:/minute.
(0444] In other embodiments, the e.thyle-neia-oiefin interpolymers have (1) a storage modulus ratio, G'(25 C)/G'(1(}0 C), of from I to 5(}, preferably from 1 to 20, more preferably from I to 10; and/or (2) a 70 C compression set of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent, down to a compression set of 0 percent.
[0045] In still other embodimeiits, the ethylenefa-olefin interpolymers have a compression set of less than 80 percent, less than 70 percent, less than. 60 percent, or less than 50 percent. Preferably, the 70 C compression set of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and may go down to about 0 percent.
[0046] In some embodiments, the ethylene,'ct-oletin interpolymers have a heat of fusion of less than 85 Jig and/or a pellet blocking strength of equal to or less than 100 pounds/foot2 (4800 Pa), preferably equal to or Iess than 50 1bs/#i~ (2400 Pa), especially equal to or less than lbsi'ft' (240 Pa), and as low as 0 Ibsfft2 (0 Pa).
100471 In other embodiments, the eth.y[ene-/a-olefin interpolymers comprise, in polymerized form, at least 50 mole percent ethylene and have a 70 C
compression set of less than 80 percent, preferably less than. 70 percent or less than 60 percent, most prelerably less than 40 to 50 percent and down to close to zero percen.t.
10048] In some embodimejits, the multi-block copolymers possess a PL)I fitting a Schtiltz-Flc>ry distribution rather than a Poisson distribution. "hhe copolymers are i'iErther characterized as having both a polydisperse b[ock distribution and a polydisperse distribution of block sizes and possessing a most probable distribution of block lengths.
Preferred multi-block copolymers are those containing 4 or more blocks or segments iiieluding terininal blocks. More preferably, the copolymers include at least 5, 10 or 20 blocks or segments including terminal blocks.
100491 Cornononier contettt may be measured using any suitable tecbniqLie, with techniclues based on nuclear magnetic resonaijce ("NMIt") spectroscopy preferred.
Moreover, ior polymers or bieticls of polymers having retative1v broad 'I"R1'T
curves, the polviner desirably is first fractionated Using, TREF into fractions eacb ha~-ing an e-lated te?"7?t?erxure raT?-C (?f1O"C or 'I hat Is, ctich eautLd tract3(?n has a collection telnf'. ,i1 . . . . _. . ~ .. . i. -- , ..t_. _ .

[00501 In another aspect, the inventive polymer is an olefin interpolymer, prGferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks (i.e., at least two blocks) or segments of two or m.ore polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer. said block interpolymer hm:fing a peak (but not.just a molecular fraction) which cIutes between 40 C and 1 3 )0'C: (but without eollecting andlor isolating individual fractions), characterized in that said peak, has a comonomer content estimated by infra-red spectroscopy w-hen expanded using a full width'half maximum (:FWIIM area calculation, has an average molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent hitiher_ than that of a comparable random ethylene interpolymer peak at the same elution temperature aiid expanded using a ftill width:'inalf maximum (FWHM) area calculation, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the blocked interpolymer. Preferably, the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer. The full width/half maximum (F'GUI,IM) calculation is based on the ratio of methyl to i-nettrylene response area I'CH;,'CHz] from the ATREb' infra-red detector, wherein the tallest (highest) peak is identitied from the base line, and then the FW1JM area is determined. For a distribution measured using an A"l`Rl~~~h peak, the FWHM
area is defiiaed as the area under the curve between T i and '1'2, where T i and T2 are points determined, to the left and right of the ATREF peah, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the A'I'RE-}' curve. A
calibration curve for comonomer content is made using random ethvlene!a-olefin.
copolyrners, plotting comonomer content from. NMR versus FWIJM area ratio of the TREF
peak. For this infra-red mthod. the calibration curve is ~:~enc,rated for the same comonomer t-vpe of iiiterest. The comonomer content of TtZEF peak of the inventive polymer can be determined by referencing this calibration curve using its EWI-1M methyl :
riiettivlene area ratio [C.l-I;iCH:fl of the TREF peak.
100511 Com.onomer content may be measured tisin~.~ anv suitable technique, with t T'.
Ãn y $:
_Ã~_ 100521 Preferably, for interpolymers of ethylene ai1d 1-octene, the block iriterpolymer has a conionomer content of the TREF fraction eluting between 40 and 13O C greater than or equal to the quantity (- (1.2013) T+ 20.07, more preferably greater than or equal to the quantity (-0.2013) T-; 21.07, where T is the numerical value of the peak elution te,niperature of the TREF fraction being compared. measured in 'C.
[00531 Figure 4 graphically depicts an ernboditnent of the block inter-polvmers oI' ethylene and 1-octene where a plot of the comonomer content versus TREF
elution temperature for several comparable ethylene;`l-octene interpolymers (random copolyn7ers) are fit to a Iine representing (-0.2013) T-'- 20.07 (solid line). The line for the equation (-0.2013) T + 21.07 is depicted by a dotted line. Also depicted are the coinonomer contents for fractions of several block ethylenell-octene interpolymers of the invention (multi-block copolymers). All of the block interpolymer fractions have signiliuantly higher 1-octene content than either line at equivalent e1ution temperatures. "1'his result is characteristic of the inventive interpolya.ner and is believed to be due to the presence of differentiated blocks within the polymer chains, having both crystalline and amorphous nature.
100541 Figure 5 graphically displays the `1"REF curve and comonoYner contents of polymer fractions for Example 5 and Comparative F discussed below. The peak elutirlg from 40 to 130 C. preferably from 60 C to 95 C for both polymers is fractionated into three parts, each part eluting over a temperature range of less than l0 C. Actual data for Exai7lple 5 is represented by triangles. The skilled artisan can appreciate that an appropriate calibration curve iiaay be- constructed for interpolymers containing different comc>non-iers aild a line usec3 as a comparison fitted to ihe 'F REF values obtained from conaparative interpolymers of the same monomers, preferably random copolymers made usin, a metallocene or other liomogeneous catalyst composition. Inventive interpolymers are characterized by ai-no~lar comonomer content greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent cyreater. more preferably at least 10 percent greater.
[0035] In addition to the above aspects and propez-ties described hc;rein, the inventive polymers can be characterized by one or more additional characteristics. ln one aspect, the it-iveiitive polviner is an oletin interpolyirier, preferably comprising et.h3-lene and one or in<>re c: polyme.ri.f~?ble comc>noiners in lsoly=ner;zed t r:n. cltaracterize.d by riia?tiple blocks or .. a . . .~ . . ~ < p y - c . . . - .., . :. . ...-. . .

ISii:i~.v3FSiiLi4ei -i`~-fractionated usin~ TRE~ incre~nents, cl~aractc;riz.ed ir~ tbat said iraction has a molar como~nomer cont~:~.t bi~er, pre.~l~:rably at least 5 percez~t lri~b.er, more prc,ferably at least 1 tl, 15, 2{3 or 2~ percent l~igher, than that of a comparable ra.nd.om ethyiene interpol~.~mer fractio~
eluting bet~vicen tl~e sazne te~mperatures, ~vberein said comparable randoi~
etb.y-lene ir~terpolymer comprises tl~e s~une comonomer(s}, preferab~y it is the same comonomer(s), and a mett ir~dex, dcnsity, a~zd rnolar co~nonorr~er content (based on the ti~-l~ole poly~ner} ti~.-ithin t Q
percent c~f that of the block~:d interpolytt~er. Preferably, the iviv~~,':'~ln o~l'~the comparable interpolymer is alst3 wit.hin 1~ percez~t of that of the b1ocl~ed interpolymer ar-d~'or tl~e co~xzparable interpolymer has a total. comonomer content within 10 wei.g[~t perce~~t o~ tl~at of the blocked interpolymer.
[00Sb~ Preferably, the above interpolyzners are it~terpolymers o# etbylene and at feast one a-olefi~, especially those interpolyi~ners baving a~vhole polyrmer density frorr~ about (1.855 to abo~.it 0.935 ~/cm', and more especially for polymers h.avin~ ~nore than about 1 r~ao[e p~reent comonomer, th~: blocked interpolyrner has a comono~r~er content of the 7'RE~F
1'raction. elutin~;
bet~veer~ 40 and 130 C greater than or equal to the quantity (-0.135fi} T+
13.89, more preferably ~reater than or equ.al to the quantity (-0.1356) T~!-- 14.93, and most preferably ~~reater tban or equal to the q~aantity (-0.2013jT ~ 21.O7, v~bere T is the numerical value of the peak ~TRIa~ elrltion te~nperature of tl~ze TREI~ fraction bein~ compared, rneasured in C.
[0057~ Preferably, for tb.e above interpolymers of ethylene and at least one alpha-oletin especiall.y those interpolymers ha~~in~ a~;hole polymer de~nsity from abo~at U.8a~ to abor~t f1.~35 l;icm~. and ~nore espec,ially for poiymcrs bavin~ more than about 1 rrtofe perce.nt cornonomer, the blocked interpolymer ~as a coz~nonom.er content of t~e T
IZI~r~ fraction eiutir~~
between 40 and 130 C ~reater than or erlual to tl~e quantity (- 0.2C~13) T
20.07, more preferably ~;reatc~r tl~an c~r eq~zal to the quantity (-0.2013) T+ 21.07, ~n~he:re T is th~; num.erical value of the peak elution temperature of tbe 'T'REF f~action being compared, measured in C.
[~(l~fi~ In sti~l another aspect, tbe iov~:z~tive polyrner is aa~ olelin i~lterpolyrner, preferably comprising etl~ylene an.d one or n~ore copoly~r~erizable comonomers in poly7~~~erized torm, chara~;teri~ed bv multiple blocks or se~r~~ents c~f t~~~o or tnore polyrnc~rize.d r~~onomc,r u~lits differil~g in c~~emical or pl~ysical proper~l:ies (blocke.~d i~.terpc~lyrt~er~). z~~ost pret~erably a nrulti-bloc~C cÃ3polyn~er, said blQclZ it~t~e~polyrner ba~.~i~~.~ a n~olec~~lar tl-action. ~ hi~:b e~rites bet~veen 4~~"C <~~~d 1 3t~"C.'. ~I~~.r~ i~rac;tic~tlat~:d ~asir~i7 "I Rl-:.l=' in~:re~~.n~:nts, ~:Ira~~ac.t~;ri~~:d in ti~at 4very t ~:.. t~:,at _. ~.
1<_~~ ~_~1 ~. . _ , ~. _ ~~' :S ~`(~~i i ~ ~,: ~ _ ._ 1 . I t ~ "

iiii~it~', pS:~~:;it l s c. zi s 1.1~Ii)~E q d.: ::'; . s;vt;r's-' ~I :i.:
11;~T? :'~.`.s ~. ,~J~S`_ ~. ~ i:, , i~~~ ~, - ~ `~

or higher. More preferably, said polymer fractions, havino at least I mole percent comonomer, has a DSC melting point that corresponds to the equation:
Tm >(-5.Sq26)(mole percent comonomer in the fraction) + 135.90.

[0059] In yet another aspect, the inventive polymer is an olefin interpolymer, preferably comprisin(i ethylene and one or more copolymerizable comonomers in polymerized forrn, characterized by multiple blocks or segments of two or more polyzneri;red monornÃ:r units differing in chemical or physical properties (blocked interpolymer), most preferabl.y a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 40 C an.d. 130 C, when fractionated using T'RF.F increments, characterized in that every fraction that has an ATREF elution temperature greater than or equal to about 76 C, has a melt enthalpy (heat of fusion) as measttred by DSC, corresponding to the equation:
Ileat of fusion (J/gm) < (3. i 718}(ATREF elution temperature in Celsius) -136.58, 100601 The inventive block interpolymers have a molecular fraction which elutes between 40 C and 130 C, when fractionated using TREF inerernents, characterized in that every fraction that has an ATREF elution temperature between 40l C and less than about 76 C, has a melt enthalpy (heat of fusion) as measured by T)SC, corresponding to the equation:
lIeat of fusion (:f.-`~m) <(i _ 13 1 2)(ATREF elution temperature in CelsiLIs) -~ 22.9'T.
ATREF Peak COnaOnarner Composition Measurement by Infra-Red Detector 100611 "T'he comonomer composition of the 'FRp:F peak can be measured using an iR4 infra-red detector available from I'olymer Char, Valencia, Spain (i'=t~~ ~, ~ :, _ ,: 0117;
100621 The "composition mode" of the detector is equipped with a iiieasurement sensor (CH2) and composition sensor ('CH;) that are tixed narrow band infra-red filters in the region.
of 2800-31100 ctri"'. The zn4asurement scnsor detects the methylc.ne (Cf12}
carbons oil tbe polymer (which directly relates to the polyiner concentration in solution) ivhile the composition sensor detects the methyl (CH,) aroaps of the polyme-r. The mathematical ratio of the cornposition si~.~~nai (C.1i3) divided by the measurement signal (CI12) is sensitive to the comonomer content ofthe measured polymer in solution and its resporise is calibrated Nvitb.
k~iÃ~vvn Ã;thvlcne z,!i?hn-olefin Ã:opofymÃ:r stanclfm]Q.

-i~-process. A polymer specific calibration can be created by measuring the area ratio of the CI-I3 to CH2 for polyrners with known comonomer content (preferably measured by NMR). The comonorner content of an ATREF peak of a polymer can. be estimated by applying a the reference calibration of the ratio of the areas for the individual CH; and CI-I~ response (i.e.
area ratio CH.;iCI-I, versus camonomer content).
[00641 The area of the peaks can be calculated using a full r,vidth/half maximum (FWI-1M) calculation after applying the appropriate baselines to integrate the individual signal responses from the TREF chromatogram. The full width/half maximum calculation is based on the ratio of methyl to methylene response area [C.I-Iij'CI-12] from the ATREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FVG'HM area is determined. For a distribution measured using an ATREF peak, the FWHM
area is defined as the area under the curve, between "I'I and T2. wb.ere Tl and T2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
100651 The application of infra-red spectroscopy to measure the coiiionorner content of polymers in this ATREF-infra-red method is, in principle, similar to that of systems as described in the following references: Markovich, Ronald P.;
Ilazlitt. Lonnie G.;
Smith, Linley; `Developme nt of gel-permeation chromatography-Eourier transforn3 inlirared spectroscopy for characterization of ethylene-based polyc>lef~in copolymers".
Polymeric Materials Science and Engineering (1991), 65. 98-1 00.; and De.slauricrs, P.J.;, Rohlfing, D.C.; Shieh, E.T.; `'Qu~antifyin~ short chain branching microstructures in etlly[ene- I -oleftl copolymers iising size exclusion chromatography and Fourier transform infrared spectroscopy (SFC-wFTIR)". Polymer (2002), 43, 59-170., both of which are incorporated by reference herein in their entirety.
100661 tn other embodiments, the inventive ethylene/a,-olef.in interpolymer is characterized by an average block index. ABI. which is V-reater than zero and up to about I.f) axld a molecular weight distribution, M,,,-M,, greater than about 13, The average block inde;x, ABI, is the iveight average of the block index (`13I") for each ot'the. polymer fractions obtained in preparative. TREF from 2()"C and I I(?"C, with an incremeiit o#~ 5 C:

AI3I 131, 7-where BI, is the block inde-x for the ith 1Taction of the inventive ethylene."a-oletzn interpolymer obtained in preparative "I-REF, and w, is the weight pereentage ofthe ith fraction.

[00671 For each polymer fraction, BI is defined bv one of the two follorAdng equations (both of which give the same BI value):

13I = II'T, - I' T1,r' or BI =_ LnP - Ln.P~-õ
1fT. - IIT,,R LrtP,, -LnP",,,, where `I`x is the preparative ATREF elution temperature for the itli fraction (preferably expressed in Kelvin), Px is the ethylene tnole fraction for tize ith fraction, which can be measured byN?VIR or IR as described above. I'Aa is the ethylene mole fraction of the whole ethylene..`a-olefin intetpoiymer (before frac-tionation). which also cail be measured by NMR
or IR. TA and PA are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystallitie segments of'the interpolyrner). As a first order approximation, the TA and PA values are set to those for high density polyethylene homopolymer, if the actual values for the ha.rd segments" are not available.
For calculations performed herein, "I'A is 372 K, PA is 1.

[00681 'TAa is the ATRET temperature for a randoi:n copolymer of the same composition atid having an ethylene mole fraction of I';\jj. T.ka can be calculated from the following equation:

Lii PA13 OE/ T ~g where a and P are two constants which can be determined by calibration using anurnber of known random etbylene copolynlers. It should be noted that a and P may vary from instrument to instrutnent. Moreover, one twotild need to create their own calibration curve with the polviner coinposition of interest and also in a sirnilar molecular weight range as the fractions. There is a slight molecular weight effect. If the calibration curve is obtained 1rom sin~ilar molecular weight ranges. such effect would be e:ssentially negligible. In some embodiments, raridom etily-len.e copolyiiiers satisfy the following relationship:

Ln P 4~7.8 ~:" l:t" n~:3 0.639 .: . ._. , . _,.

vzm.'. ar _i~-ConverseCy, Pxo is the ethylene mole fraction for a random copolymer of the same composition and having an ATREF temperature of T.X. wliich can be caleulated from Ln I'xfl czr I`x + P.
100701 Once the block index (BI ) for each preparative "1 REF fraction is obtained, the weight averaoe block index, ABI, for the whole polymer can be calculated. In some embodiments, ABI is greater than zero but less than about 0.3 or from about 0.1 to about 0.3.
In other embodiments, ABI is greater than about 0.3 and up to about 1Ø
Preferably, ABI
should be 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 some errmbodiments.. ABI is in the range of from.
aboLit 0.3 to about 0.9, from abotit 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 em.bodiments. ABI is in the range of from about 0.4 to about 1.0, from about 0.5 to about 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 1.0, or lroin about 0.9 to about 1Ø
[0071] Another characteristic of the inventive ethylene/a-oletin interpolymer is that the inventive ethylene!a-ole-tin interpolyiner comprises at least one polymer fraction which can be obtained by preparative TREF, wherein the fraction has a block index greater than about 0.1 and up to about 1.0 and a molecular weiaht distribution, M";'MR, greater than abotit 1.3.
In some embodiments, the polymer fraction has a block index 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 Lip to about 1.0, or greater than about 0.9 and up to about 1Ø In other embodiments, t.kte polymer fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to abottt 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1Ø In still other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than greater than about 0.3 and u.p to about 0.5 , or greater than about 0.2 and up to about 0.5.
about 0.4 and up to about 0.5. In yet other einbodinients, the pr3lyine-r fraction has a block index greater than about 02) aiid lip to about {).9, greater than about 0.3 ) and up to about 0.8.
(Treater than about 0.4 and up to about 0.7, or greater thali abolit 0-5 and tiip to about 0.6.
100721 For copolymers ofethylene and an a-oletin., the inve,ntive polymers preferably Pc,,;se;s5 (1) a 1'IN of at least more preferably at least 1.5, sit least 1..7. or at least 2.0, and , ast L.6m U
~t ~. ~ - Ilyc~pt :. J

s~~~

ethylene content of at least 50 weight percent, (~} a(3ass transition tempcrature. T, of less than -25 C, more preferably less than -30 C; arzdior (5) one and only one [0073] Further, the inventive polymers can have, alone or in combination with anv other properties disclosed herein, a storage modtilus, G', such that log (G') is greater than or eclilal to 4001cPa, preferably greater than or equal to 1.0 MPa, at a#etnperature of 100 C.
Moreover, the inventive polymers possess a relatively flat storage modulus as a function of ternperature in the raaigc: from 0 to 100 C (illustrated in Figure 6) that is characteristic of block copQlymers, and heretofore unknown for an olefin copolymer, especially a copolymer ofethyl.ene and one or more C3-g aliphatic a-olefins. (By the term "relatively flat" in this context is meant that log G' (in Pascals) decreases by less than one order of ma~nitud.e between 50 and 100 C, preferably between 0 and 100 C).
[11074] The inventive inteFpolymers may be further characterized by a thermoznechanical analysis penetration depth of 1 mm at a temperature of at least 90 C as well as a flexural modulus of from 3 kpsi (20 MPa) to 13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have a thermomechanical analysis penetration depth of 1. mm at a temperature of at least 104 C as well as a flexural modulus of at least 3 kpsi (20 Wa). They may be characterized as having an abrasion resistance (or volume loss) of less than 90 mm3.
Figure 7 shows the TMA (1 mm) versus flex modulus for the inventive polymers, as compared to other known polymers. The inventive polyniers have significantly better flexibility-heat resistance balance than the other polyrn.ers.
[00751 Additionally, the ethyleiieia-olefin interpolymers can have a melt index, 1,, from 0.(11 to 2000 gI10 niinutes, preferably from 0.01 to 1000 g/ 10 minutes, more preterab[v from 0.01 to 500 gI10 minutes, and especially from 0.01 to 100 g'10 minutes. In certain embodiments, the etbvEene/a-olefin inte.rpolym.ers have a rnelt index. 12, l:xom 0_01 to 10 gli10 minrites, from 0.5 to 50 gl/40 ininutes, from 1 to 30 g/10 minutes, from 1 to 5g;ll0 miiiutes or frc~i-n 0.3 to 10 9,=10 minutes. In certain e-mbodianents, the rn.elt index.for the ethvlene/a-olefin polvzners is 1g.'10 minutes. 3~ll.0 ininutes or 5g:i10 minutes.
[0076[ The polyniers can have molecular weights, M, 9rotil 1,000 g/mole to D,000,000 g/mole. preferably frotii 1000 gi:"mole to 1,0(}0,000, more preferably from 1000 g;'inole to 300,000 girnole, and especially from 10,000 g,~mole to 300,000 ~~mole. The density of the inventi;-e polvnaers can be from 0.80 to 0.99 fr:'crn 3 and nre#~:er.tblv t:oA
etl}xvlenc: containin<4 thc ~ ~ `~r.
raii gc:- _ ~_ .. _. , . 7 1 [00771 The process of rnaking the polymers has been disclosed in the following patent applications: U.S. Provisional Application No. 60.`553,906, filed Marcli 17, 20Ã14; U.S.
Provisional Application No. 60r'662,937, filed March 17, 2{}05; U.S.
Provisiotral Application No. 60=`662,939, filed March 17, 20(}5; UT.S. Provisional Appl.icationNo.
60/662,938, tiled March 17, 26{}5;1'C`I' Application No. PCT;'US20U51fO[?8916, filed March 17,2005, PCT
Application No. PCTIliS2005`008915, filed March 17,2005; and PCT
Appiication'vo.
PCTtL52005:008917, filed March 17, 2Ã105, all of which are incorporated by reference herein in thi~ir entirety. For example, one such method comprises contactin(y ethylene and optionally one or more addition polytnerizable monomers other than ethylene, under addition polymerization conditions with a catalyst composition comprising:
the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonom.er incoiporation index, (B) a second olefin polymerization catalyst Izaving a comonomer incorporation index less than 90 percent, preferably less than 50 pereent, most preferably less thaii 5 percent of the comonomer incorporation index of catalyst (A), and (C) a chain shuttling agent.

100781 Representative catalysts and chain shuttlin.g agent are as follocvs.
100791 Catalyst (A l) is [N-(2,6-di(1-niethylethyl.)phenyl)amido)(2-isopropy[plienyl)(Ct-naphthal~.~n-2-diyl(6-pyridin-2-diyl)mcthane)]hafnium dimethyh prepared according to the teachings of WO 0340195, 2003liS0204017, USSN 1011429,024, filed May 2, 2003, and WO
04/24740.

p CH(rr-i3), (~~~ sc:)-r1c %t~
Hf o (H3C)-E[C

A2 !N ¾ ~ ~ I J
m~ ~ ~

ofW[) 03i'40195, '2003US02040I7, USSN 10<<`429,024, filed May 2. 2003, and WO
04/24740.

CH
/
N N
H~

(H,C)21iC CH3 E'H3 [00811 Catalyst (A')) is bis[:,Ni,N""-(2,4,6-tri(rnethylphcnyl)amida)c.thylenediaminelhaf'nium dibenzvl.
/ C~-13 H3C v---n CH~j I-iN--- WX~ X,, 0.17C6I-.1~
\ CH, ~
H3C' :
C 1't3 100821 Catalvst (A4) is bis((2-oxcwl-3-(di.bcnzo-If,1-pyzrolc -l-y-l)-5-(methyl)phcnyl)-2-pbenox~~mcthyl)cyclz3hexane-l,2-diyl zirconium (IV) dibcnzvl, prepared substalitially according to the teachings of L S-A-2{}f)4/04l 01.03), -~ ~
HXfC11~ eE42ChF15 o~ ~re-~~ ~"~~-~
(~'3~

100831 Catalyst (BI) is l,2-bis-(3,5-cli-t-but.ylplienvie:ne)(1-(N-(1-~nctI-:N,1c.thvl)iniminc);)niet'nvf )(2..oXovl') r:rcc>nitiam dibenzyi -`~`~_ C(CH;);
f 1AC.H.S)j C \ ! C(CtF3)3 ZCX"
o / 'k N-H(CFF;)2 X..:.-CH,Ct;H;
(CH;};

100841 Catalyst (B2) is 1,2-bis-(3,5-di-t-butylphen.ylene)(1-(iN-(2-methvlcycloh.exy1)-immino)rnethyl}(2-oxoy 1) zirconium dibenzyl C(CH;);
1-i;C
_~v ~ / o C(:CH3)3 zrX2 (H3C)~C~ \ ~ ~
CH~
-"({-.E~~3)3 100851 Catalyst (C1) is (t-butylamido)dimethyl(3-N-pyrrolyl-1,2.3,3a,7a-rl-inden-l-yl)silanctitanium dimethyl prepared substantially according to the techniques of USP
6,268,444:

(Ff~C.')2~i~ Ti(CH3)2 N
[0086] Catalyst (C?) is (t-hutylamido)di(4-i1iethylplien\~ 1~)(? i~lethvl-1233 )a,7a-rll-inden-1-vljsilanetitaniuni diine.thyl prcpared substantiallt- according to the tcachinITs of't;S-;Ik-?00z/t}04?86:

-.,..

HiC

C H, Si~ R.CH;.32 N

[00871 Catalyst {C3} is (t-butylamid )di(4-methylpheny[)(2-methyl-1,2;3, 3a,8a-q-s-indac-en-I-yl)silanetitanium di.methyl prepared substantially according to the teachings of US-A-2D03~'00428fi:

tt;C

Si~ Ti(E'H3)~
1{3C:

[00881 Catalyst (D l) is bis(di.m.cthyldisiloxane)(indenc-l-yl)zirc-onium diehlQt ide available from Sigma-Aldrich:

(ti3c)2si~ Zi-c1, [0089[ Shuttling Agents "hhe shuttling a<Z;ents e.mployed include diethylzinc.
di(i-b tyI)zinc, cli(n-hexyl)zinc-, triethvfaltiminum. trioctylaEuniinum, triethyl-allium, i-butyialuminum bis(dimtthylft-butyi)sil xanci. i-butylaluminum bis(di(triinetb.ylsilyl)an)ide), n-oÃ:tvlaiuminu1n diÃp}'ridine-2-methoxide?. b'<(n .)ctadÃ.cvl~i-btitN
ls~luminuin, i-~ ~-._- 9.
i , _ .. .. _ . _ .
.. .. ,, . ..: , . ... _ L-~~-e .. . .Ii I..;. ., . - . . i.,. ... - . _ i ... . ^ ? , ...- -~-azacycloheptaneamide), n-octylaluminum bis('-.3,6,7-dibenzo-l-azacycloheptarieamide), n-octylaluminum bis(dimetb.yl(t-butyl)siloxide. ethylzinc (2,6-diphenylpbenox.ide), mid ethylzinc (t-butoxide).
100901 Preferably, the foregoing process takes the form of a continuous solution process for forTning block copolymers, especially multi-block copolym.ers, pref:erably linear multi-block copolymers of tvv~o or more monomers, more especially ethylene and a C3-20 olelin or cycloolefin, and most especially ethylene and a C4_20 a-olefin, using multiple catalysts that are incapable of interconversion. That is, the catalysts are cb.eznically distinct. Under continuous solution polymerization conditions, the process is ideally suited for polymerization of mixtures of monomers at high monomer conversions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes advantaged compared to chain grouth, ai1d multi-block copolymers. especially -inear inulti-block copolymers are formed in high efficiency.
[00911 The inventive interpolymers may be differentiated frotn conve.ntional, random copolymers, physical blends of polymers, and block copolymers prepared via sequential inonomer addition, fluxional catalysts, anionic or cationic living polyznerization techniques.
In particular, corrlpared to a random copolymer of the sax-ne monomers and monomer content at equivalent crystallinity or modulus, the inventive interpolymers have better (higher) heat resistance as measured by melting point, bigh.er TMA penetration ternperature, higher high-temperature tensile strength, and/or higher high-temperature torsion storage modulus as dLtennined by dynamic mechanical anaiysis. Compared to a random copolymer containing the same rnonoi-ners and monomer content, the inventive interpolymers have lower compression set, particularly at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear strength, higIier blocking resistance, faster setup due to higher crystallization (soliditic-atioiz) temperatLire, higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better oil and filler acceptance.
t00921 The inventive inteipoiytners also exhibit a uniqak~ crystallization and braiachincv distribution relationship. 'I"hat is, the inventive interpolymers have a reiatively large difference bem,,een the tallest peak tenlperature nieasure~:d tÃsing C.ItYS'1 AF and DSC as a f`Unction of heat (>l' fiusion, especially as ct. ;:re:i to i=aridoni cc)polvtrze.rs i:ontaiiaiilg the sarrc a - -i~r 2tal. :;" Pa, :tv. it is b itt ~A.
zx_ this uaiqu~ of the _?~_ comonomer in blocks vvithin the polyrner backbone. In particular. the inventive interpolymers may c-ornprise alternating blocks of differin.a comonoMer content (including homopolymer blocks). The inventive interpolymers may also comprise a distribution in number and:`or block size of polymer blocks of differing density or comonomer content, which is a Schultz-Floi-v type of distribution. In addition, the inventive interpolymers also have a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus, and tnorphology. ln a preferred embodiment, the microcrystalline order of the polymers deinon.strates characteristic spherulites and lamellae that are distinguishable from random or block copolymers, even at PDI values that are less than 1.7. or even less than 1.5, down to less than 1.3.
100931 Moreover, the inventive interpolymers may be prepared using techniques to iiifluence the degree or level of blockiness. That is the amount of comonomer and len~,~th of each polynier block or segment can be altered by controlling the ratio and type of catalysts and shuttling agent as well as the temperature ol~` the polymerization, and other polymerization variables. A surprising benefit of this phenomenon is the discovery that as tl-te degree of blockiness is increased, the optical properties, tear strength, and hi"h temperature recovery properties of the resulting polynler are improved. In particular, haze decreases while clarity, tear strength, and high temperature recovery properties increase as the average number of blocks in the polymer increases. By selecting shuttling agents an.d catalyst combinations having the desired chairi transferring ability (high.
rates of shuttiing, with low levels of chain te,rmiiiation) other 1"orms of polymer termination are effectively suppressed. Accordingly, little if any 13-hy(irid.e eiiinination is observed in the polymerization of ethylenei'cc-o[etin comonomer mixtures accordin- to embodiments of the invention, and the possessing little or resulting crystalline blocks are highly, or substantially completely, linear, no long chain branching.
100941 Polymers with highlv crystalline chain ends can be selectively prepared in accordaiiee with embodiments of the invention. In elastomer applications.
reducing the relative yLiantity of polyrner that terminates with aii ai7iorphous block redtices the, intermoleeular dilutive effect on crvstalliiie rc(~ians. "1'his result can be obtained by cboosing, chain shuttling agents and c-ataiysts having an appropriate response to hvdrouen or other chain terminating agents. SpeciTicall~ , if the c.atalv,t whic;h produces hiphiy cry4talline i :. 4;.ISY }? USC ItblC; ~Or .._17.

ic i f.?1cC'i-mxat s.ioI7. Iyf7I<.,r ,'.;-mation). th1',iI th:;
~~a-crystalline polymer segments will preferentially populate the terminal portions of the polymer. Not only are the resulting tet-minated groups crystalline, but upon termination, the highly crystalline polymer forming catalyst site is once again available for reinitiation of polymer forsnation. The initially formed pol~-rner is therefore another highly crystalline polymer scanaent. Accordingly, both ends of the resulting multi-block copolymer are, preferentially highly crystalline.
[0095] The etliylene a-olefin interpolymers used in the embodiments of the invention are preferably interpolymers of ethylene with at least one C3-Q,0 a-olefin.
C.opolyrners of ethylene and a C;-CZp a-olefin are especially preferred. The interpolymers may further comprise C4-C18 diolefin and/or alkenylbenzen.e. Suitable unsaturated comonomers useful for polyrnerizing with ethylene include, for example. ethylenically unsaturated monomers, conjugated or nonconjugated dienes. polyenes, alkenylbenzenes, etc. Examples ofsuch cam.onorners include C3-C20 a-olefins such as propylene, isobutylene, 1-butene, I -hexene, 1-pentene, 4-methyi-I -pentene, 1-heptene, I -octene, 1-nonene, I-decene, and the like. 1-butene and I -octene are especially preferred. Other suitable rnonomers include styrene, halo-or alkyl-substitute.d styrenes, vinylbenzocyclobutane, ,4-hexadiene, I.?-octadiene, and naph.thenics (e.g., cyclopentene, cyclohexene and cyclooctene).
100961 While ethylene'o,-oletin interpolymers are preferred polymers, other ethylene/olefin polymers may also be used. Otefins as used herein refer to a family of nnsattiirated hydrocarbon-based compounds with at least one carbon-carbozl double bolid.
Depending on the selection of c-atalysts, at-iy o[etin may be used in embodiinents of the invention. Preferably, suitable oEefins are C3-C7o aliphatic and aromatic compounds containijig vinylic unsaturation, as well as cycEic comporrnds, such as cvc-lobutene, cyclopentene, dicyclope-n.tadiene, and norbornene, including bnt not lirnited to, norbornene substituted in the 5 and 6 position with. CI-C2(} hydrocarbyl or cyclohydrocarbyl groups.
Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefin compounds.
100971 Examples of olefin rnonomers include, but are not limited to propyleiie, isobutylene, 1-butene, I-pentene, I-bexene, 1-beptene, 1-octene, 1-noiiene, I -decene, and I-dt>dL:;enc. i t~ t~ f w~ e: e, I h~ ~ t~e~ 1~e. 1(~ctaclc c, ne. I-clc(j =enc.. 3-n ~uthyl- I-but,_: rie. 3-<
v11~?' .
11.cI1[ . C i(iiii tt T. CA ~I3 2 d tt3 1 -~,_ I.3-pentadiene, 1,4-bexadicne, 1.5-hexadiene, 1,7-oct.adie'ne, 1,9-de.cadiene, other C4-C40 a-olefins. and the like. In certain enibodiments, the a-olefin is propylene,1-buteue, I-pentene,l -hexene, 1 -octene or a combination thereof. Although any hydrocarbon containing a vinyl group potentially may be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the inonozner becomes too high.
100981 'The polymerization processes described herein are well suited for the production of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene., p-methyl styrezie, t-butylstyrene, and the like. In particular, interpolymers cornprisin, ethylene and styrene can be prepared by tollowing thc, teachings herein.
Optionally, copolymers comprising ethylene, styreile and a C3-C20 alpha olefin, optionally comprising a C4-C20 diene, having improved properties can be prepared.

[0099] Suitable non-conjugated diene monomers can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include, but are not Iii:nited to, straight chain acyclic dienes, such as 1,4-hexadiene, 1.6-octadiene, 1,7-octadiene. 1,9-decadiene, branched chain acyclic dienes, such as 5-rnethyl-1,4-hexadiene; 3.7-diniethyl-l,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dillydrotnyricene and dihydroocinene, single ring alicyclic dienes, such as 1,3-c-yclopentadiene; 1,4-eyclohexadienc; 1,5-cycEooctadiene and 1,5-eyclododecadiene, atid inulti-rin.g alicyclic f'Lised and bridged ring dienes, such as tetcahyd:roindene, methyl tetrahydroindene, dicyclopentacliene, bicyclo-(2,2,1)-bepta-2,5-diene;
alkenyl, alkylidene.
cycioalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (::41NB); 5-propenyl-2-norborntne, 5-isopxopyliderle-2-norbornene, 5-(4-cyclopentenyl)=2-norborrrel3e, 5-cycloh.eYylidene-2-norbornerze, 5-vinyl-2-norbornene. and norbornadiene. Of the dienes typically used to prepare EPDMs, the particulariy preferred dienes are 1,4-bexadiene (HD), 5-ethylidene-2-norbornene (EIvB). 5-vinylidezie-2-norboniene (VNB), 5-metbvlen.e-2-norbornene ( MNB), arld dicyclopentadiene (DCPD). '1'he especially preferred dietie-s are 5-cthylide.ne-2-norbomene (ENB) and 1.4-hexadieue (1-1D).
[01041 One class of desirable polymers that cati be niade in accordance wit.b lbod:n ela5tot~-icric 3r:- r-õ mc _ ~'A`

one o . . , a., e . p rl~'~~r~1.3 ~.Slti:-~SL.~~ ~c where R* is a linear or branched alkyl group of from I to 12 carbon atoms.
Examples of suitable a-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, and 1-octene. A particularly preferred a-olefin is propylene.
The propylene based polymers are generally referred to in the art as EP or EPDM polymers.
Suitable dienes for use in preparing such polymers, especially multi-block EPDM type polymers include conjugated or non-conjugated. straight or branched chain-, cyclic- or polycyeiic- dienes comprising from 4 to 20 carbons. Preferre-d dienes include 1,4-pentadiene, 1,4-bexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadi4ne, and 5-butylidene-2-norbornen.e. A particularly preferred diene is 5-ethylidenc-2-norbornene.
[0101] Because the diene containing polymers comprise alternating segments or Hocks containing greater or lesser quantities of the diene (including none) and a-olel-in (including none), the total quantity of diene and a-olc.fin may be reduced without loss of subsequent polymer properties. That is, because the diene and a-olefin monomers are preferentially incorporated into one type of block of the polymer rather than uniformly or randomlv throughout the polymer, they are more efficiently utilized and subsequently the crosslink density of the polymer can be better controlled. Such crosslinkable elastomers and the cured products have advantaged properties, including higher tensile stren~th and better elastic recoverv.
101021 In some embodiments, the inventive interpolymers made with two catalysts incorporating differing quantities of cotnonomer have a weiglit ratio of blocks f'ortned tflereby from 95:5 to 5:95. `I`he elastomeric polymers desirably have an ethylene content of li=om 20 to 90 percent, a diene content of from 0.1 to 10 percent, ancl an a-oiefin content of from 10 to 80 perce:nt, based on the total weight of the polynaer. Further preferably, the multi-block elastomeric polymers have an ethylene content of l:rom 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an a-olefin content of from 10 to 40 percent, based on the total weight of the polymer. Pref'erred polymers are high molecular weight polymers, having a weight average z=nolecular weight (Mw) from 10.000 to about 2,500.000, preferably from to 500.000, more preferably froin 20.000 to 350,000, and a polydispersit.y less than more prelerably less than 3.0, and aMc>oncy viscosity (N,1L (1.i-4) 125"C..) from i to 250.
More preferabiy. such poiyme:rs have an ethylenc contetit from 65 to 75 percelit, aÃl.iene c _ontent froni 0 to 6 perc.ent, and an ft-ole-fin o.-a_ nt frotn 20 to '3 5 percent.
. ,~, ,..
a1.` ..1 ..1 ,i=a:iCl)I' P
4_1C~L.i~t . st;. '.-'.ip.)u. et7n feI"I1~~ai, a. , 3l~irsaL
~Y#
. , l"

ethylenically unsaturated mono- and di-Cunctional carboxylic acid anhydrides.
salts thereof and esters thereof. Such functional groups may be grafted to an ethylene,`Ot -olefin itlterpolymer, or it may be copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene. the functional comonomer and optionally other comonomer(s). Means for grafting functional groups onto polyetb.ylene are described for example in L.S. Patents Nos. 4,762,890, 4,927,888, and 4,950,541, the disclosures of these patents are incorporated herein by reference in their entirety. One particularly useful functioz-tal group is malic anhydride.
101041 The amount of the functional. group present in the functional interpolymer can vary. The functional ;roup can typically be present in a c-opolymer-lype functionalized interpolymer in an aznount of at least about 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent. The functional group will typically be present in a copolymer-type l~unctionalized interpolymer in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.

Testing Methods (01051 ln the examples that follow, the following analytical techniques are employed:
GPC Method for Samples 1-4 and A-C

101.(36) An autoinated liquid-handling robot equipped with a heated needle set to 160 C is cised to add enough 1,2,4-trichlort>benzene stabilized with 300 pptn lonol to each dried polymer sample to give a final. concentration of 30 mg/mL. A small glass stir rod is placed into each tube and the samples are heated to 160 C for 2 hours on a heated, orbital-shaker rotating at 250 rpm. The concentrated po[viiier solution is then diluted to I
mg%~~nl using the autornate-d liquid-handling robot and the heated needle set to 160 C.
101071 A Symyx Rapid Cil'C system is used to determine the molecular weight data for each saniple. A Gilson 350 pump set at ?.0 rnl:`min flow rate is used to puinp helium-purged 1.2-dichlorobenzenc; stabilized with 300 ppm lonol as the mobile phase throu,.h three 1'lg~:l micrometer {pin} Mixed B 300mrn x 7.5mm columns placed in series and heated to 1 60 C. A Polymer Labs ELS 1000 I3etector is uscd %&-ith the Evaporatoi' <'.~t to 250"C. the .
Nebt[l,zt r`" to 16 c'i`. ir,, :l: I .c} St 80 ~. "~"l d400-66T. "FbC . t.: 1 Ãlito a 2 kj LL~ IC7O`
. ... `~ -polymer samples using two switched loops and overlapping injections are used.
The sample data is collected and analyzed using Sy~~}x EpochTM sof-tvvare. Peaks are inanually integrated and the molecular iveight information reported uncorrected. against a polystyrene standard calibration curve.

Standard CRYSTAF Method (0108) Branching distributions are dettrinined by crystallization. analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,=1 trichlorobenzene at 160 C
(0.66 mg/mL) for I hour and stabilized at 95 C for 45 minutes. The sai-nplinl; temperatures range t:rom 95 to 30 C at a cooling rate of 0.2 C!min. An infrared detector is used to measure the polymer solution concentrations. 'rhe cumtilative soluble concentration is measured as the polymer crystallizes while the temperature is decreased. The analytical derivative of the cumulative.-proti.le reflects the short chain branching distribtrtion of the polymer.
[01091 The CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYS'I'AF Software (Version 2001.b, Polyir-erChar, Valencia, Spain). T'he CRYSTAl' peak finding routine identifies a peak temperature as a maximum in the dWIdT curve and the area between the largest positive inflections on e:ither side of the identified peak in the derivative curve. To calculate the CRYSTAF curve, the preferred processing parameters are with a temperature limit of 70 C and with smoothing, paraz~.eters above the temperaturc, Iii-nit of 0.1. and below the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1T=1 and A-C) 101.101 Differential Scanning Calorimetry results are determined using a TAI
model Q1000 DSC equipped with an RCS cooling accessory and an autosampier. A
nitrogen pur"e gas flow of 50 rnI/'min is used. The sample is pressed into a thin film and melted in tfle press at about 175'C and then air-cooled to room temperature (25 C). 3-10 mg of material is then cut into a 6 nim diameter disk, accurately vveighed. p[aced in a light aluminum pan (ca 50 rng), and then crimped shut. 7"he thermal behavior of the sample is investigated with the tolln,~ving te.niperattiire profile. The sample is rapidly heated to I80 C and held isotherrnal for 3minute.s in order to reniove any previc>tls thermal historv, -1`he sample is theii cooled to -, - . .. 3 ' i v"5t.'sa .y~ ~ i.. , '' ~
a. : ~i ~ : ? ~~I~ ~d I' t ~t~` C t ~"te s~iIY1P,~t is ~a~.t ,'~~~ <~t~ I t ~., ,. .
i 3t.;- ~C at :(~,~...1~~~in. l.~:ati~~~~ rate, 1_1_ . ..r~~ s d re r .,:~i_ [01111 The DSC melting peak is measured as the maximum in heat now rate {W,`g}
with respect to the linear basc:linedrawn betkNreen --'?O C and end of melting. The heat of fusion is measured as the area under the melting curve between -30 C and the end of melting using a linear baseline.

GPC Method (Excluding Samples 1-4 and A-C) 101121 The gel permeation ellrom.a.tographic system consists of either a Polymer Laboratories Model PL-2 10 or a Polymer Laboratories Model PL-220 instrument.
'l'lie column and carousel compartments are operated at 140 C. Three Polymer Laboratories 10-micron Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene. The samples are prepared at a concentration of 0.1 grams o#'polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160 C. The injection volume used is 100 microliters and the flow rate is 1.0 rnl /rninute.
[01131 Calibration of the GPC column set is pertormed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6"cocktail" mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.025 grains in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,004, and 0.05 grar-ns in 50 milliliters of solvent For molec.ul.ar weights less than 1,000,[100. The polystyrene standards are dissolved at 80 C with gentle agitation for 30 mirtutes. The narrow staridards mixtures are rur, f'irst and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak inolecular weights are, converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J.
Polym. Sci., Polvm. Let., 6, 621 (1968)): Mpj:jsetj,,.-c õc =- 0.431(Mp,,i}-,tyr nd=
101141 Polyethylene equivalent molecular w-ei~;~.t calculations are performed using Viscotek TriSEC- software Version 3Ø

Compression Set 101151 Ctj;rt-i 'on 5 measured according to AS"1'M D-395. The, sample is prepared , _. 2.0 .
l _~
~IlId s~ e; [~l .2 Iiii7la ~.'.~~ I~2~"13_ and ~~'.,5 ti:~.I'~i t:~I~.i~Y~~;1d~it:
, ... l IIN ni:ys of 12. .` . - ,G .~~ . .. , .~ ~cs are ._i'i__ ..~.f ,.. .
...,.~ Ã~M i- }24i3idQ

( 7_ ., . I':, x t'. f minutes at 190 C, followred by 86 MPa for 2 minutes at 190 C. followed by cooling inside the press with cold running water at 86 MPa.

Density [01161 Samples for density measurement are prepared according to ASTM l) 1928.
Measurements are made within one hour of sample pressing using ASTM I3792, Method B.
F[exural/Secant MOClulus/ Storage Modulus [0117] Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790. Storabe modulus is measured according to ASTM D 5026-01 or equivalent technique.

Optical properties [01181 Films of 0.4 mm thickness are compression molded usitag a hot press (Carver Model #4095-4PR1001 R). `T`he pellets are placed between polytetrafluoroethylene sheets, heated at 190 C at 55 psi {380 kPa) for 3 minutes, followed by 1.3 MPa for 3 minutes, and then 2.611iPa for 3 minutes. The film is then cooled in the press with running cold watcr at 1.3 MPa for 1mintite. 'I'lie compression molded films are used for optical measiire.rrm.ea:ts, tensile behavior, recovery, and stress relaxation.
[01.191 Clarity is measured using BYK Gardner Haze-gard as specified in AS"1"M
D 1746.
101201 45 gloss is measured using BYK Gardner Cilossinete.rMicrogloss 45 as specified in ASTM D-2457.
[0121) Internal haze is measured using BYK Gardner Haz.e-gard based on ASTM D

Procedure A. Mineral oil is applied to the filrn surface to remove surface scratches.
Mechanical Properties - Tensile, Hysteresis, and Tear [01221 Stress-strain behavior in uniaxial tension is measLired using ASTM D

microter-sitL specimens. Samples are stretched with an. Instron at 500% inir-I at ? 1 C;.
Tensile strength and elongation at break are reported froni an average of 5 specimens.
[0123] 100% and 300% o I-lyste.resis is determined from cyclic loading to 100%
and 300%
stnains usin _ ASTM D 1-08 microtensilkz sp~ %.in'ie:ns with an ln,tron-1-m instrument. Th~
3 Cvclic exl-_, ~
aji.t'''ct a?1L trI the 'cFWC expci>~_tii~, ~~1c sailiple 1a '. ijtl j'.: 1ir the ici cTT2nerattirE be foi ~ ie52Sm, . In the .~.~-2FC, 300% strain cyclic experiment, the retractive stress at 150% strain irom the #irst unloading cycle is recorded. Percent recovery for all experinae=nts are calculated from the first unloading cycle using the strain at which the load rettLrned to the base line. 'The percent recovery is defined as:

E. ~
%Recoti-ery= x100 where cf is the strain taken for cyclic loading and Fti is the strain where the load returns to the baseline during the 1" unloading cycle.

101241 Stress relaxation is measured at 50 percent strain and 37 C for 12 hours using an InstronTM instrument equipped with an environmental chaniber. The gauge geometry was 76 m.m x 25 mm x 0.4 mm. After equilibrating at 37 C for 45 rnin in the environmental chamber, the sample was stretched to 50% strain at 333% min.-~. Stress was recorded as a function of time for 12 hours. 'T'he percent stress relaxation after 12 hours was calculated using the formula:

% xS-tress Relaxation ~ l G~~ lv x 100 LO
where Lo is the load at 50% strain at 0 time and L12 is the load at 50 percent straizl after 12 hours.

101251 Tensile notched tear experimeiits are carried oiit on samples having a density of 0.88 glcc or less using an In,stronT~ instrument. 'Tlze geomc try consists of a gauge se ctioii of 76 mm x 13 mm x 0.4 m.rn witli a 2 mm notch c-Lit into the sample at half the specirnen length.
'I'he saznple, is stretched at 508 rnm min-' at 21 C until it breaks. The tear energy is calculated as the area under the stress-elongation curve up to strain at maximum load. An average of at least 3 specimens are reported.

TMA
101261 Thermal X-1eclzanical Analysis (Penetration TernperatLrre) is conducted on 30tnm diameter x 3.3 mi-n. thick, coilipres5ion molded discs, formed at 18Ã1 C and 10 MPa molding i tr 111 ~ 1i t 4aT'd then air q3It r1Clled. i i i'i2St1'i Tn=: `n a a ImCr. 1.5 )416')is api)iiCl,i iii talc' ~tI ldi ti of the `iYS.21:1pa.: disc with . ;'~ . I'h.' is I'aI:~," at _5 CP11I1 from 25gC. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe has penetrated 1 mm into the sample.

DMA
101271 Dynamic Mechanical Analysis (DMA) is measured on compression molded disks formed in a hot press at 180 C at 10 MPa pressure for 5 minutes and then water cooled in the press at 90 C f min. Testing is conducted usiiig an ARFS controlled strain rheometer (TA
instruments) equipped with dual cantilever fixtures for torsion testing.
101281 A 1.5mm plaque is pressed and cut in a bar of dimensions 32x12mm. The sample is clamped at both ends between fixtures separated by lflmm (grip separation AL) and subjected to successive temperature steps from -lOQ C to 200` C(S"C per step).
At each temperature the torsion modulus G' is measured at an angular frequency of 10 radfs, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure dlat the torque is sufficient and that the measurement remains in the linear regime.
101291 An initial static force of 10 g is maintained (auto-tension mode) to prevent slack in the sample when thernial expansion occurs. As a consequence, the grip separation. AL
increases with the temperature, particularly above the melting or softening point of the polymer sample. "rhe test stops at the maximum temperature or when the gap betvvc:en the fixtures reaches 65 mm.

Melt Index [01301 ti=leit index, or I2, is measured in accordance with ASEM D 1238, Condition 190"C!2.16 kg. Melt index, or I70 is also measured in accordance with ASTM D
1238, Condition 1)0 C110 kg.

ATREF
101311 Analytical temperature risintz elution fractionation (ATREF) analysis is conducted accordinc, to the method described in U.S. I'a.teiit No. 4.798,081 and Wilde, L.; Ryie, 1".R.;
Knobeloc-h, D.C-.; 1'eat. l.R.. Determination qf'Brcrnchinl,; Dislt-ihittion.S
in Pol-teth.ylere and Ethy,Iene C."opolylm~.~r-s. J. Polym. Sci., 20, =141-455 (1 982), which are incorporated bv reference hereira i i t1-1: r:~ ~tir::ty. The cc~i-npositi.oii to be analyzed is dissolved in trichl~?r l~h~~~ed c: ='l=~~e i11 ,~ ~,ti = 4teÃ,1 sli".) i: ltiilng E l~; i ;:vZ~3 ~~e =_. `LK ~. _ . . . . , c5~ ~1.$ili~1 .e'... ~ ~.

generated by eluting the crystallizeti pÃ~lyiner sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenrene) from 20 to 120 C at a rate of 13C NMR A.nalysis 101321 The samples are prepared by addin~,7approximatelv 3a of a 50.1150 mixture of tetrachloroethane-d`: orthodichlorobenzcrre to 0_4 g sample in a 10 mm NM.R
tube. The samples are dissolved and homogenized by heating the tube and its contents to 150 C. The data are collected using a JEOI_ F'clipseT'" 400MHz spectrometer or a Varian Unity I'lusTM
400MHz spectrometer, corresponding to a$3C resonance frequency of 100.5 MHz.
The, data are acquired usin, 4000 transients per data file with a 6 second pulse repetition delav. To achieve minimum signal-to-noise for qLiantitative analysis, multiple data files are added together. The spectral width is 25,000 I-Iz with a minimum tile size of 32K
data points. The samples are analyzed at 130 C in a 10 mm broad band probe. The comonomer incorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol_ Chem.

Phys,, C29, 201-317 (I989), which is incorporated by reference herein in its entirety.
POtymer Fractionation by TREF

[01331 Large-scale TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of l,2,4-trichlorobenzene (TCB)by stirring for 4 hours at 1 60 C. The polymer soIutioll is forced by 15 psig (100 kPa) nitro(len onto a 3 inch by 4 foot (7.6 c-m x 12 cnr) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 lzm) spherical, technical quality glass beads (available from Potters Industries, H.C 30 Box 20, Brownwood, TX, 76801) and stainless steel, 0.028" (0.7mm) diameter cut wire shot (available from Pellets, Inc. 63 Industrial Drive, North Tonawanda, NY, 14120). The column is immersed in a thermally controlled oil jackEt, set initially to 160 C:. The column is first cooled ballistically to 125 C, then slow cooled to 20 C at 0.04 C per ii7iuute and held for one hour. Fresh "I`C.B is introduced at about 65 ml;r$nin while the teinperature is increased at 0.167 C
per minute.
101341 Approximately 2000 inI portions of eltza.nt from the preparative TREF
column are collected in a 16 station, heated fractiori collector. 'rhe poiN"mer is concentrated in each fraction using, a rotary evaporator until about 50 to 100 nil of the polynier solution renlains.

-,cbor %~ sitl~.r$'-L~ ~.,~i e, s 6t<,';.;$
` $S ! !';: ~. ' LC$$1 :i.. _4 1 polytetrafluoroethylene coated i:ilter paper (available from Osmonics Inc., Cat4 I50WP0475Q). Tbe; filtrated fractions are dried overnight in a vacuum oven at 60 C and weighed on an analytical balance before further testing.

Melt Strength (01.351 Melt Strength (MS) is measured by using a capillary rlieometer fitted with a 2.1 mm diameter, 20:1 die with an entrance angle of approximately 45 degrees.
After equilibrating the samples at 190 C for 10 minutes. the piston is rtzn at a speed of 1 inch/minute (2.54 cmiminute). The standard test temperature is 190 C. 'T-he sample is drawn uniaxially to a set of accelerating nips located 100 mm below the die with an acceleration of 2.4 mm/sec2. "[`he required tensile force is recorded as a function of the take-up speed of the iiip rolls. 't'he maximum tensile force attained during the test is defined as the melt strength.
In the case of polymer melt exhibiting draw resonance, the tensile force before the onset of draw resonance was taken as melt strength. The melt strength is recorded in centiNetutons ("cN"").

Catalysts [0136) The term "overniglZt", ifused, refers to a time of approximately 1.6-18 hours, the term "room temperature", refers to a temperature of 20-25 C, and the term `n3ixed alkanes"
refers to a commercially obtained mixture of C6-9 aliphatic hydrocarbons available ujider the trade desionation Isopar E'( , .from. Exxon..Mobil Chemical Company. In the event the name of a compoLind herein does not conforrn to the structural representation thereot'. the structural representation shall control. The synthesis of all metal cornplexcs and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dty box techniques. All solvents used were H1'LC grade and were dried before their use.
[0137] MMAO refers to modified methylalumoxane, a triisobutylaluminum modified met17vlalumoxane available commercially from Akzo-Noble Corporation.
101381 'l'he preparation ol' catalyst (B 1) is conducted as fol lows.
a) Yreparation ot (1-methvlethvl)('-bydroxv-3,5-di(t-but~~l)phenvl)methti~linrine S-Di-t-but% lsalie,,rlaldeh.yde (3.00 g) is added to 10 mL of isopropylam.ine.
'I'he i' ~,r s ~t3tiirs.

Ã:;:u,r vaiC:uum C3 i ~.'.`b. St,lld ~Ã}t percent -.~:

b) Preparation of 1,2-bis-"3,5-di-t-butvl henvlene) l- N- I-methvlethvl immino Ãnethvl "2-oxovl zirconium dibenzvl A solution of (I-m ethviethyl)(2-hydroxy-3,5-di(t-butyt)phen yl)iÃnirÃe (605 mg. 2.2 mmol) in w mL toluene is slowly added to a solution of Zr(CH2Ph)4 (500 mg, 1.1 rnmol) in 50 mL toluene. The resulting dark yellow solution is stirred for 30 minutes.
Solvent is removed under reduced pressure to yield the desired product as a reddish-brown solid.

[0I391 The preparation. of catalyst (132) is conducted as follows.
a) Pre ara.tion of 1- 2-methvlcvclohex 1 eth l(2-oxovl-3.5-di t-butvl hen yl imine 2-Methylcycl.ohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL), and di-t-butylsalicaldehyde (10.00 ~, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25 C for 12 hours. The resulting yellow solid precipitate is collected by filtration and washe.-d with cold methanol (2 x 15 mL), and then dried under reduced pressure. The yield is 11. 17 g of a yellow solid. 'T-I NMR is consistent with the desired product as a mixture of isomers.

b) Preparation of bis- l- 2-metilvlcvclohex rl e.th -1 2-oxo yl-3.5-di t-but 1 hen l immino zircorÃium dibenzyl A solution of (1-(2-Ãnethti-lcyclohexyl)ethyl)(2-ox,oyl-3.5-di(t-butyl)phÃ:nyl)im.ine (7.6:3 g, 23.2 nimol) in 200 mL toluene is slowly added to a solution of Zr(CH2Ph)4 (5.28 ~.
I 1.6 mmoi) in 600 niL toluene. 'The resultinl; dark yellow solution is stirred for 3 liour at 25 C. The solution is diluted further with 680 mL toluene to give a solution having a concentration of 0.00783 M.

[01401 Cocatalyst I A mixture of rnethyldi(Ci4_1 y alkyl)aÃnmonium salts of tetrakis(pentaflLÃorophenyl)borate (here-in-after armeenium boratc). prepared by reaction of a I.on, chain trialkylamine (Armeen"'4 M2H"T'. available froÃn. Akro-Niabel, Inc.). FiCI and Li[T3(Cf;P,)41, substantially as disclosed in USP 5,919,9883, Ex. 2.
101411 Cocatalyst 2 Mixed C14-,s alhyldimethvlanmonium salt of bis(.tris{Pentli:luorophenyl)-alÃtmane)-2-undecvli.midarolide, prepared according to USP
6e' )9 ~ f_... .5.

SA~A2;, di{o lt~~:, iC ~;~.~,. =~)a trioetylaluminum (SA5), trietbylgallium (SA6), i-butylalurninum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminum bzs(di(trimetbylsilyl)arriide) (SA8), n-octylaluminum di(pyridine-2-r-nethoxide) (SA9), bis(n-octadecyl)i-butylalun.-iarzum (SA10), i-butylaluminum bis(di(n-pentvl)arnide) (SAl I), n-octylaluminurn bis(2,6-di-t-butylphenoxide) (SA1~.?), n-octylaluminunr di(ethyl(1-naphthyl)amide) (SA13), ethylaluminum bis(t-butyldimethylsiloxide) (SA 14), ethylaluminum di(bis(trimethylsilyl)amide) (SA
15), ethylaluminum bis(2.3,6,7-dibenzo-l-azacycloheptarzeamide) (SAl6), n-octylaluminum bis(2,3,6,7-dibenzo- l-azacycloheptaneamide) (SA 17), n-octylaltiminum bis(.dimethyl{t-butyl}siloxide(SA 18), ethylzinc (2,6-diphenyiplrc:noxide) (SA 19), and ethylzizrc (t-butoxide) {SA20}.

Exaanples T.-4. Comparative A-C

General High Throughput Parallel Polymerization Conditions [01431 Polymerizations are conducted using a high throughput, parallel polymerization reactor (PPR) available from Syrnyx "T-eclrnologies, Inc. and operated substantially according to US Patents No. 6,248,540, 6,030,917, 6,362,309, 6,306,658, and 6,316,663.
Ethylene copolymerizations are conducted at 130 C and 200 psi (1.4 MPa) with ethylene on demand using 1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1 equivalents when MMAO is preseiit). A series ot'polymerizations are conducted in a parallel pressure reactor (PPR) contained of 48 individual reactor cells in a 6 x 8 array that are fitted with a pre-weighed glass tLibe. The working volume in each reactor cell is 6000 ~iL. Each cell is temperature and pressure controlled with stirring provided by individual stirring paddles.
'T"he monomer gas and quench gas are plumbed directly into the PPR unit and controlled by automatic valves. Liquid reagents are robotically added to each reactor cell by syringes and the reservoir solvent is niixed alkanes. l`he order of addition is mixed alkanes solvent (4 ml), ethylene, T-octe-ne comojiomer (t ml), cocatalyst I or cocatalyst 1/E9?1!IAO
mixture, sliuttling agent, and catalyst or catalyst niixture. When a mixture of cocatalyst I and MMAO or a mixture of t,~vo catalysts is Ãised, the reagents are premixed in a sniall vial immediately prior to addition to the reactor. When a reagent is omitted in an expe.riment, the above order of addition is otherwise rnaintaizied. Polymerizations are conducted for approxirnate-ly 1-2 nii: 1 nii l prt ri-: ~n~:!:,ie cc>ns_il t1 ls a_ reac.bi J.

.L`,:._ . ~ . .. ..... , , . .i.. .... ~ _..., .., . . . . Y 3 ,. ... , r. . .._,~s _.., zi ut"twC~ ~t~i i_ =_ts~it~ c~t ["3 ~ ~.. ~ e dried .~~)~

polymer are weighed and the difference between this weight and the tare wei-ht gives the net yield of polymer. Results are contained in`T'able 1. In Table 1. and elsetivl-ierc in the application, comparative compounds are indicated by an asterisk (*).
[0144] Examples 1-4 demonstrate the synthesis of linear block copolymers by the present invention as evidenced by the t'orinat.iou of a very narrow MWD, essentially monomodal copo[ynier when DEZ is present and a bimodal, broad molecular weight distribution product (a mixture of separately produced polymers) in tbe absence of DEZ. Due to the fact that Catalyst (Al ) is knotkPn. to incorporate more octene than Catalyst (B 1), the different blocks or segments of the resultinM copolymers of the invention are distinguishable based on branching or density.
Table I
Cat. (A 1) Cat (B1) Cocat M.V1AO shuttling Ex. mo[ unol ( znol) Lmo[ agYÃ.n.t (vmoL) Yield ~, Mn Mw,M17 heylsl A* 0.06 - 0.066 0.3 - 0.1363 300502 3.32 -B* - 0.1 0.110 0.5 - 0.1581 36957 1.22 2.5 C* 0.06 0.1 0,176 0.8 - 0.2038 45526 5.30' 5.5 1 0.06 0.1 0.192 - DEZ (8.0) 0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 - DBZ (80.0) 0.1468 2161 1.12 14.4 3 0.06 0.1 0.192 - '1"C:A (8.0) 0.208 22675 1.71 4.6 4 0.06 0.1 0.192 - TEA (80.0) 0.1879 3338 1.54 9.4 1 C6 or higher chain content per 1000 carbons 2 Bimodal molecular weight distribution [0145] It may be seen the polymers produced according to the invention have a relatively narrow polvdispersi.ty (Mw/Mn) and larger block-copolymer content (trimer, tetramer, or larger) than polymers prepared in the abseiace of the shuttling agent.
101461 F'ur-ther characterizing data for the polvmers of Table 1 are determined by reference to the figures. More specifically DSC and A`C'REF results show the following:
101471 The DSC curve for the polvrner of example 1 shows a l 15.7 C melting point (Tzn) with a heat of fusion of 158.1 .l;'g. The corresponding CRYSTAF curve shows the tallest peak at 34.5 C with a peak area of 52.9 percent. -hbe difFerence between the DSC Tm and tbe Tcrystaf is 81.2 C.

101481 The DSC curve for the polymer of example 2 shows a peak with a 11)9.7 C-me-lting point (Trn) with a heat of fusion of 214.0 .i.'g- Tbe corresponding CRYSTAF curve the tallest peak x '0.2'C with a pcak areao;~57.() percent. The di.fic.reiiwe betv"een the ~ C, 0 11 alnd ~.-(0149] The DSC curve for the polymer of example 3 shows a peak with a 120.7 C
melting point (Tm) with a heat of fusion of 160.1 Jtg. The corresponding C.RYSTAF curve shows the tallest peak at 66.1 C with a peak area of 71.8 percent. Tbe difference between the DSC Tm and the Tcrystaf is 54.6 C.

(0150] The DSC curve for the polymer of example 4 shows a peak with a 104.5 C
melting point (Tm) with a heat of fusion of 170.7 JIg. The corresponding CRYSTAF curve shows the tallest peak at 30 C with a peak area of 18.2 percent. The difference between the DSC 'I'm and the Tcrystaf is 74.5 C.

101511 The DSC curve for comparative A shows a 90.0 C melting point (Tm) with a heat of fusion of 86.7 Jib. "I"he corresponding CRYSTAF curve shows the tallest peak at 48.5 C
with a peak area of 29.4 percent. Both of these values are consistent with a resin that is low in density. The difference between the DSC Tm and the Tcrystaf is 41.8 C.

101521 The DSC curve for comparative B shows a 129.8 C melting point (Tm) with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curve shows the tallest peak at 82.4 C witlr a peak area of 83.7 percent. Both of these values are consistent with a resin that is high in density. The difference between the DSC Tm and the T ervstaf is 47.4 C.

101531 The DSC curve for comparative C shows a 125.3 C meltint, point ("1'ni) with a heat of fusion of 143.0 Jj`g. '~t'he correspondin- CRYSTAF curve shows the tallest peak at 81.8 C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 C-. The separation between the two peaks is consistent with the presc ce of a high crystalline and a Eow crystalline polymer. The difference between the DSC 'htn and the 4'crystaf is 43.3 C.
Examples 5-19 Comparatives D-F Continuous Solution P Ivmerization Catalyst A1/B2 + DEZ

[0154] Continuous solution palyn-ierizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (lsapar~'m E available from ExxonMobil Chemical C:nmpany), ethylene at 2.70 lbs/hour (1.22 kg./hour), 1-octene, and by-drooen (where used) are snppfied to a 3.8 L reactor equipped with a jacket for telnperature control and an internal thermocouple. The solvent feed to the reactor is measured by ama.ss-f1ow controller. A variable speed Ãliaphragzn pump controls the solv~:nt Ae a I _ re to t~,~ At th_ ;ide flush 1:1 t Ov L,ont$roA

valves or by the rnanual adjustment of needle valves. "1'he remaining solvent is combined with l-octene., etb.ylene, and hydrogen (where used) and fed to the reactor. A
mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent,'monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalNrst component solutions are metered using pumps and mass flow meters and are combined ~~ith the catalyst flush solvent and introduced into the bottom of the reactor. The reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactoz--All exit lines from the reactor are steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static rnixer. "1'he product stream is then heated by passing through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilizinl; extruder and water cooled pelletizer. Process details and results are contained in Table 2. Selected polymer properties are provided in 'T'able 3.

= .r, rv L-, ..... ,.... - -. r^-3 v-~; - G3 , _.. N ..... ...E hr r, c~.i ., -- 11 [ C/? p ~ .....~ r.. ..... .... ,., " . ..... ..... .... .... =,-~ %'~ . ~ .-~ ~ `
[( 7 ~ .....
v ~ ^ ~ C'~.7 e+7 , .. ^Jp M co c~~ f^> h~ n rv r , -t m -7 C~ r9 ~ aocrr~ ~, o"~ oa~ c; (7~.~.nc c o3_ ~
r-- kn -rEn-^Nr-,r-ooea~.-o:~~n~r;:c, - - - - _.. - - - - - - - .,., -(.= ,J ^ t~7 CR ^ t`~ ~ C^~ V; d' G't ~F 6`GC7 CC C('rs 'L^
nt rn e - - rn N't V-) ry ~~' .~ (~ C~ ^-^= Vr OG C3 f V ~4 ^~ L`= v t C C~+ .['~ Q GO ,r",'^~õ
p =.-~- "~ ^^ C~I -^^ Q ^-~ O C =- C? C ^ ~ ^^^
C.J i.zõ

M f^~ f+l rr7 m f^. fn rrl M 111 M CV
t-~
rn N 41.

'i' "CS J
Lr 5 S C~ ~O e+~ 00 v~"
N O 7 J .T.. ^^ '"J N ^ ^ N =~
"~ ^"'W... X i C> C~..= O O , .. ^J C C v^ ... C7 ~.. C.=. . ~ """"
-Z crr fn r*; r+; . , rr? .. . , , , . .. _ . ~'.

y-I,,,E ~n r =~ .:~ ~ ^
r= e^a "= ;~
rn ~v . . U (`i . . . . = . . hd F^7 C 1 t"~ C~7 N C'l C`f f`.E Ã
à . . . . . . . .~ ~. .....i J ~~ .~ ~
~.w .... :r h;

J
171 j ^' C3 ~'-i .: ~ ~ . .. = , , , , . , ~ . , t^Y . . - - _ _.. _ ~ :~ ,- - -. - .__. .- ,_, ._, - - -I i ~ E E ~][ 3 n~~!ÃI~~O~O~C^, CS~!"'': ",J"N~Ãf;' ~N'^IÃ1'~~{~-~j'~= ~[3p' Ã E 7 E
~- E
f ~~~) n a-~t3 ~~N ch ~ n et r~ ~^ oo N~ m;~;vy N ^
]~.G~:aO`ao i~^1.-~ ~ o o^ cr c~t~x r~ ^
^ rn -- M L CJ ~O L` N
~ V r ~ rt CJ .^~ O N c' G~~ ^^

~l' Ãn O Ãr ~-. ~f' ÃYt ~G E ~t M ~' ^ ,~~./ r N'N~N ~-';N~N N -=~~ --~lCk ~
~fN N
. rh = .~ I ~" ^` '_' ,^~ ...

i. L ~ M ~ -~ ' v , U / . ~ `.C [~ n ~D ~I' 7 3 .~ g c'1 y" W

E~ T ri e~ ~~ r, r r= C7 0~ s~ w~ e^ e~ ^~1 ~t r~ .~
_ _ S. = O[O[Q O~_ ,C+ -==..ltr, M ~J' - =N CyE~ S"'ijO-C^, '.~`i "~' .^~.lN `.:
G ~../,....:~ ~-f . v.^e: 'JQ [~Ã~ -2``~~1~-~
n !

;e! r{ II = .
s~""
~
~~,,,, '~. E r^ r G't I`^ ~ [ - ~~.,~ ~ ; t`-~ r. < - ~=~= . 73 ~ ~ . N
r~ I Ã ; E ! ~ ~ ~
L Ev':C ~ .~~, ~ ~C^d !=- ^~,~)v~F(--~ ~~
: ; `[-. -;=--k- --i~-~- r"~'r~, ...=~.~ ~r.

.~-__...._......._........._._ ..~
..,.___,..._.____,..~_~....~..,......_......._....,..s.._.......s.,~..rr....._.
_z._~.~ -[01551 "I`he resultinL, polymers are tested by DSC and A.'I-'REE as with previous exai-nples.
Resuits are as follows:
101561 The DSC curve for the polymer of example 5 shows a peak with a 119.6 C
melting point (Tm) with a heat of fusion of 60.0 J/g. The corresponding CRYS`I"Ap' c-urve shows the tallest peak at 47.6 C with a peak area of 59.5 percent. "I'he delta between the DSC.
Tm and the Tcrvstaf is 72.0 C.

101571 The DSC curve for the polymer of example 6 shows a peak with a 11.5.2 C
melting point (Tm) with a heat of fusion of 60.4 J/g. "T'he corresponding CRYSTAF curve shows the tallest peak at 44.2 C with a peak area of 62.7 percent. The delta between the DSC
Tm and the Tcrystaf is 71.0 C.
101581 The DSC curve for the polymer of exarnple 7 shows a peak with a 121.3 C
melting point with a heat of ftision of 69.1 J'g. The corresponding CRYSTAk' curve shows the tallest peak at 49.2 C with a peak area of 29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1 C.
101591 The DSC curve for the polymer of'exarnple 8 shows a peak with a 123.5 C
melting point (Tm) with a heat of fusion of 67.9 11g. The corresponding CRYSTAF curve shows the tallest peak at 801.1 C with a peak area of 12.7 percent. The delta between the DSC
Ti:n and the "Tcrvstaf is 43.4 C.
101601 The DSC curvc for the polymer of example 9 shows a peak with a 124.6 C
melting point (Taii) with a heat of tiusion of73.5 Jlg. The correspondilig CRYSTAF curve shows the tallest peak at 80.8 C with a peak area of 16.0 percent. The deltabetwer;ii the DSC
"T'ir3 and the Tcrtistaf is 43.8 C.
101611 `I'he DSC curve for the polymer of example 10 shows a peak with a 115.6 C
rneltin- point (Tm) with a heat of ftision of 60.7 JAY. The corresponding CRYSTAF curve shows the tallest peak at 40t.9 C with a peak area of 521.4 percent. The delta between the DSC
"I'm and the Tcrystaf is 74.7 C.
101671 Tbe DSC curve for the polymer of e.xa.mple. 11 shows a peak with a 1 B
.fi `C
l-nclting point (Tm) with a heat of ftision of 70.4 if-. The corresponding CRYSTAF curve sho-~vs the tallest peak at 39.6 C with a peak area of 25.2 percent. 'I`he delta bew;=e:en the DSC
land the lcr~ i * s 74.1r.'.

ri ) with a heat t.i ! L: I i i}il.`% , i ti[. .: IRAf;tdrVe _~. _ shows no peak equal to or above 30 C. (Tcrystaf for purposes of further calculation is therefore set at 34 C). The delta between the DSC Tm and the Tcrystaf is 83.2 C.

t01641 The DSC curve for the polymer of example 13 shows a peak with a 114.4 C
melting point (Tm) with a heat of fusion of 49.4 i'g. The corresponding CRYSTAF curvYe shows the tallest peak at 33.8 C with a peak area of 7.7 percent. The delta between the DSC
Tm and the Terystaf is 84.4 C.
101651 The DSC for the polvmer of example 1.4 shows a peak with a 120.8 C
melting point (Tm) with a heat of fusion of 127.9 J/(,,. The corresponding CRYSTAF
curve shows the tallest peak at 72.9 C with a peak area of 92.2 percent. The delta between.
the DSC Tm and the, Terystaf is 47.9 C.
[0166] The DSC curve for the polymer of example 15 shows a peak with a 1] 4.3 C
melting point (Tm) with a heat of fusion of 36.2 Pa. The corresponding CRYSTAF
curve shows the tallest peak at 32.3 C with a peak area of 9.8 percent. The delta between the DSC
Tm and the Tcrystaf is 82.0 C.
101671 The DSC curve for the polymer of example 16 shows a peak with a 116.6 C
melting point (; I'm) with a heat of fusion of 44.9 ,lIg. The corresponding CRYSTAF curve shows the tallest peak at 48.0 C with a peak area of 65.0 percent. The delta between the DSC
Tm and the Tcrystaf is 68.6 C.
101681 The DSC curvc for the polymer of example 17 shows a peak with a 116.0 GC
meltin~ point (Tm) E~-ith a heat of fusion of 47.0 T/~,t. 'I`hc corresponding CRYSTAF curve shows the tallest peak at 43.1 C with a peak area of 56.8 percent. The: deita between the DSC Tm and the I'crystaf is 72.9 C.
101691 The DSC curve for the polymer of example 18 shows a peak witli a 120.5 C
melting point ("l`m) with a heat of fusion of 141.8 Jig. The corresponding CRYSTAF curve shows the tallest peak at 70.0 C with a peak area of 94.0 percent. The delta between the DSC Tm and the Tcrystaf is 50.5 C.

101701 'T'he DSC curve for the polymer of example 19 shows a peak with a 124.8 C
melting point (Trz) wit1i a heat of fusion of 174.8 J/g. l'be corresponding l;
CRYS"i,Af' curve shows the tall;.st peak at '19.9 C with a peak area of 87.9 percent. The delta between the DSC ..i...I-1? . %,staf:=_s 45.tJ C

1~~1 74 ~ 4"h, l~~`t; ~- ~ ~t~. c.omp-arative D ~ neak iiltCl= 'j.;= " ~' ~ ~ ; ~.~~
:~ ~ ~vi~

shows no peak equal to and above 30 C. Both of these values are consistent with a resin that is low in density. The delta betvveen the DSC Tm and the Tcrystaf is 7.3 C.

[01721 The DSCcurve for the polymer of comparative E shows a peak with a 1~4.0 C
melting point (Tm) with a heat of fusion of 179.3 Jig. The corresponding CR.YSTAF curve shows the tallest peak at 79.3 C with a peak area of 94.6 percent. Both of these values are consistent with a resin that is high in density. The delta between the DSC Tm and the Tcrystaf is 44.6 C.
101731 "I`he DSC curve for the polymer of comparative F shows a peak with a 11.4.8 C
meltin- point (Tm) with a heat of t'usion of 90.4 J/g. The corresponding CRYSTAF curve shows the tallest peak at 77.6 C with a peak area of 19.5 percent. The separation. between the two peaks is consistent with the presence of both a high crystalline and a low crystalline polymer. The delta between the DSC Tm and the Tcrystaf is 47.2 C.

Physical Property Testing 101741 Polymer samples are evaluated for physical properties such as high temperature resistance properties, as evidenced by TMA temperature tzstinf-), pellet blocking strength, high temperature recovery, high temperature compression set and storage modulus ratio, G'(25"C )'G'( l QO C)- Several coinmercialiy available polymers are included in the tests:
Comparative G* is a substantially linear ethyle:ne/ 1-octerie copolymer (A.pp'IN'I"I`Y?J, available 1'rom"I'he Dow Chemical Company), Comparative H* is an elastomeric, substantially linear ethylene/ 1-octene copolymer (AhTINITY'3~EG8if)0, available frorn `I"he Dow Chemica[ Company), Comparative I is a substantially linear ethylene%1-octene copolymer {AFFTtiITY*PLI840, available from The Dow Chemical Company), Comparative J is a hydrogenated styrene/butadienelstyrene triblock copolymer (KRA"I'ONTM
G1652, available from KRA'I'ON Polymers). Comparative K is a thermoplastic vulcanizate ('I'PV, a polyolefin blend containing dispersed therein a crosslinked elastomer). Restilts are presentecl in Table 4.

`1`able 4 l-ligb. Temperature Mechanical Properties ~ T1vIA-imrn Pellet Blocking 300 % Strain Coinpression penetration Strengtkt G'(25 C); Recoverv (80 C) Set (70 C) Ex. { C) lb/Ft (kPa) G'(1Ã)0 C) ( erce:nt) recr~t) D* 51 9 Failed E* 130 18 F~ 1 141(6,8) 9 Failed 1.00 5 104 (}(0) 6 81 49 6 110 - 5 i 152 7 li3 - 4 84 43 18 1.11 4 Failed j41 17 108 0(4) 4 82 47 G* 75 463 (22.2) 89 Failed 100 H* 70 213 (14.2) 29 Failed 100 1* H1 tl - -J* 107 5 Failed 100 K* 152 - 3 40 101751 In Table 4, Comparative F (which is a physical blend of the two polymers resultino froni simultaneous polymerizations using catalyst A1 and 131) has a 1 m.ni penetration temperature of about 70 C, while Examples 5-9 have a lmin penetration temperature: of 100 C or greater. Further. examples 10-19 all have a 1 mm penetration temperature of greater than 85 C-, with most having 1 mrn "i`MA temperature of greater than 90"C or even greater than 100 C. This shows that the novel polymers have better dimensional stability at higher temperatures compared to a physical blenc[.
Comparative J (a commercial SEBS) has agooci 1 mm TMA temperature of about 107'C, but it has very poor (high temperature 70"C) compression set of about 100 percent and it also failed to recover (sample broke) during a high temperature (80'C. ) 300 percent strain recovery.
Tlius the exemplified polymers have aunique, combination of properties unavailable even in some cominerciallv available, high performance thermoplastic elastomers.

'01761 Sinnila=1~. i _ a'. (ot)od: tz . { ._ r.._. -..
?)`"C"}, f-t (Comparative F) ba:s a st(iri:tE?;"s.', I.i.l{7(.it,IeL1` eiii'k) =. 'a ~cxtttiC)z.i, ~ iiz` ~,A~'YI"t:r (Comparative G) of similar density has a storage modulus ratio an order of tnagnitude greater (89). It is desirable that the storage modulus ratio of a polymer be as close to 1 as possible.
Such polymers will be relatively unatTected by temperature, and fabricated articles made from such polymers can be usefully employed over a broad temperature range.
This feature of low storaue anodulus ratio and temperature independence is particularly useful in elastomer applications such as in pressure sensitive adhesive formulations.
101771 The data in Table 4 also demonstrate that the polymers of the invention possess improved pellet blocking strengtb. In particular, Example 5 has a pellet blocking strength of 0 MPa, meaning it is free t7.owing under the conditions tested, compared to Comparatives F
and G which show considerable blocking. Blocking strength is important since bulk shipment of polymers having large blocking strengths can result in product clumping or sticking together upon storage or shipping, resulting in poor handling properties.
[01781 High temperature (70 C) compression set for the inventive polymers is generall.y, good, meaning generally less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent. In contrast, Comparatives F, G, 11 and J all have a 70 C
compression set of 100 percent (the max:imum possible value, indicatino no recovery). Good high temperature compression set (low numerical values) is especiallv needed for applications such as gaskets, window profiles, o-rings, and the like.

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. . . - - - . , - . - .. - . .. ~.y.i r . C1 50 101791 Table: 5 shows results for mechanical properties for the new pollvmers as well as for various comparison polymers at ambient temperatures. It may be seen that the inventive polyrners have very good abrasion resistance when tested aecordint-, to ISO
4649, generally showing a volunie loss of less than about 90 mzn', preferably less than about 80 mm', and especially less thazz about 50 mm'. In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance, t0I801 Tear strength as measured by tensile notched tear strength of the inventive polymers is generally 1000 mJ or higher, as shown in Table 5. Tear strength for the inventive polymers can be as high as 3000 mJ, or even as high as 5000 mJ.
Comparative polymers generally have tear strengths no higher than 750 W.
101811 Table 5 also shows tl-iat the polyniers of the invention have better retractive stress at 150 percent strain (demonstrated by higher retractive stress values) than some of' the comparative samples. Comparative Examples F, G and li have retractive stress value at 150 percent strain of 400 kPa or less, while the inventive polymers have retractive stress values at 150 percent strain of 500 kPa (Ex. 1.1) to as high as about l 100 1CI'a. (Ex. 17)-I'olymers havinc) higher than 150 percei-zt retractive stress values would be quite usefiil for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics. Other applications include diaper, hygiene, aiid medical garment waistband applications, such as tabs and elastic bands.
101:821 Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for the inventive polyr-ne.rs as coinpared to, for Lxample, Comparative G. Lowe-r stress relaxation nieans that the polymer retains its force better in applications such as diapers and other garments where retention of elastic properties over long time periods at body temperatures is desired.

_~~-O ti~esting Table 6 f'oEymer Optical Properties Ex. Internal Haze (percent) Clarity ( ercetit) 45 Gloss (percent) p* 84 22 49 G* 5 73 56 ' 6 33 69 53 1 a 7 74 69 G* 5 73 56 il* 12 76 59 1* 20 75 59 101831 The optical properties rcporteci in Table 6 are, based on compression molded films substantially laekin!"; in orientation. Optical properties of the polyiners may be varied over wide ranges, due to variation in crystallite size, resulting from variaÃiori in the cltianTity ofc:hain shuttling agent employed in the polymerization.

Extractions of Multi-Block Co iFiners [0184] Extraction studies of the polymers of.'examples 5, 7 and Comparative E
are conducted. In the experiments, the polymer sample is weighed into a glass fritted e_xtraction thimble and fitted into a Kumagakva type extractor. The extractor with sample is purged with nitrogen, and a 50OmL round bottom flask is charged with 350 rnL of diethyl ether.
The flask is then rit.teÃI to the extractor. "1`he ether is heated while being stirred. Tiineis noted ~N-b.en the ether begins to condense into the tbftnble, and the extraction is allowed to proceed under n.ifrogen for 24 hours. At this time, heating is stopped and the soluti.on is allowed to cool. Any etlier reniaining in the extractor is returned to the flask. 'I'he ether in tl n a. 4N..i-" 7~ _ rc3t121 t~, ~~ _ s a nse C 5 ', pur,(-,e, and the residue dried under vacuum ove,rrriaht at 40 C. Anv remaining ether in the extractor is purged dry with nitrogen.

101851 A second clean round bottom flask charged with 350 ml, of'hexane is then connected to the extractor. The hexane is heated to reflux with stirring and maintained at reflux for 24 hours after hexane is first noticed condensing into the thimble.
Heating is then stopped and the flask is allowed to cool. Any hexane remaining in the extractor is transferred back to the flask. The hexane is removed by evaporation under vacuum at ambient temperature, and any residue remaining in the flask is transferred to a weighed bottle using successive hexane washes. The hexane in the flask is evaporated bv a nitrogen purge, and the residue is vacuum dried overnight at 40 C.

[01861 The polymer sanlple remaining in the thimble after the extractions is transferred from the thimble to a weighed bottle and vacuum dried overnight at 40 C.
Results are contained in "Fable 7.
Table 7 etlaer ether C8 hex aai hexane C~ residue ~~t. soluble solLible mole soluE~le soluble i~aolc. C~ mole Sani Ee (g) (g) (ercent) percent' f(percent) ercerlt perccnt C.omp. 1.097 0.063 5.69 12.2 0.245 22.35 13.6 6.5 F*
k~x. 5 1.006 0.041 4.08 - 0.040 3.98 14.2 1 1.6 F>x.7 1.092 0.017 1.59 13.3 0.012 1.10 11.7 9.9 Determined by "C: NMR

Additional POlvmer Exam le"9 A-J, Continuous Solution Potvmerizati n Catalvst A1./B2 + DEZ

For Exam les 19A-I

101871 Continuous solution polvmerizations are carried out in a camputer controlled well-mixed reactor. Purified mixed alkanes solvent (Isopar''m E available froin Exxon Mobil. Inc.). ethylene, 1-octeire. and lrvdrogen (dvhere used) are carn.bined ancl fed to a 27 ~_Ya11on reactor. The feeds to the reactor are measured by mass-flow controllers. Tl-le temperatr.u=e of the feed stream is controlled bv use of aolvcol cooled heat exchanger before etate.rin~,r the reactor. The catalyst component solutions are metered using pumps and mass flow meters. 'f he reactor is run liquid-full at approxitnatelv 550 psi, pressure. Upol1 11-t '"F I('tr'r, i'.'_?t r a1?d ?ddi ` ,: ar e ?3o1 ; ; . , ; - = _:. _ ._ _ .,.
: . ` _ ._. , . _ ., x :. ... _ .~:_ unreacted monomers are removed during the devolatization process. 'I'he polymer melt is pumped to a die for underwater pellet cutting.

For Exam le 19J

[01881 Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alk:anes solvent (IsoparTM E available from ExxonMobil Chemical Company). ethylene at 2.70 ibsihour (1.22 kg,Ihour), 1-octene, and hydrogen (where used) are supplied to a 3.8 L
reactor equipped with a jacket for temperature control and an internal thermocouple.
The solvent feed to the reactor is measured by a mass-flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator. "I`llese flows are measured b_v Micro-Motion mass flow meters and controlled by control valves or by the manual adjustment of needle valves.
The remaining solvent is combined with 1 -octene, ethylene, and liydrogen (where used) and fed to the reactor. A mass flow controller is used to deliver hydrogen to the reactor as needed.
The temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst component solutions are metered using pumps and mass flow meters and are combined with.
the catalyst flush solvent atid introduced into the bottom of the reactor. The reactor is ri-n liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product is reinoved through exit lines at the top o#'the reactor. All exit lines from the reactor are steam traced and insuiated..
Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the Ãnix.ture through a static mixer, The product stream is then heated by passin~ thro~~~;h a heat exchanger before devolatilization.
The polymer product is recovered by extrusion using a devolatili:zing extrtiidcr and water cooled pelletizer.

101891 Process details and results are contained inTable 8. Selected polymer properties are provided in Tables 9A-C.

10I901 In Table 9B, inventive examples 19F and 19C`~ show low iiiiznccliate set of around 65 70 % strain aftcr 500% d-:iongation.

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:3 kx x x :A x õ~-Examples 20 and 21 10:1911 'I'he ethvleneia-olelin. interpolyrrier ot'Examples'0 and 21 Niv ere made in a substantially similar manner as Examples 19A-1 above with the polymerization conditions shown in Table 11 below. The polymers exhibited the properties showii in Table 10. Table 10 also shows any additives to the polymer.
Tahle 10 - Properties and Additives of Examples 20-21 ExatnpEe 20 Example 21 Density (g/cc) 0.8800 0.8800 mI: 1.3 1.3 DI Water 100 DI Water 75 Irgafos 168 1000 Irgafos 168 1000 Additives Irganox 1076 250 Irganox 1076 250 Irganox 1010 200 Irganox 1010 400 Chimmasorb Chimmasorb I-iard segment split (FVI /tr) 35% 35%
101921 Irganox 1.010 is Tetrakisinethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamaie)rnethane. Irganox 1076 is Octadeeyl-3-(3`,5-di-t-butyl-4`-hydroxyphenyl)propionate. Irgafos 168 is Tris(2,4-di-t-butylphenyl)phosphite.
Cb.itnasorb 2020 is 1,6-Ilexanedia.mine, N,N'-bis('-',2,6,6-tetra7nethvl-4-piperidiiiyl)-polyiner with 2,3.6-trichloro-1.3.5-triazine, reaction products with, N-butyl-l-butanaz-nine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

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"iYYll ~ tt m -~v !~ ~ _. - ..... .. . _ Fibers Suitable for the D'veci Fabrics and Textile Articles of the Present Invention 101331 The present invention relates to dyed fabrics sLaitable for textile articles such as shirts, pants, socks, swimsuits_ etc. The fabrics may be made in any manner but typically are either woven or knit. Woven fabrics of the present invention are typically characterized by a stretch of at least about about 10 percent measured according to ASTM D3107 whereas knit fabrics of the present invention are typically characterized by a stretch of at least about 30 percent measared according to ASTM
D2594.

[0194) The dyed fabrics are usually comprised of 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 suitable crosslinking agent. As used herein, <`crosslinkinb agent" is any means which cross-links one or more, preferably a majority, of the fibers. Thus, crosslinking agents may be chemical compounds but are not necessarily so. Crosslinking agents as used herein also include electron-beam irradiation, beta irradiation, garnma irradiation, corona irradiation, silanes, peroxides, allyl compounds and UV radiation with or without crosslinking catalyst. U.S.
Patents No, 6,803,014 and 6,667,351 disclose electron-beam irradiation tnethods that can be tised in einboclii-nents of the invention. Typicallv, enough fibers are crosslinked in an anrount sLich that the fabric is capable of being dyed. This amount varies depending Lipon the specific polymer employed and the desired properties. However, in some embodiments, the percent of cross-linked polymer is at least aboLit 5 percent, preferably at least abotit 10, more preferably at least about 15 weight percent to about at most 75, preferably at most 65, preferably at most about 50 percent, more preferably at most about 40 percent as measured by the wei(,?ht percent of gels formed according to the method described in Example 25.
[01951 The fibers typica]ly have a filament elongation to brea.k of greater than aboLIt 200%, preterably greate;r thari about 2I0%, preferably -reater than about 220%, preterab[y greater than aborit 230 fl, preferablv greater than about 240 o, pre#erablygreater than about 250%. preferably- greater than about 760 o, preferably greater than about 2~1"'. r e1erab3. _re:ater tha.n,',out 280" n , .1_ itlli- _a.

elongation t' load at 100% elongation of greater than or equal to about 1.5, preferably greater than or equal to about 1.6, preferably 4,reater than or equal to about 1.7.
preferably greater than or equal to about 1.8.
preferabiv greater than or equal to about 1.9, preferably greater than or equal to about 2.0_ preterabl.y greater than or equal to about 2.1. preferably ~reater than or equal to about 2.2, preferably greater than or equal to about 2.3, preferably greater than or equal to about 2.4, and nlay be as high as 4 according to ASTM D2731-01. (under force at specified elongation in the finished fiber form).
[01961 The poEyolefin may be selected from any suitable ethylene olefin block polymer. A particularly preferable olefin block polymer is an ethylene/a-olefin interpolymer, wherein the ethyleneia-olefin interpolymer has one or more of the following characteristics beforc crosslin.king:
(1) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, ;VIw: VIn, greater than about 1.3; or (2} at least one molecular fraction cMhich elutes between 40 C- and 130 C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about l; or (3) an.Mw/Mn from abotrt 1.: to about 3.5, at least one melting pc>int, "I'm, in degrees C:elsius, and a density, d, in grams/cubic eentimeter, wherei.n thenuniericai values of:'Trn and d correspond to the relation.ship:

T,ry, > -2002.9 - 4538.5(cl) - 2422.2(d) 2 ; or (4) an Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ~l-I in Jfg, and a delta qtiiantity, AT, in dearees Celsius defined as the temperature dif#erence between the tallest DSC peak and the tallest CRYSTAF
peak.
tiN-herein the niirnerical values of AT and AH have the f'ollowina relationships:

AT >-D.1299(A.1l) 62.81 for Af-f greater than zero and up to 130 J/
A'I' > 48 C for AH greater than 130 .l1'g , wherein the C.RYSTAF peak is determined using at least 5 percent of the cuznulative polymer, and if less than 5 percent of the polymer has an identifiable CRYS`1:AF peak, then the CRYSTAF temperature is 30"C; or (5) an elastic recovery, Re, in percent at 300 percent strain and I
cycle measured with a cornpression-molded film of the ethylene/n,-olefin interpolymer, and has a density, d, in granas;`cubic. centimeter, wherein the numerical valties of Re and d satisfy the l'ollowing relationship when etb.vlene/a-olefin interpolymer is substantially free of a cross-Iiiiked phase:

Re > 1 481-162g(d); or (6) a molecular fraction which elutes betweert 40 C and 130"C
vuhen ftaetionated usini! TREF, characterized in that the fraction has a molar comonQmer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the vhole polymer) within 10 percent of that of the etbylene/a-olctin interpolynner; or (7) a storage modulus at 25 C, G'(25 C), and a storage modulLrs at 100 C. G'(10t) C), wherein the ratio of G'(25 C) to G'(100 "C:) is in the range of about 1:1 to about 9: i.

[01971 The fibers may be made into any desirable size and cross-sectional shape depending upon the desired application. For nranv applications approxiti-iately round cross-section is desirable due to its reduced friction. 11owever, other shapes such as a trilobal shape, or a flat (i.e., "ribban" like) sliape can also be employed.
Denier is a textile term i~~hiclr is defined as the ,rams of the fiber per 9000 nreters of that tiber's pen(yth. Preferred denier sizes depend upon. the type of fabric and desired applications.
Tvpically, knit fabric-s comprise a majority of the fibers having a denier fi-om at least about I. preferably at Icast about 20. pre,ferablv at least aboLit 50, to at most about 180. pref:c:rabt~, ~i -nost 150, r~referab1N- ,ifi raiost aborat 100 .?. T1 1?ret r5I.;' at 101981 Dependin(i upon the application the fiber may take ar,y suitable form including a staple fiber or binder fiber. Typical exaniples may include a homofil fiber, a bicomponent fiber, a meltblow-n fiber, a nieltspun tiber. or a spunbond fiber.
In the case of a bicomponent fiber it inav have a sheath-core structure; a sea-island structcre; a side-by-side structure; a matrix-fibril structure; or a segmented pie struetu.re. Adirantaneously, conventional fiber form.in") processes may be employed to make the aforementioned fibers. Such processes include those described in, for example, U.S. Patents No. 4,340,563; 4,663,220; 4,668,566; 4,322,027. and 4,413,110}.

[01991 Depending upon. their composition, the fibers may be made to facilitate processing and unwind the same as or better t`roin a spool than other tibers.
Ordinarv fibers when in round cross section often fail to provide satisfactory unwinding perforrnance due to their base polymer excessive stress relaxation. This stress relaxation is proportional to the age of the spool and causes filaments located, at the very surface of the spool to lose grip on the surface, becoming loose filament strands.
I_ater, when such a spool containing conventional fibers is placed over the rolls of positive feeders, i.e. Memminger-IRO, and starts to rotate to industrial speeds, i.e. 100 to 300 rotations/minute, the loose fibers are thrown to the sides of the spool surface and ultimately fall off the edge of the spool. This failure is ku.own as derails which denotes the tendency of conventional fibers to slip off the shoulder or edge of the package which disrtiipts the unwinding process and ultimately causes machine stops.
`I'he above fibers may exhibit dera.ilinc, to the same or a much less signiticant degree which possibly allows greater throughput.
[02001 Another advantage of the fibers is that defects such as fabric faults and elastic filament or fiber breakage may be equivalent or reduced as compared to conventional fibers. That is, use of the above ti.bers may reduce, buildup of fiber fragments on a needle bed -- a problem that often occurs in circular knit inachines when polymer residue adheres to the needle surface. `1'lrus, the fibers may redti.ce the corresponding f:abric breaks caused by the residue when the #ibers are being made into, e.u. fabrics oi1 a circular knitting tnachiile.
,,.: , ... . _ 11)2t3I1 'latti;~
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elastic olctin fibers require that tlaese guides be i-nade of rotating eletne.nts such as pulleys as to m.inimize friction as machine pdrts, such as evelets, are heated up so that machine stops or filament breaks could be avoided ciurin4 the circular knittinfz process. That is, the frictioti against the guiding elements of the machine is reduced by using the inventive fibers. Further information concerrzi g circular knitting is found in. for example, Bamberg Meisenbach. "Cir-cular Knitting: TechrzoIvk, Process, Structures, Yarns, Qiialrty ", 1995, incorporated herein by reference in its entiretv.
Additives [0202] Antioxidants, e.g., 1RGAFOS'-X 168, 1RGANOXfg) 101.0, IRGANGX*1, 3790, and C.1:TIMASSORB~~~ 944 iiiade by Ciba Geigy C,orp., may be added to the ethylene polymer to protect against undo degradation during shaping or fabrication operation andlor to better control the extent of grafting or crosslinking (i.e., inhibit excessive gelation). In-process additives, e,g. calcium stearate, water, lluoropolymers, etc., may also be used for purposes such as for the deactivation of residual catalyst and/or improved processability. TIXliVIN~,R~ 770 (from Ciba-Geigy) can be used as a light stabilizer.
102031 The copolymer can be #i[led or unfilled. lf 17illed, then the amount of filler present should not exceed an amount that would adversely affect either lieat-resistance or elasticity at an elevated teniperature. If present, typically the amount of filler is between 0.01 atrd 80 wt % a based on the total weight of the copoi3-mer (or if a blend of a copolymer and one or more other polymers, then the total weight of the blend). Representative fillers include kaolin clay, magnesium hydroxide, zinc oxide, silica and calcium carbonate. In a preferred embodimeiit, in which a filler is present, the filler is coated with a material that will prevent or retard any tendency that the filler mi-ht otlierwise have to interfere with the crosslinlcitig reactions.
Stearic acid is illustrative of sLÃch a filler coating.
[02041 To reduce the 1'riction coefficient of the f bers. various spin finish formulations can be used, such as naetallic soaps dispersed in textile oils (see l~or exaniple. t.:.S. I'atentNo_ 3,039,40~5 or U.S. 1'~, .jt _X:-a. 6,65,2e599", suri-actants in a base <~ ~~~~ssc t;S
fo . ..- ~. _'. ._ . . '~~. ~ _. . ~
-~~=t-Application No. 10/933,721 (published as LS200501423360) discloses spin finish compositions that can also be used.

Fabrics [0205] '1"he present invention is directed to improved, dyed textile articles comprising an olefin block copolNFmer. For purposes of the present invention, "textile articles" includes fabric as well as articles, i.e., garments, made from the fabric ineluding, for e.xarnple, clothing and other items in need of coloring. By knitting it is meant intertwininc, yarn or thread in a series of connected loops either by hand, with knitting needles, or on a machine. The present invention may be applicable to any type ol'knitting including, for example, warp or weft knitting, flat knitting, and circular knitting. Particularly preferred warp knits inclLid.e tricot and raschel while preferred weft knits include circular, flat, and seamless. However, the invention is particularly advantageous wben. employed in circular knitting, i.e., knitting in the round, in. which a circular needle is employed. The present invention may also be applicable to any type of woven fabric.
102061 'f he dyed fabrics oi'the present invention preferably comprise one or more elastic fibers wherein the elastic fibers comprise the reaction product ot'at least one ethylene olefin block polymer and at least one crosslinking agent wherein the ethylene olefin block polymer is an ethylene!a-olefn interpolymer, wherein the ethylene/c1-olefin interpolymer has one or anore of the following characteristics prior to crosslinking:
(1) an average block index greater than zero and up to abotLt 1.0 and a moleci.rlar weight distribution, Mw/Mn, grreater thaii about 1.3; or (2) at least one molecular tiaction which elute5 between 40 C, and 1' WC when fractionated using TREF, characterized in that the fraction has a block i7idex of at least 0.5 and up to about 1; or (3) an Mw/Mn from about 1.7 to aboLit 3.5, at least one ine,lting point, T'm. in degrees Celsius, and a dcnsitv, d. in gams,-cubic centimeter, w1lerein the rit alues of ":: m and d correspond to th _ .-,ship:

_~~~;_ (4) an iv1w:/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, AH in Ji`g, and a delta quantity, AT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF
peak, wherein the numerical values of AT and AH have the following relationships:

AT --0.1Z99(AH) = 62.81 for AH greater than zero and np to 130 Jrs_=, AT ? 48 C for AH greater than 130 J/g, wherein the CRYSTAF peak is defier-mined using at least 5 percent of the cuniulative polymer, and if less than 5 percent of the polymer has an identifiable C:RYSTAF pcak, then the CRYSTAF temperature is i0 C; or (5) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compressiorr-molded film of the ethylenela-olelin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d sati5fy the following relationship when ethylene/a-olefin inte.rpolymer is substantially free of a cross-linked phase:

Re >1481-1629(d); or (6) a molecular fraction which elutes between 40'C. and 130j C
when fractionated using TREF, characterized in that the fraction has a--izolar comonomer content of at lea~st 5 percent laig.ber than that of a comparable randoni ethylene interpolymer fraction elating between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and m.olar comonomer content (based on the whole polymer) within 10 percent of that of the ethylenefa-oleiin interpolymer; or (7) a storage inodulus at 25 C, G'(25 C.), and a storaue modulus at 100 C., G'(100 C:), wherein the ratio ofG'(?5 C) to Ci '(100 "C.} is in the range of about 1:1 to about 9:1.

102071 "fhe amount of polynier in the d_ct;il-,ric :ries depcn.din<~,~ upon the 1)(~;t ~ r r~: ;aõ ttitl fl8e d Cs fat11' ;_)C:"IlI 5.
;t .. = } e t:

typically comprise less than about 50, preferably less than about 40, preferably less than about 30, prefera.bly less than about 20, more preferably less than about 1Ã1 weight percent e:thylene/o-olelin interpolymer. The ethylene;'u-olefin interpolymer may be in the form of a fiber and may be blended with another suitable pcslyrner, e.g.
polyolefins such as random ethylene copolymers, HDPE, LLDPE. LDPE. liI.DPE-polypropylene homopolymers, copolymers, plastomers and elastomers, lastol, a polyamide, etc.
[0208] The ethylenet'a-olefin interpolymer of the fabric may have any density but is usually at least about 0.85 and preferably at least about 0.865 1;/cm' (ASTM D
792). Correspondingly, the density is usually less than about 0.93, preferably less than about 0.92 g/cm3 (ASTM D 792). The etliylene/cc-olefin interpolymer of the fabric is eharacterized by an uncrosslinked melt index of from about 0.1 to about 10 g!10 minutes. If crosslinking is desired, then the percent of cross-linked polymer is often at least 10 percent, preferably at least about 20, more preferably at least about 25 weight percent to about at most 90, preferably at most about 75, as measured by the weiglit percent of -;e1s formed.
[02091 The fabrics often comprise another material selected from the group consisting of rayon, nylon, viscose. polyester such as microfiber polyester, polyamide, polypropylene, cellulose, cotton, flax, rarmie, hern.p, svool, silk, linen, bamboo, tencel, mohair, other natural fibers, other sythetic fibers, and mixtures thereof.
Often the other niaterial comprises the majority of the fabric, ln such case it is preferred that the other material comprise from at least about 50, preferably at least about 60.
preferably at least about 70, preferably at least about 80, sometimes as much as 90-95, percent by weight o.f the fabric.
102101 'I'hc ethvlene/a-olefi.n interpolymer, the other material or both may be in the fornl of a Iiber. Preferred sizes include a denier from at least about L.
preferably at least about 20, preferably at least about 50. to at most about 180, preferably at most about 150, preferably at most about 100, preFerably at most about 80 clenier.
102111 Particularly prefcrred circular knit fabrics comprise ethylene;'et-olefin interpolymer in the form of a fiber in an amount of from about 5 to about'fl percent (b~- 4 the = .' ' , . l~..t: _ 1_ .? = )retcrrew s. , r, f" or.=s 6f about 30 percent (by weight) of the fabric in the fornt of a fiber. Often such warp knit and circular knit fabrics also comprise polyester or aticroliber polyester.
102121 The fabric, particularly knit fabrics, often have less than about 5, preferably less than 4, preferably less than 3, preferably less than 2, preferably less than 1, preferably less than 0.5, preferably less than 0.25. percent shrinkage after wash according to AATCC 135 in either the horizontal direction, the veqical direction, or both. '1iore specifically, the fabric (after heat setting) often has a dimensional stability of from about 7% to about +7%, preferably -5% to about S%, preferably from about -3% to about 4-3%, preferably -2% to about --2%, more preferably -I
% to about -1 /a in the lengthwise direction, the widthwise direction, or both according to AATCC135 IVAi. In addition, the fabrics often have less shrinkage after wash aecording to AATCC 135 IVAi than a comparable fabric of elastic fibers with a higher amount of crosslinking.
102131 Knit fabrics can be made to stretch in two dimensions if desired by controlling the type and arriount of eth.ylene/a-ole~~in interpolymer and other materials.
Knit fabrics may sometimes be characterized by a stretch of at least about 30 percent measured according to AS"I-M D2594. Similarly, the fabric can be made such that the &uowth in the lengthwise and widthwise directions is less than about 7, preferably less than about 5, preferably less than about 4, preferably less t.han about 3, preferably less than about 2, preferably less thair about 1, to as little as 0.5 percent according to ASTM D 2594. Using the same test (AS"1'M D 2594) the lengthwise growth at b0 seconds can be less than about I5, preferably less than about 12, preferably less than about 10, preferably less than about 8%. Correspondin-ly, using the same test (AS"I'M D 2594) the widthwise growth at 60 seconds can be less than about 20, preferably less than about 18, preferably less than about 16, preferably less than abotit 13%. In regard to the 60 minute test of ASTM D21594, the widthwise growth can be less than about I0, preferably less tlaan about 9, preferably less than about 8, preferably less than about 6% ~~-hile the lengthwise growth at 60 minutes can be less than about 8, preferably less than about 7, preferably less tlian about 6, preferably less than about 5%. "fhe- lo .er iyrowth described above allows the fabrics of the inventiori to t' .., ..~ ;t l~.ss t': a , ,u I. " I
- - . ,.- _ ` .... . .. _.. i . . .
.,~,8m size. In contrast to knit fabrics, tv oven fabrics ma.y be characterized bv a stretch of at least about 10 percent measured according to ASTM D3107.
142141 Advantageously. knit fabrics of the present iaivention caii be made without a substantial number of breaks and using a knitting machine comprising an eyelet feeder system, a pulley system, or a combination thereof. Thus, the circular knitted stretch fabrics having improved tnoldabi.lity while having acceptable dimensional stability (lengthwise and widthwise), acceptable growth and sla.rinkage, the ability to be heat set at low temperatures while controlling size, .iow moisture regain can be made without significant breaks, with high throughput, and without derailing in a wide variety of circular knitting machines.
Dyeing [02151 The dyed fabrics of the present invention may be made by virtually any dyeing process. For example, many useful techniques are described in Fundamentals of Dyeing and Printing, by Garry Mock, North Carolina State Ciniversity 2002, ISBN 9780000033871. One advantage of the fabrics of the present invention is that they may often be contacted with the dye at a temperature of at least about 130 C to produce a dyed fabric wherein the fabric exhibits a growth to stretch ratio of less than 0.5, preferably less than 0.4, prefcrably less than 0.35, pref'erably less than 0.3, preferably less than 0.25, preferably less than 0.2, preferably less than 0.15, preferably less than 0.1, preferably less than 0,05. Advantaf;eously, the resulting dyed fabrics of the present invention are often characterized by a color change of greater than or equal to about 3 a.0, preferably areater thayr or equal to about 3.5, more preferably greater than. or equal to about 4.0 according to AATCC
evaluation after a first wash by AA`I'CC6I-2003-2A. Another advantage is that the fabrics of the present invention may sometimes exhibit a color change of greater than or equal to about 2.5, preferably ~.,.reater than or equal to about 3Ø more preferably (yreatir than or equal to about 3.5 according to r1ATCC eva.luation after a second wash by AATCC.6I-2003-2rL. In essence this a-neans that the dyed I'abric5 of the present invention ina~,,' exhibit less fading when subjjected to launderin-than conventional d~:d fabrics.

d~'Ã liczg;rlcs t11"s.tS' C=tce?i a coI; atl(:' u' or equal to about 600, preferably of greater than or equal to about 650, preferably of greater th.an or equal to about 700, preferably of greater than or equal to about 750, as measured with a spectrum photometer. Advantageousiv, the color is substantially retained even after a first and second wash. For examplÃ;. the dyed fabrics may be characterized by a color strength after a first wash by AATCC6I-2003-2A that is at least about 90, pref.'erably at least about 95, more preferably at least about 97 percent of the color strength after dying whereiii each color strength is measured with a spectrum photometer. The dyed fabrics may sometimes also be characterized by a color strength afler a second wash by AATCC61-2003-2A that is at least about 90, preferably at least about 92.5, niore preferably at least about 94 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

[0217] While not wishing to be bound by any theory it is believed that the reason the dyed fabrics of the present invention dye darker is due to the fibers of the olefin block polymer. 'I'hat is the olefin block polynler fzbers dye, to a lesser extent allowing the other rnaterial to get darker. Also, a higher dycing temperature can be employed with less fiber breakaue when oletin block polymers are used as the fibers. In a similar manner it is believed that the reason the dyed fabrics fade less upon laundering is that the olefin block polymer fibers are not dyed to as great of an extent as fibers made with other polymers. In this manner, the olefin block polymers cannot fade or bleed as much.

EXAMPLES
Exampte 22 - Fibers of elastic ethylenela-Olefin interpolymer j02181 The elastic ethyItne/a-olefan interpolymer (oIe-fin block polymer) of Example. 20was used to make monofilament fibers of 40 denier having an approximately round cross-section. 13efore the fiber was made the following additives were added to the polymer: 7000 ppm f'DMSO(polydimethvl siloxane), 3000 ppm CYANOX 1790 (1.3,4-tris-(4-t-butyC-3-hydroxy-2,6-dimethylhenzyl)-1.3,5-triazine-2,4 b-(1H,3H,5H)-trione, and 3000 ppm CH1iL9<1SOR13 944 Poly-[[6-(I,1,3.3-Te I 1.
pi ,~
< Fxt ':3 ',`,~x ~,iiuu ~ca x73a's a ~z9ti =~i wNIila ci t:ttef;,2' ~'P
'TÃ}

diarncter, a spin temperature of 299~C, a winder speed of 650zn'mi.nute. a spin finish of 2%, a cold draw of 6%, and a spool weight of 150g. "I"he fibers were then crosslinked using a total of 176A kGv irradiation as the crosslinking agent.
Example 23 - Hard yarns of fibers [0219] A hard yam was made that comprised the elastic fibers ohl;xample 22 and 150 den.ier, 288 filament polyester. 'I'he filament of microfiber is fine as 0.52 denier per filament. Two comparative examples were also made. One comparative example hard yam employed 40 denier Eibers of a random ethylene-octene copolymer made with a line speed of 450 rnlmin and the same 150 denier, 288 tilarnent polyester f1bers. The ran.dom ethylcrre-octene copolyrner had an average nrelt index of 3.0 ;Il Omin, a density of 0.875 g/cm3 and was crosslinked with a dosage of of 166.4 kGy irradiation as the crosslinking agent. The second comparative example hard yarn was made with multi-filament fibers of Lycrarm 162 C polymer and. the, same 150 denier, 288 filainent polyester fibers.
Example 24 - Dyeing 102201 An experiment was designed to evaluate the elastic fiber color stainin.-and the color darkness of microtiber polyester based fabrics. The experiment evaluated the disperse dyestufi'staining on the ribers coniprised of olefiin block polymers, the fibers comprised of Lycra" 162C, and the fibers comprised of random ethylene-octene copolymer. 1grarn of each of the three different types of fibers and 9 (Trams of micro-fiber polyester fabric (witness fabric) that made the hard yam was loaded in a lab rapid dycing machine tliat is shown in Figure 8. 'I:'he dyeing and reduction wash process as shown in l~igure 9 was then conducted on each of the three different types of libers. Clariant dyestuff Foron Black S-WF was used to dye the fibers and fabrics into black. The Lycra based fibers were dyed at 125 C since this elastic tiber may uildergo severe damage at higher temperatures. The other two types of (7ibers ~-ere dyed at 135 'C. The specin-ten.s of alter dyeing, after Is` reduction Aash and after 2"d reduction ik-ash were collected for evaltiiation.
(0221] The three dif.'ferent t}-pes of fibers after dycing and reduction wash were evaluated visnaIl,. The po]ycster micro Eiber fabric was also tesiud to get color f -Ti b E ~~
-~ ~ I~ i~b - , ~Tl,yth { N ~' Ii~ '` ~ -:}~-photometer (Datacolor mociel-600PLUS). 1-ligh KiS value represented darker color.
Color change was measured according to AATCC 61-2003 LA that repoz-ts the color difference between ori-inal specimen and the speciinen. after wash. The quotation ranges #ron3 1-5 by arey scale according to AATCC evaluation procedure. A Iow er grade indicates a bigger color change and therefore less colorfastness. The specimens after dyeing, aftcr I5Ã reduction wash. and after 2rt reduction wash were washed by AATCC b 1-2003-2 A and the color change before and after was measured.
102221 Color staining is also based on the test of AATCC 61-2003-2A. A multi-fiber test Eabric that consists of acetate, cotton, polyamide, acrylic and wool fiber, is attached to the specimen to wash. The test grades 1-5 and a lower grade means heavier color staining. Textile industry practice is to use the grade result of polyamide as an indication of color staining.
102231 Lab dips of the three different types of elastic fibers after dyeing, after 1 S`
reduction wash and after 2d reduction wash were done. The results indicated good colorfastness and darker color for the fabrics comprising the olefin block polymer.
Table 12 shows the elastic fiber color staining after dyeing, after I"reduction wash and after 2 d reduction wash. More dyestuff uptake makes darker color on elastic fiber itself. High dyesttrff uptake is positive to obtain dark colors but can be detrimental if it bleeds out during washing (home laundry). "I`he I..ycrarl"
fiber sllows darkest color after dy'eing, after I" redtaction wash and after 2"" reduction wash. The raiidom ethyleine-octene copolymer and olefin block polymer fiber shows lighter color staining. The specimens are very siiirilar after dyeing, after I'r reduction wash and after 2" d reduction wash. The olefin block polymer fiber shows less dyestuff uptake that helps better colorfastness in micro fiber polyester fabric colorfastness.
Table 12 Color staining Random Testing item Lycra 162C ethylene Olefin block octene polymer copnlr mer i Elastic Fiber color stain after Darkest Li=Yhter Zi,~hter ; dyeing h1astic liber Color stait-t after Darkest I..iLhter I,iuyhter 1.~'R ci ~
~ .
~.~er C:3t,,,. ;:ffs,f :C

- i".'. . t . .. . i i -^7'~

[02241 Table 13 shows the color strenath. (K; S) value of rnicro fiber polyester tabric. The higher value otKiS represented darker color. Witness micropoly-ester fabrics d.ved with random ethylene-octene copolymer and olefin block polymer tibers showed darker black compared with L,ycra. While not wishing to be bound to any theory it is believed that this result is due to the higher dyein~ temperature employed.
There were no significant differences among the sanipies after dyeing, after 1 reduction wash and after 2"d reduction wash. However, the microfiber polyester of olefin block polymer can reach a darker color.
Table 13 Color strength(K/S) value of fabrics Ranciam Testing item Lycra 162C ethylene- Olefin block octene polymer c ol rner Micro PES witness fabric 423.38 755.77 774.71 Color strength (K/S) after dveing Micro PES witness fabric K/S 414.68 783.83 753.67 after l" RC
Micro PES ~-itness fabric K/S 411.73 75s.00 739.86 affier 2"d RC

102251 "I"able 14 shows the color change value otmicro fiber polyester after dycing, after lst reduction ikash and after 2" reduction wash. 'I"he higher value t-nea s lighter color change. All specimens show good color change results.
Tab[e 14 Result of color change of micro polyester Random Olefin Testin~ item Lyera ethylene- block 162C octene co~salymer ~olyrner Micro PES witness fabric Color 4 4 4 change after dyeing %Iicro 1'I_:S witness fabric Color chanue after I't RC

'vficro PES witness fabric Color [ 4 4 4 chan,~,e after 2"d RC - . ~ le 1ess ~: ir --, ,,_ color staining. There is no obvious difference between the results shown after 1.'t and 2"d reduction wash_ The dyed, witness fabrics of random. ethylene-octene copolymer and olefin block polymer are darker than the dyed Lycra fabric and this has an effect on the color fastness as given in Table 12 . None of the results involve fabric heat setting.
Table 15 Color staining to polvarmide fabric Randona. Olefin ethy lene-Testing item Lycra 162C block octene polymer co . ol ymer Micro PES witness fabric Color ~ 2.5 2.5 fastness to wash after dyeing Micro PES witness fabric Color 3.5 3.5 3.5 fastness to wash after 1 st RC
Micro PES witness fabric Color 3.5 3.5 3.5 fastness to wash after 2nd RC

[0227] Three single jersey knits are use in this test. They are micro fiber polyester hard yarn knitted with 40 denier Lycra, 40 denier random ethylen.e-oetene copolymer and 40 denier olefin block polymer fiber. The knitting speed, elastic draft and the fabric weight of ereige are given in Table 16.

Table 16 Fabric description of various elastic fiber contented fabric Sample Speed ~ D.R. Greige r mLycra 162C 12.4 2.6 203 bl rti Random ethylene- 12.4 2.6 1701;/mi ctene co olvmer lerin Block 20 3 .2 186g,='rt1 Polymer 102281 Random ethylei.it-oc-tr;ne copoltirner and olefin block polymer greige are scoured at 85~C for 1-0 minntes, dried at 13 5"C for 45 mintites, tensionless dryed at 13C}C for 60 minutes, set at 165'C for 120 seconds (15 yards per minute) a120%
overtee.d, and tinished. The and reduction conditions are -i,, cli in Fioure 9 for ra l 3 . _h ;

Table 17 Fabric weight of various elastic fiber contented fabric Sample ID Finished weight Lycra 162C 269 g/ t71 andom ethylene- 210 gr m ctene co olvmer lefin Block 190gi M2 Polymer [02291 Table 18 shows the test result of AATCC 61-21003-2A, random ethylene-octene copolymer and olefin block polymer both have excellent performance in color chan~;e compared with I..vcra 1.62 before or after heat setting. The reason is random ethylene-octene copolymer and olefin block polymer fiber were dyed at 135 C.
the disperse dyestuff has better reaction in this temperature. In the dye lot of micro-fiber polyesteriLycra, there is un-reacted disperse dyestuff because of low dyein.g temperature that stained on fabric and bleeds out that znakes specimen color fading during testing. Random ethylene-octene copolyiner and OBC both has good color fastness to polyamide compared with Lyera. Lycra shows poor color fastness after heat settina. 'l`he reason is the disperse dyes migrated durin.g 185"C high temperature heat setting.

Table 18 Test result of color change and color fastness of fabrics Random ethylene- Olefin Block Testing item Lycra 162C octene Pa[vmer co olvmer Color change after RC 3 4 4 Color change after heat setting 2.5 4 4 Color fastness to wash after 3 3.5 3.5 RC
Color fastness to wash aftc;r ? ~ 3.5 4 heat settini 102301 Three finished fabrics after heat setting v,,-ere tested by spectrum photometer (Da,tacolor naodel-6(I0hLt S }. Tabi~ 19 s}iows the color strength (K/S) ti~a:tt i: 1 =ts C~~ll doni ~ it~c.
dild .<Lc:cdarker coÃ~ -vith the k e_.~~
'-mtaiation.
m~~_ Table 19 Eabrie width of crreicre and finished goods Rat-ldom ethylene- OBC EXP
Testing item Lvcra 162C octene 6116 co olvmer Color strength (K;`S) 4 54.23 747.55 774.18 Example 25 - Varying Amounts of Fiber Crosslinking [0231] The elastic ethylenefo,-olefi n interpolymer of Example 20 was used to make monofilament fibers of 40 denier having an approximately round cross-section.
Before the fiber was made the following additives were added to the polymer:

ppm. PDMSO (polydimethyl siloxane). 3000 ppm CYANOX 1790 (1,3,5-tris-(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3.14,5H)-trione.
and 3000 ppm CHI.MASORB 944 Poiy-[[6-(1,1,3,3-tetrarrnethy-lbutyl)amino]-s-triazine-2,4-diyll[2,2,6,6-tetramethy1-4-piperidyl)iminojhexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)iminoJ] and 0.5% by weiglat "1"i0,. The fibers were produced using a die profile with circular 0.8 mm diameter, a spin temperature of 299 C, a winder speed of 650numinute., a spin finish of 2%, a cold draw of 6%, and a spool weight of 150g.
Fibers were then crosslinked using varying amounts of irradiation from an e-beam as the crosslinking acent.
[02321 'I"he gel content versus the amount of irradiation is shown in Figure 11.
The gel content was determined by weighing out an approximately 2-i nrg iiber sample to 4 significant tigure accuracy. The sample is then combined with 7 ml xylene in a capped 2-dratn vial. The vial is heated 90 mint.ites at 125 C to 135 C, with inversion mixing (i.e. turrting vial upside down) every 15 minutes, to extract essentially all the non-crosslinked polymer. Once the vial has cooled to approxiniately 25 C, the xylene is decanted from the gel. The grel is rinsed in the, vial with a small portion of fresh xylenes. The rinsed gel is transferred to a tared aluminum weighing pan. The tared dish with gel is vacuum dried at 125"C: for minutes to remove the xyleiie by evaporation. The pan with dried gel is weighed on an analytical balatice. The gel content is calculated based ojr the extracted gel '~kreipht cndori==inal fiib':'rA. i~; :e i' shov".E tK ';,ncl;":,I

that the precise relationship between the amount of crosslinking and e-beam dosage may be atficted by a~,7ivcn polvmer's properties, e.g.. molecular rveight or melt index.
ml7

Claims (47)

1. A dyed fabric comprising 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 and wherein said fabric is 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.

2. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 3.5 according to AATCC evaluation after a first wash by AATCC61-2003)-2A.

3. The dyed fabric of Claim 1 wlierein said fabric is characterized by a color change of greater than or equal to about 4.0 according to AATCC evaluation after a first wash by AATCC61-2003-2A.

4. The fabric of Claim 1 wherein the fabric is a woven fabric which is characterized by a stretch of at least about 10 percent measured according to ASTM
D3107.

5. The fabric of Claim 1 wherein the ethylene olefin block polymer is an ethylene/.alpha.-olefin interpolymer characterized by one or more of the following characteristics prior to crosslinking:
(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
T m > -2002.9 + 4538.5(d) - 2422.2(d)2, or (b) has a Mw/Mn from about 1.7 to about 3.5. and is characterized by a heat of fusion, .DELTA.H in J/g, and a delta quantity, .DELTA.T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of .DELTA.T and .DELTA.H
have the following relationships:
.DELTA.T > -0.1299(.DELTA.H) + 62.81 for .DELTA.H greater than zero and up to 130 J/g, .DELTA.T> 48°C for .DELTA.H. greater than 130 J/g, wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; or (c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured width a compression-molded film of the ethylene/.alpha.-olefin interpolymer, and has a density. d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/.alpha.-olefin interpolymer is substantially free of a cross-linked phase:
Re > 1481-1629(d); or (d) has a molecular fraction which elutes between 40°C and 130°C

when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/.alpha.-olefin interpolymer; or (e) is characterized by a storage modulus at 25°C, G'(25°C), and a storage modulus at 100°C, G'(140°C), wherein the ratio of G'(25°C) to G'(100°C) is from about 1:1 to about 10:1; or (f) at least one molecular fraction which elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution, Mw/Mn. greater than about 1.3 or (g) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3.

6. The fabric of Claim 1 wherein the fabric is a knit fabric which is characterized by a stretch of at least about 30 percent measured according to ASTM D2594.

7. The fabric of Claim 1 wherein said elastic fibers comprise from about 2 to about 30 weight percent of the fabric.

8. The fabric of Claim 1 wherein said fabric further comprises polyester, nylon, cellulose, cotton, flax, ramie, hemp, wool, silk, linen, bamboo, tencel, mohair, other natural fibers, and mixtures thereof.

9. The fabric of Claim 8 wherein said polyesters is microfiber polyester.

10. The fabric of Claim 8 wherein the polyester comprises at least about 50 percent by weight of the fabric.

11. The fabric of Claim 9 wherein the microfiber polyester comprises at least about 50 percent by weight of the fabric.

12. The fabric of Claim 5 wherein the ethylene/.alpha.-olefin interpolymer is blended with another polymer.

13. The fabric of Claim 5 wherein the ethylene/.alpha.-olefin interpolymer is characterized by a density of from about 0.865 to about 0.92 g/cm3 (ASTM D792) and an uncrosslinked melt index of from about 0.1 to about 10 g/10 minutes.

14. The fabric of Claim 1 wherein the fabric is a knit fabric and comprises a majority of the fibers that have a denier of from about 1 denier to about 180 denier.

15. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 2.5 according to AATCC evaluation after a second wash by AATCC61-2003-2A.

16. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 3.0 according to AATCC evaluation after a second wash by AATCC61-2003-2A.

17. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 3.5 according to AATCC evaluation after a second wash by AATCC61-2003-2A.

18. A dyed fabric comprising 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 and wherein said fabric is characterized by a color strength after dying of greater than or equal to about 600 as measured with a spectrum photometer.

19. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after dying of greater than or equal to about 650 as measured with a spectrum photometer.

20. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after dying of greater than or equal to about 700 as measured with a spectrum photometer.

21. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after dying of greater than or equal to about 750 as measured with a spectrum photometer.

22. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 90 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

23. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 95 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

24. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 97 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

25. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a second wash by AATCC61-2003-2A that is at least about 90 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

26. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a second wash by AATCC61-2003-2A that is at least about 92.5 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

27. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a second wash by AATCC61-2003-2A that is at least about 94 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

28. The fabric of Claim 18 wherein the fabric is a woven fabric and is characterized by a stretch of at least about 10 percent measured according to ASTM
D3107.

29. The fabric of Claim 18 wherein the ethylene olefin block polymer is an ethylene/.alpha.-olefin interpolymer characterized by one or more of the following characteristics prior to crosslinking:

(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
T, > -22002.9 - 4539.5(d) - 2422.2(d)2, or (b) has a MW/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, AH in J/g, and a delta quantity, .DELTA.T. in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of .DELTA.T and .DELTA.11 have the following relationships:
.DELTA.T > -0.1299(.DELTA.H) + 62.81 for .DELTA.H greater than zero and up to 130 J/g, .DELTA.T > 48°C for AH greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; or (e) is characterized by an elastic recovery, Re, in percent at 300 percent strain and I cycle measured with a compression-molded film of the ethylene/.alpha.-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/.alpha.-olefin interpolymer is substantially free of a cross-linked phase:
Re > 1481-16219(d); or (d) has a molecular fraction which elutes between 40°C and 130°C

when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/.alpha.-olefin interpolymer; or (e) is characterized by a storage modulus at 25°C, G'(25°C), and a storage modulus at 100°C. G'(100°C), wherein the ratio of G'(25°C) to G'(100°C) is from about 1:1 to about 10:1; or (t) at least one molecular fraction which elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1. and a molecular weight distribution, Mw/Mn, greater than about 1.3 or (g) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3.

30. The fabric of Claim 18 wherein said elastic fibers comprise from about 2 to about 30 weight percent of the fabric.

31. The fabric of Claim 18 wherein said fabric further comprises polyester, nylon, or mixtures thereof.

32. The fabric of Claim 18 wherein said polyester is microfiber polyester.

33. The fabric of Claim 31 wherein the polyester comprises at least about 80 percent by weight of the fabric.

34. The fabric of Claim 32 wherein the microfiber polyester comprises at least about 80 percent by weight of the fabric.

35. The fabric of Claim 28 wherein the ethylene/.alpha.-olefin interpolymer is blended with another polymer.

36. The fabric of Claim 28 wherein the ethylene/.alpha.-olefin interpolymer is characterized by a density of from about 0.865 to about 0.92 -g/cm3 (ASTMD
792) and an uncrosslinked melt index of from about 0.1 to about 10g/10 minutes.

37. The fabric of Claim 18 wherein a majority of the fibers have a denier of from about 1 denier to about 180 denier.

38. In a process of producing a dyed fabric wherein said fabric comprises one or more elastic fibers comprised of the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent, wherein said process comprises contacting said fabric and said dye at a temperature above room temperature and then drying said fabric wherein the improvement comprises contacting said fabric and said dye at a temperature of at least about 130°C to produce a dyed fabric wherein the fabric exhibits a growth to stretch ratio of less than 0.5.

39. The process of Claim 38 wherein said dyed fabric exhibits a growth to stretch ratio of less than 0.25.

40. The process of Claim 38 wherein said dyed fabric is characterized by a color change of greater than or equal to about 3.0 according to AATCC evaluation after a first wash by AATCC61-21003-2A.

41. The process of Claim 38 wherein said dyed fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 90 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

42. The process of Claim 38 wherein said process is conducted in the substantial absence of penetration agents.

43. The process of Claim 38 wherein said dyed fabric is characterized by a color strength after dying of greater than or equal to about 600 as measured with a spectrum photometer.

44. The process of Claim 3 8 wherein said dyed fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 90 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.

45. The process of Claim 38 wherein the ethylene olefin block polymer is an ethylene/.alpha.-olefin interpolymer characterized by one or more of the following characteristics prior to crosslinking:
(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
T m >= -2002.9 + 4538.5(d) - 2422.2(d)2, or (b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, .DELTA.H in J/g, and a delta quantity, .DELTA.T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of .DELTA.T and .DELTA.H
have the following relationships:
.DELTA.T > -0.1299(.DELTA.H) + 62.81 for .DELTA.H greater than zero and up to 130 J/g, .DELTA.T >= 48°C for .DELTA.H greater than 130 J/g, wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; or (c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/.alpha.-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/.alpha.-olefin interpolymer is substantially free of a cross-linked phase:
Re > 1481-1629(d ); or (d) has a molecular fraction which elutes between 40°C and 130°C

when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/.alpha.-olefin interpolymer; or (e) is characterized by a storage modulus at 25°C, G'(25°C). and a storage modulus at 100°C, G'(100°C), wherein the ratio of G'(25°C) to G'(100°C) is from about 1:1 to about 10:1; or (f) at least one molecular fraction which elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution, Mw/Mn, greater than about 1.3 or (g) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3.

46. The fabric of Claim 1 wherein the fabric is a woven fabric and comprises a majority of the fibers that have 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 a stretch of at least about 10 percent measured according to ASTM D2594.