Title of Invention

FUNCTIONALIZED ETHYLENE/ALPHA-OLEFIN INTERPOLYMER COMPOSITIONS

Abstract The invention relates to functionalized interpolymers derived from base olefin interpolymers, which are prepared by polymerizing one or more monomers or mixtures of monomers such as ethylene and one or more co monomers, to form an interpolymer products having unique physical properties. The functionalized olefin interpolymers contain two or more differing regions or segments (blocks), resulting in unique processing and physical properties.
Full Text
FUNCTIONALIZED ETHYLENE/α-olefinINTERPOLYMER COMPOSITIONS FIELD OF THE INVENTION
[1] This invention relates to functionalized ethylene/α-olefininterpolymer
compositions.
BACKGROUND AND SUMMARY OF THE INVENTION
[2] Base interpolymers have been prepared by polymerizing one or more
monomers or mixtures of monomers such as ethylene and one or more comonomers, to form interpolymer products having unique physical properties such as two or more differing regions or segments (blocks), which provide unique physical properties. Such olefin interpolymers are described in PCT Application No. 2005/08917, filed March 17, 2005, which is incorporated herein, in its entirety, by reference.
[3] Despite the discovery of the multi-block interpolymers as discussed above,
there remains a need to develop olefin interpolymers, which are well suited as compatibilizing agents for compatibilizing incompatible polymer blends; and thus, which can be used to develop new polymer alloys. There is also a need to develop olefin interpolymers for use in the development of products with targeted differentiated properties. For example, there is a need to develop olefin interpolymers for compounding or polymer modification formulations, each used to improve the processibilty and performance of the resulting polymer composition, and/or to improve the properties of the final polymer product andyor to improve the cost-efficiency of producing the final product. There is a need for improved polymers for the modification of engineering thermoplastics and polyolefins, resulting in new resins with improvements in one or more of the following properties: viscosity, heat resistance, impact resistance, toughness, flexibility, tensile strength, compression set, stress relaxation, creep resistance, tear strength, blocking resistance, solidification temperature, abrasion resistance, retractive force, oil retention, pigment retention and filler capacity. It would be useful if such olefin interpolymers could be blended into thermoset systems, such as cpoxies, unsaturated polyesters, and die like, prior to curing, or during curing, to improve the performance of the cured thermoset in properties, such as, for example, impact resistance, toughness and flexibility.

[4] In addition* there is a need to develop olefin interpolymers for use in coatings,
adhesive and tie layer applications, where such polyolefins provide strong adhesion to polar and/or nonpolar substrates, improve paintabiHty an/or printability, provide good flexibility, and provide structural and chemical stability over a broad service temperature range. Substrates may include, but are not limited to, other polyolefins, polyamides, polyesters, polycarbonate, other engineering thermoplastics, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, cellulose, glass, and metals. At least some of the aforementioned needs and other are met by the following invention.
[5] The invention provides fimctionalized derivatives of the segmented or multi-
block interpolymers, as described herein, and provides for compositions comprising the same. The functionalized interpolymers of this invention often exhibit lower viscosities for better melt flows and lower operating temperatures in various processing applications. The invention also relates to methods of using these functionalized interpolymers in applications requiring unique combinations of processing elements and unique physical properties in the final product. In still another aspect, the invention relates to the articles prepared from these functionalized interpolymers. These functionalized multi-block interpolymers and polymeric blends, containing the same, may be employed in the preparation of solid articles, such as moldings, films, sheets, and foamed objects. These articles may be prepared by molding, extruding, or other processes. The functionalized interpolymers are useful in adhesives, tie layers, laminates, polymeric blends, and other end uses. The resulting products may be used in the manufacture of components for automobiles, such as profiles, bumpers and trim parts, or may be used in the manufacture of packaging materials, electric cable insulation, coatings and other applications.
[6] In one aspect, the invention provides a composition, comprising at least one
functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer having at least one melting point, Tm, in degrees Celsius, and a density, d*, in grams/cubic centimeter, and wherein the numerical values of the variables correspond to the relationship:
Tm > -2002.9 + 4538.5(d*) - 2422.2(d*)2, and
wherein the interpolymer has a Mw/Mn from 1.7 to 3.5.

[7] In another aspect, the invention provides a composition, comprising at least
one functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer having the following:
a) a Mw/Mn from 1.7 to 3.5,
b) a delta quantity (tallest DSC peak minus tallest CRYSTAF peak) greater than the quantity, y*, defined by the equation: y* > -0.1299(AH) + 62.81, and
c) a heat of fusion up to 130 J/g, and
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, and wherein AH is the numerical value of the heat of fusion in J/g.
[8] In another aspect, the invention provides a composition comprising at least
one functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer that has a delta quantity (tallest DSC peak (measured from the baseline) minus tallest CRYSTAF peak) greater than 48*C, and a heat of fusion greater than, or equal to, 130 J/g, and 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.
[9] In another aspect, the invention provides a composition comprising at least
one functionalizcd olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer that has a mole percent of at least one commoner in a TREF fraction between 40°C and 130°C, as determined according to the following formula:
y > (-0.2013(TREFElutionTemp.) + 21.07), wherein uy?'>s the mole percent comonomer(s) in the TREF fraction between 40°C and 130°C.
[10] In another aspect, the invention provides a composition, comprising at least
one functionalized multi-block interpolymer, and wherein the functionalized multi-block interpolymer is prepared from a multi-block interpolymer that comprises, in polymerized form, ethylene and one or more copolymerizable comonomers, and wherein said muti-block interpolymer comprises two or more segments, or blocks, differing in comonomer content.

crystallinity, density, melting point or glass transition temperature, and wherein the multi-block interpolymer is functionalized with at least one compound, selected from the group consisting of unsaturated compounds containing at least one heteroatom.
[11] In yet another aspect, the invention provides a process for preparing a
functionalized multi-block interpolymer of the invention, said process comprising, reacting the multi-block interpolymer with the at least one compound, and at least one initiator, and wherein the at least one initiator generates 0.01 millimoles to 10 millimoles radicals per 100 grams of the multi-block interpolymer, and wherein the at least one compound is present in on amount from 0.05 to 10 parts per hundred gram of the multi-block interpolymer.
[12] In another aspect, the invention provides a composition, comprising at least
one functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer comprising ethylene and one or more copolymerizable comonorners in polymerized form, and wherein said olefin interpolymer comprises multiple blocks or segments of two or more polymerized monomer units, said blocks or segments differing in chemical or physical properties (blocked interpolymer), and wherein the olefin interpolymer has a molecular fraction which elutes between 40°C and 130°C, when fractionated using TREF increments, and wherein said fraction has a molar comonomer content higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, and wherein said comparable random ethylene interpolymer comprises 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, and wherein the olefm interpolymer is functionalized with at least one unsaturated compound containing at least one heteroatorn.
[13] In another aspect, the invention provides a composition, comprising at least
one functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer comprising ethylene and one or more copolymerizable comonorners in polymerized form, and wherein the olefin interpolymer comprises multiple blocks or segments of two or more polymerized monomer units, said blocks or segments differing in chemical or physical properties (blocked interpolymer), and wherein the olefin interpolymer has a peak (but not just a molecular fraction) which elutes between 40°C and 130°C (but without collecting and/or isolating individual fractions), and wherein said peak, has an average comonomer content, determine by infra-red spectroscopy when expanded

using a full width/half maximum (FWHM) area calculation, higher than that of a comparable random ethylene interpolymer peak at the same elution temperature and expanded using a full width/half maximum (FWHM) area calculation, and wherein said comparable random ethylene interpolymer comprises 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, and wherein the olefin interpolymer is functionalized with at least one unsaturated compound containing at least one heteroatom.
[14] In another aspect, the invention provides a composition, comprising at least
one functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer comprising ethylene and one or more copolymerizable comonomcrs in polymerized form, and wherein the olefin interpolymer comprises multiple blocks or segments of two or more polymerized monomer units, sais blocks or segments differing in chemical or physical properties (blocked interpolymer), and wherein the olefin interpolymer has a molecular fraction which elutes between 40°C and 13(fC, when fractionated using TREF increments, and wherein those fractions that have a comonomer content of at least about 6 mole percent, have a melting point greater than about 100°C, and wherein those fractions having a comonomer content from about 3 mole percent to about 6 mole percent, have a DSC melting point of about 110°C or higher, and wherein the olefin interpolymer is functionalized with at least one unsaturated compound containing at least one heteroatom.
[15] In another aspect, the invention provides a composition, comprising at least
one functionalized olefin interpolymer, and wherein the functionalized olefin interpolymer is formed from an olefin interpolymer comprising ethylene and one or more copolymerizable comonomers in polymerized form, and wherein (he olefin interpolymer comprises multiple blocks or segments of two or more polymerized monomer units, said blocks or segments differing in chemical or physical properties (blocked interpolymer), and wherein the olefin interpolymer has a molecular fraction which elutes between 40°C and 130°C, when fractionated using TREF increments, and wherein every fraction that has an ATREF elution temperature greater than, or equal to, about 76°C, has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation: Heat of fusion (J/gm)
fusion) as measured by DSC, corresponding to the equation: Heat of fusion (J/gm) |16] The invention also provides for crosslinked derivatives of the aforementioned
functionalized olefin interpolymcrs. The invention also provides for additional embodiments of the above compositions, functionalized interpolymers, and processes, all as described herein, and for combinations of two or more of these embodiments. The invention further provides for articles, each comprising at least one component that comprises, or is formed from, a composition as described herein, and provides for processes for preparing the same.
BRIEF DESCRIPTION OF THE DRAWINGS
[17] Figure 1 shows the melting point/density relationship for multi-block base
interpolymers (represented by diamonds) as compared to traditional random copolymers (represented by circles) and Ziegler-Natta copolymers (represented by triangles).
[18] Figure 2 shows plots of delta DSC-CRYSTAF as a function of DSC Melt
Enthalpy for various polymers. The diamonds represent random ethylene/octene copolymers; the squares represent polymer examples 1-4; the triangles represent polymer examples 5-9; and the circles represent polymer examples 10-19. The "X" symbols represent polymer examples A*-F*.
[19] Figure 3 shows the effect of density on clastic recovery for unoriented films
made from multi-block base interpolymers (represented by the squares and circles) and traditional copolymers (represented by the triangles which are various Dow AFFINITY* polymers). The squares represent multi-block base ethylene/butene copolymers; and the circles represent multi-block base ethylene/octene copolymers.
[20] Figure 4 is a plot of octene content of TREF fractionated ethylene/1 -octene
copolymer fractions versus TREF elution temperature of the fraction for the polymer of Example 5 (represented by the circles) and comparative polymers E and F (represented by the "X" symbols). The diamonds represent traditional random ethylene/octene copolymers.

[21] Figure 5 is a plot of octene content of TREF fractionated ethylene/l-octene
copolymer fractions versus TREF elution temperature of the fraction for the polymer of Example 5 (curve 1) and for comparative F (curve 2). The squares represent Example F*; and the triangles represent Example 5.
[22] Figure 6 is a graph of the log of storage modulus as a function of temperature
for comparative ethylene/l-octene copolymer (curve 2) and propylene/ethylene- copolymer (curve 3) and for two ethylene/l-octene multi-block base interpolymers made with differing quantities of chain shuttling agent (curves 1).
[23] Figure 7 shows a plot of TMA (1mm) versus flex modulus for some multi-
block base polymers polymers (represented by the diamonds), as compared to some known polymers. The triangles represent various Dow VERSIFY* polymers; the circles represent various random ethylene/styrene copolymers; and the squares represent various Dow AFFINITY* polymers.
[24] Figure 8 is an FT1R spectrum of Multi-block R22 base interpolymer grafted
with 0.77 wt% maleic anhydride. The boxed portion of the spectrum indicates the carbonyl region of the spectrum (2000-1500 cm*1).
[25] Figure 9 represents an overlay of the carbonyl regions of the FTIR spectra of,
from top to bottom, Multi-block R22 base interpolymer grafted with 0.77% MAH; Multi-block R21 base interpolymer grafted with 0.76% MAH; EO870 grafted with 0.58% MAH; and unfunctionalized EO870.
[26] Figure 10 is a FTIR spectrum of Multi-block R22 base interpolymer, grafted
with 3.50 wt% vinyltriethoxystlane (VTES). The boxed portion of the spectrum indicates the Si-O-C region of the spectrum (1400-900 cm'1).
|27] Figure 11 is an overlay of the Si-O-C absorption regions of the FTIR spectra
of, from top to bottom, Multi-block R22 base interpolymer grafted with 3.50% VTES; Multi-block R21 base interpolymer grafted with 3.53% VTES; EO870 grafted with 3.59% VTES; and unfunctionalized EO870.
[281 Figure 12 is a graph showing the comparison of thermal properties of
AFFINITY® GA1950, Multi-block 500, si-AFFINITY® GA 1950, and si-Multbblock 500.

[29] Figure 13 is a graph showing the comparison of mechanical properties of
AFFINITY®GA1950, Multi-block 500, si-AFFINITY®GA 1950, and si-Multi-block 500.
[30] Figure 14 is a graph showing the comparison of storage modulus G' of
AFFINITY® GA1950, Multi-block 500, si-AFFINITY® GA 1950, and si-Multi-block 500.
|31J Figure 15 is a graph showing the comparison of tan delta of AFFINITY®
GA1950, Multi-block 500, si-AFFINITY® GA 1950, and si-Multi-block 500.
[32] Figure 16 is a graph showing the melt strength modification of a multi-block
interpolymer functionalized with various amounts of peroxide.
[33] Figure 17 is a graph showing the melt strength modification of a multi-block
interpolymer functionalized with various amounts of (bis) sulfonyl azide.
[34] Figure 18 is a graph showing the melt shear rheology (viscosity versus
frequency) of a multi-block interpolymer functionalized with various amounts of peroxide.
[35] Figure 19 is a graph showing the melt shear rheology (viscosity versus
frequency) a multi-block interpolymer functionalized with various amounts of (bis) sulfonyl azide.
[36] Figure 20 is a graph showing the 70 °C compression set of a multi-block
interpolymer functionalized with various amounts of (bis) sulfonyl azide and the 70 °C compression set of a multi-block interpolymer functionalized with various amounts of peroxide.
DETAILED DESCRIPTION OF THE INVENTION
General Definitions
[37] "Polymer" means a polymeric compound prepared by polymerizing
monomers, whether of the same or a different type. The generic term "polymer" embraces the terms "homopolymer," "copolymer," "terpolymer" as well as "interpolymer."
[38] "Interpolymer" means a polymer prepared by the polymerization of at least
wo different types of monomers. The generic term "interpolymer" includes the term
'copolymer" (which is usually employed to refer to a polymer prepared from two different

prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
139] The term "ethylene/α-olefininterpolymer" generally refers to polymers
comprising ethylene and an a -olefin having 3 or more carbon atoms. Preferably, ethylene comprises the majority mole fraction of the whole polymer, i.e., ethylene comprises at least about SO mole percent of the whole polymer. More preferably ethylene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial remainder of the whole polymer comprising at least one other comonomer that is preferably an α-olefinhaving 3 or more carbon atoms. For many ethylene/octene copolymers, the preferred composition comprises an ethylene content greater than about 80 mole percent of the whole polymer and an octene content of from about 10 to about 15, preferably from about 15 to about 20 mole percent of the whole polymer. In some embodiments, the ethylene/α-olefininterpolymers do not include those produced in low yields or in a minor amount or as a by-product of a chemical process. While the ethylene/a-olefin interpolymers can be blended with one or more polymers, the as-produced ethylene/a-olefin interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
[40] The ethylene/α-olefininterpolymers comprise ethylene and one or more
copolymerizable α-olefincomonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/α-olefininterpolymers are block interpolymers, preferably multi-block interpolymers or copolymers. The terms "interpolymer" and copolymer" are used interchangeably herein. In some embodiments, the multi-block copolymer can be represented by the following formula:
(AB)0 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 segment and "Bw 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 chain. In other words, the block copolymers usually do not have a structure as follows.
AAA—AA-BBB—BB

[41] In still other embodiments, the block copolymers do not usually have a third
type of block, which comprises different comonomer(s). In yet other embodiments, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
[42] The multi-block polymers typically comprise various amounts of "hard" and
"soft" segments. "Hard" segments refer to blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, and preferably less than about 2 weight percent based on the weight of the polymer. In some embodiments, the hard segments 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 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
[43] The soft segments can often be present in a block interpolymer from about 1
weight percent to about 99 weight percent of the total weight of die 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 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from 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. Conversely, 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 methods and calculations are
disclosed in a concurrently filed U.S. Patent Application Serial No. (insert when
known). Attorney Docket No. 385063-999558, entitled "Ethylene/α-olefinBlock Interpolymers", filed on March 15f 2006, in the name of Colin L.P. Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclose of which is incorporated by reference herein in its entirety.
[44] The term "crystalline** if employed, refers to a polymer that possesses a first
order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with the term "semicrystalline". The term "amorphous" refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.
[45] The term "multi-block copolymer" or "segmented copolymer" refers to a
polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear maimer, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylcnic functionality, rather than in pendent or grafted fashion. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, the density, 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-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property. The multi-block copolymers are characterized by unique distributions of 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 polymers desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. When 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 preferably from 1.4 to 1.8.
[46] "Impact-modifying amount of ethylene/α-olefinmulti-block interpolymer" is a
quantity of ethylene/α-olefinmulti-block interpolymer added to a given polymer composition such that the composition's notched Izod impact strength at room temperature or below is

maintained or increased as compared to said given composition's notched Izod impact strength at the same temperature without the added ethylene/α-olefinmulti-block interpolymer.
[47] In the following description, all numbers disclosed herein are approximate
values, regardless whether the word "about" or "approximate** is used in connection therewith. They may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical range with a lower limit, RL and an upper limit, Ru, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=RL+k*(Ru-RL), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 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.
Ethylene/α-olefinInterpolymers
[48] The ethylene/α-olefininterpolymers used in embodiments of the invention
(also referred to as "inventive interpolymer" or "inventive polymer") comprise ethylene and one or more copolymerizablc a-olcfin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably a multi-block copolymer. The ethylene/α-olefininterpolymers are characterized by one or more of the aspects described as follows.
[49] In one aspect, the ethylene/α-olefininterpolymers used in embodiments of the
invention have a Mw/M„ from about 1.7 to about 3.5 and at least one melting point, T,„, in degrees Celsius and density, d, in grams/cubic centimeter, wherein the numerical values of the variables correspond to the relationship:
Tm > -2002.9 + 4538.5(d) - 2422.2(d)2, and preferably
Tra> -6288.1 + 13141(d) -6720.3(d)2, and more preferably
Tm> 858.91 - 1825.3(d) + 1112.8(d)2.

[50] Such melting point/density relationship is illustrated in Figure 1. Unlike the
traditional random copolymers of ethylene/a-olefins whose melting 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 130°C when density ranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, die melting point of such polymers are in the range of about 115°C to about 125 °C when density ranges from 0.875 g/cc to about 0.945 g/cc.
[51] In another aspect, the ethylene/α-olefininterpolymers comprise, in
polymerized form, ethylene and one or more a-olefins and are characterized by a AT, in degree Celsius, defined as the temperature for the tallest Differential Scanning Calorimetry ("DSC") peak minus the temperature for the tallest Crystallization Analysis Fractionation ("CRYSTAF") peak and a heat of fusion in J/g, AH, and AT and AH satisfy the following relationships:
AT > -0.1299(AH) + 62.81, and preferably
AT > -0.1299(AH) + 64.38, and more preferably
AT >-0.1299(AH) + 65.95,
for AH up to 130 J/g. Moreover, AT is equal to or greater than 48 °C for AH greater than 130 J/g. The CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (that is, the peak must represent 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. and AH is the numerical value of the heat of fusion in J/g. More preferably, the highest CRYSTAF peak contains at least 10 percent of the cumulative polymer. Figure 2 shows plotted data for inventive polymers as well as comparative examples. Integrated peak areas and peak temperatures are calculated by the computerized drawing program supplied by the instrument maker. The diagonal line shown for die random ethylene octene comparative polymers corresponds to the equation AT = -0.1299 (AH) + 62.81.
[52] fn yet another aspect, the ethylene/α-olefininterpolymers have a molecular
fraction which elutes between 40°C and 130°C when fractionated using Temperature 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 between the same temperatures, wherein the comparable random ethylene interpolymer contains 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 block interpolymer Preferably, the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the block interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the block interpolymer.
[53] In still another aspect, the ethylene/α-olefininterpolymers are characterized by
an elastic recovery. Re, in percent at 300 percent strain and 1 cycle measured on a compression-molded film of an ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefininterpolymer is substantially free of a cross-linked phase:
Re>1481-1629(d); and preferably
Re>1491-1629(d); and more preferably
Re>1501-1629(d); and even more preferably
Rc>1511-1629(d).
[54] Figure 3 shows the effect of density on elastic recovery for unoriented films
made from certain inventive interpolymers and traditional random copolymers. For the same density, the inventive interpolymers have substantially higher elastic recoveries.
[55] In some embodiments, the ethylene/α-olefininterpolymers have a tensile
strength above 10 MPa, preferably a tensile strength > 11 MPa, more preferably a (ensile strength > 13MPa and/or an elongation at break of at least 600 percent, more preferably at least 700 percent, highly preferably at least 800 percent, and most highly preferably at least 900 percent at a crosshead separation rate of 11 cm/minute.
[56] In other embodiments, the ethylene/α-olefininterpolymers have (I) a storage
modulus ratio, G'(25°CyG,(I00°C), of from I to 50, preferably from 1 to 20, more preferably from 1 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
[57] In still other embodiments, the ethylene/α-olefininterpolymers have a 70°C
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.
[58] In some embodiments, the ethylene/α-olefininterpolymers have a heat of
fusion of less than 85 J/g and/or a pellet blocking strength of equal to or less than 100 pounds/foot2 (4800 Pa), preferably equal to or less than 50 lbs/ft2 (2400 Pa), especially equal to or less than 5 lbs/ft2 (240 Pa), and as low as 0 lbs/ft2 (0 Pa).
[59] In other embodiments, the ethylene/α-olefininterpolymers 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 preferably less than 40 to 50 percent and down to close zero percent.
[60] In some embodiments, the multi-block copolymers possess a PDI fitting a
Schultz-Flory distribution rather than a Poisson distribution. The copolymers are further characterized as having both a polydisperse block 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 including terminal blocks. More preferably, the copolymers include at least 5,10 or 20 blocks or segments including terminal blocks .
[61] Comonomer content may be measured using any suitable technique, with
techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred. Moreover, for polymers or blends of polymers having relatively broad TREF curves, the polymer desirably is first fractionated using TREF into fractions each having an eluted temperature range of 10°C or less. That is. each eluted fraction has a collection temperature window of 10°C or less. Using this technique, said block interpolymers have at least one such fraction having a higher molar comonomer content than a corresponding fraction of the comparable interpolymer.

[62] In another aspect, the inventive polymer is an olefin interpolymer, preferably
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 more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a peak (but not just a molecular fraction) which elutes between 40°C and 130°C (but without collecting and/or isolating individual fractions), characterized in that said peak, has a comonomer content estimated by infra-red spectroscopy when expanded using a full width/half maximum (FWHM) area calculation, has an average 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 peak at the same elution temperature and expanded using a full width/half 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 (FWHM) calculation is based on the ratio of methyl to methylene response area [CH3/CH2] from the ATREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between T| and T2, where T\ 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. A calibration curve for comonomer content is made using random ethylene/a-olefm copolymers, plotting comonomer content from NMR versus FWHM area ratio of the TREF peak. For this infra-red method, the calibration curve is generated for the same comonomer type of interest. The comonomer content of TREF peak of the inventive polymer can be determined by referencing this calibration curve using its FWHM methyl: methylene area ratio [CH3/CH2J of the TREF peak.
[63] Comonomer content may be measured using any suitable technique, with
techniques based on nuclear magnetic resonance (NMR) spectroscopy preferred. Using this

technique, said blocked mterpolymers has higher molar comonomer content than a corresponding comparable interpolymer.
[64] Preferably , for interpolymers of ethylene and 1-octene, the block interpolymer
has a comonomer content of the TREF fraction eluting between 40 and 130°C greater than or equal to the quantity (- 0.2013) 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 temperature of the TREF fraction being compared, measured in °C.
[65] Figure 4 graphically depicts an embodiment of the block interpolymers of
ethylene and 1-octene where a plot of the comonomer content versus TREF elution temperature for several comparable ethylene/1 -octene interpolymers (random copolymers) are fit to a line 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 comonomer contents for fractions of several block ethylene/1-octene interpolymers of the invention (multi-block copolymers). All of the block interpolymer fractions have significantly higher 1-octene content than either line at equivalent elution temperatures. This result is characteristic of the inventive interpolymer and is believed to be due to the presence of differentiated blocks within the polymer chains, having both crystalline and amorphous nature.
[66] Figure 5 graphically displays the TREF curve and comonomer contents of
polymer fractions for Example 5 and comparative F to be discussed below. The peak eluting 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 10°C. Actual data for Example 5 is represented by triangles. The skilled artisan can appreciate that an appropriate calibration curve may be constructed for interpolymers containing different comonomers and a line used as a comparison fitted to the TREF values obtained from comparative interpolymers of the same monomers, preferably random copolymers made using a metallocene or other homogeneous catalyst composition. Inventive interpolymers are characterized by a molar comonomer content greater than the value determined from the ralibration curve at the same TREF elution temperature, preferably at least 5 percent greater, nore preferably at least 10 percent greater.
[67] In addition to the above aspects and properties described herein, the inventive
>olymers can be characterized by one or more additional characteristics. In one aspect, the

inventive polymer is an olefm interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 40°C and 130°C, when fractionated using TREF increments, characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10, 15,20 or 25 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer comprises the same comonomer(s), preferably it is the same comonoraer(s), and 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.
[68] Preferably, the above interpolymers are interpolymers of ethylene and at least
one a-olefin, especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm3, and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130°C greater than or equal to the quantity (-0.1356) T + 13.89, more preferably greater than or equal to the quantity (-0.1356) T+ 14.93, and most preferably greater than or equal to the quantity (~0.2013)T + 21.07, where T is the numerical value of the peak ATREF elution temperature of the TREF fraction being compared, measured in °C.
[69] Preferably, for the above interpolymers of ethylene and at least one alpha-
olefin especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm'\ and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and I30°C greater than or equal to die quantity (-0.2013) 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 temperature of the TREF fraction being compared, measured in °C.

it 1 mol percent comonomer, has a DSC melting point that corresponds to the
(-5.5926)(mol percent comonomer in the fraction) + 135.90.
En yet another aspect, the inventive polymer is an olefm interpolymer, mprising ethylene and one or more copolymerizable comonomers in

[73] The comonomer composition of the TREF peak can be measured using an ER4
infra-red detector available from Polymer Char, Valencia, Spain (http://www.polvmerchar.com/).
[74) The "composition mode" of the detector is equipped with a measurement
sensor (CH2) and composition sensor (CH3) that are fixed narrow band infra-red filters in the region of 2800-3000 cm"1. The measurement sensor detects the methylene (CH2) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH3) groups of the polymer. The mathematical ratio of the composition signal (CHj) divided by the measurement signal (CH2) is sensitive to the comonomer content of the measured polymer in solution and its response is calibrated with known ethylene alpha-olefm copolymer standards.
[75] The detector when used with an ATREF instrument provides both a
concentration (CH2) and composition (CU3) signal response of the eluted polymer during the TREF process. A polymer specific calibration can be created by measuring the area ratio of the CH3 to CH2 for polymers with known comonomer content (preferably measured by NMR). The comonomer 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 CH3 and CH2 response (i.e. area ratio CH3/CH2 versus comonomer content).
(76] The area of the peaks can be calculated using a fill] width/half maximum
(FWHM) 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 [CH3/CH2] from the ATREF infrared detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between Tl and T2, where T1 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.
[77] The application of infra-red spectroscopy to measure the comonomer content
of polymers in this ATREF-infra-rcd method is, in principle, similar to that of GPC/FTK systems as described in the following references: Markovich, Ronald P.; Hazlitt, Lonnie G.;

Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers". Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P.J.; Rohlfing, D.C.; Shieh, E.T.; "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTCR)**, Polymer (2002), 43,59-170., both of which are incorporated by reference herein in their entirety.
[78] In other embodiments, the inventive ethylene/α-olefininterpolymer is
characterized by an average block index, ABI, which is greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 13. The average block index, ABI, is the weight average of the block index ("Br) for each of the polymer fractions obtained in preparative TREF from 20°C and 1MFC, with an increment of 5°C:

where BI; is the block index for the ith fraction of the inventive ethylene/α-olefininterpolymer obtained in preparative TREF, and w; is the weight percentage of the ith fraction.
[79] For each polymer fraction, BI is defined by one of the two following equations
(both of which give the same BI vahie):

where T* is the preparative ATREF elution temperature for the ith fraction (preferably expressed in Kelvin), Px is the ethylene mole fraction for the ith fraction, which con be measured by NMR or IR as described above. PAB is the ethylene mole fraction of the whole ethylene/α-olefininterpolymer (before fractionation), which also can be measured by NMR or JR. TA and PA are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer). 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 "hard segments" arc not available. For calculations performed herein, TA is 372°K. PA is 1.

[80] TAB is the ATREF temperature for a random copolymer of the same
composition and having an ethylene mole fraction of PAB. TAB can be calculated from the following equation:

where a and P are two constants which can be determined by calibration using a number of known random ethylene copolymers. It should be noted that a and p may vary from instrument to instrument. Moreover, one would need to create their own calibration curve with the polymer composition of interest and also in a similar molecular weight range as the fractions. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, such effect would be essentially negligible. In some embodiments, random ethylene copolymers satisfy the following relationship:

Txo is the ATREF temperature for a random copolymer of the same composition and having an ethylene mole fraction of Px. Txo can be calculated from LnPx =* a/Txo + P. Conversely, Pxo is the ethylene mole fraction for a random copolymer of the same composition and having an ATREF temperature of Tx, which can be calculated from La Pxo = ct/Tx + P.
[81] Once the block index (BI) for each preparative TREF fraction is obtained, die
weight average block index, AB1, 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 1.0. 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 embodiments, ABI is in the range of from about 0 J to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, 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 from about 0.9 to about 1.0.
[82] Another characteristic of the inventive ethylene/α-olefininterpolymer is that
the inventive ethylene/α-olefininterpolymer comprises at least one polymer fraction which can be obtained by preparative TREF, wherein the fraction has a block index greater than

about0.1 and up to about i.O and a molecular weight distribution, MJMn, greater than about 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 up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the 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 about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In still other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0.5, or greater than about 0.4 and up to about 0.5. In yet other embodiments, the polymer fraction has a block index greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0.7, or greater than about 0.5 and up to about 0.6.
[83] For copolymers of ethylene and an a-olefin, the inventive polymers preferably
possess (1) a PDI of at least 1.3, more preferably at least 1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, up to a maximum value of 5.0, more preferably up to a maximum of 3.5, and especially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g or less; (3) an ethylene content of at least 50 weight percent; (4) a glass transition temperature, TK, of less than -25°C, more preferably less than -30°C, and/or (5) one and only one T™.
[84] Further, the inventive polymers can have, alone or in combination with any
other properties disclosed herein, a storage modulus, G\ such that log (C) is greater than or equal to 400 kPa, preferably greater than or equal to 1.0 MPa, at a temperature of 100°C. Moreover, the inventive polymers possess a relatively flat storage modulus as a function of temperature in the range from 0 to 100°C (illustrated in Figure 6) that is characteristic of block copolymers, and heretofore unknown for an olefin copolymer, especially a copolymer of ethylene and one or more Cj-g aliphatic a-olefins. (By the term "relatively flat" in this context is meant that fog G' (in Pascals) decreases by less than one order of magnitude between 50 and 100°C, preferably between 0 and 100°C).
[85] The inventive interpolymers may be further characterized by a
thermomechanical 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 MPa).

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 polymers have significantly better flexibility-heat resistance balance than the other polymers.
[86] Additionally, the ethylene/α-olefininteipolymers can have a melt index, I2,
from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10 minutes, more preferably from 0.01 to 500 g/10 minutes, and especially from 0.01 to 100 g/10 minutes. In certain embodiments, the ethylene/α-olefininterpolymers have a melt index, h, from 0.01 to 10 g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes, from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certain embodiments, the melt index for the ethylene/α-olefinpolymers is lg/10 minutes, 3 g/10 minutes or 5 g/10 minutes.
[87] The polymers can have molecular weights, Mw, from 1,000 g/mole to
5,000,000 g/molc, preferably from 1000 g/mole to 1,000,000, more preferably from 10,000 g/mole to 500,000 g/mole, and especially from 10,000 g/mole to 300,000 g/mole. The density of the inventive polymers can be from 0.80 to 0.99 g/cm3 and preferably for ethylene containing polymers from 0.85 g/cm3 to 0.97 g/cm3. In certain embodiments, the density of the ethylene/α-olefinpolymers ranges from 0.860 to 0.925 g/cm3 or 0.867 to 0.910 g/cm3.
[88] The process of making the polymers has been disclosed in the following patent
applications: U.S. Provisional Application No. 60/553,906, filed March 17,2004; U.S. Provisional Application No. 60/662,937, filed March 17,2005; U.S. Provisional Application No. 60/662,939, filed March 17,2005; U.S. Provisional Application No. 60/5662938, filed March 17,2005; PCT Application No. PCT/US2005/008916, filed March 17,2005; PCT Application No. PCT/US2005/008915, filed March 17,2005; and PCT Application No. PCT/US2005/008917, filed March 17,2005, all of which are incorporated by reference herein in their entirety. For example, one such method comprises contacting ethylene and optionally one or more addition polymeriznble 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 comonomer incorporation index.

(B) a second olefin polymerization catalyst having a comonorner incorporation index less than 90 percent, preferably less than 50 percent, most preferably less than 5 percent of the comonorner incorporation index of catalyst (A), and
(C) a chain shuttling agent
[89] Representative catalysts and chain shuttling agent are as follows.
[90] Catalyst (Al) is [N-(2,6-di(l-methylethyl)phenyl)amidoK2-
isopropylphenyl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafiiium dimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, USSN 10/429,024, filed May







[100] Shuttling Agents. The shuttling agents employed include diethylzinc, di(i-butyl)zinc, di(n-hexyl)zincv triethylaluminum, trioctylaluminurn, triethylgallium, i-butylaluminum bis(dirnethyl(t-butyl)siloxane), i-butylaluminum bis(di(trirnethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)i-butylalurninum, i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(l-naphthyl)arnide), ethylaluminum bis(t-butyldimethy]siloxide)v ethylaluminum di(bis(trimethylsilyl)amide)v ethylaluminum bis(2,3,6,7-dibenzo-l-azacycloheptaneamide), n-octylaluminum bis(2,3f6,7-dibenzo-l-azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), and ethylzinc (t-butoxidc).
[101] Preferably, the foregoing process takes the form of a continuous solution process for forming block copolymers, especially multi-block copolymers, preferably linear multi-block copolymers of two or more monomers, more especially ethylene and a Cn-20 olefin 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 chemically 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 growth, and multi-block copolymers, especially linear multi-block copolymers are formed in high efficiency.
[102] The inventive interpolymers may be differentiated from conventional, random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition, fluxional catalysts, anionic or cationic living polymerization techniques. In particular, compared to a random copolymer of the same monomers and monomer content at equivalent crystallinity or modulus, the inventive interpolymers have better (higher) heat resistance as measured by melting point, higher TMA penetration temperature, higher high-temperature tensile strength, and/or higher high-temperature torsion storage modulus as determined by dynamic mechanical analysis. Compared to a random copolymer containing the same monomers and monomer content, the inventive interpolymers have lower compression set, particularly at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, faster setup due to higher crystallization (solidification) temperature, higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better oil and Filler acceptance.
[103] The inventive interpolymers also exhibit a unique crystallization and branching distribution relationship. That is, the inventive interpolymers have a relatively large difference between the tallest peak temperature measured using CRYSTAF and DSC as a function of heat of fusion, especially as compared to random copolymers containing the same monomers and monomer level or physical blends of polymers, such as a blend of a high density polymer and a lower density copolymer, at equivalent overall density. It is believed that this unique feature of the inventive interpolymers is due to the unique distribution of the comonorncr in blocks within the polymer backbone. In particular, the inventive interpolymers may comprise alternating blocks of differing 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-Flory 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 morphology. In a preferred embodiment, the microcrystalline order of the polymers demonstrates characteristic sphemlites 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 13.
[104] Moreover, the inventive interpolymers may be prepared using techniques to influence the degree or level of blockiness. That is the amount of comonomer and length of each polymer block or segment can be altered by controlling the ratio and type of catalysts and shuttling agent as well as the temperature of the polymerization, and other polymerization variables. A surprising benefit of this phenomenon is the discovery that as the degree of blockiness is increased, the optical properties, tear strength, and high temperature recovery properties of the resulting polymer 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 and catalyst combinations having the desired chain transferring ability (high rates of shuttling with low levels of chain termination) other forms of polymer termination are effectively suppressed. Accordingly, little if any P-hydride elimination is observed in the polymerization of ethylene/α-olefincomonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, possessing little or no long chain branching.
[105] Polymers with highly crystalline chain ends can be selectively prepared in accordance with embodiments of the invention. In elastomer applications, reducing the relative quantity of polymer that terminates with an amorphous block reduces the intermolecular dilutive effect on crystalline regions. This result can be obtained by choosing chain shuttling agents and catalysts having an appropriate response to hydrogen or other chain terminating agents. Specifically, if the catalyst which produces highly crystalline polymer is more susceptible to chain termination (such as by use of hydrogen) than the catalyst responsible for producing the less crystalline polymer segment (such as through higher comonomer incorporation, regio-error, or atactic polymer formation), then the highly crystalline polymer segments will preferentially populate the terminal portions of the polymer. Not only are the resulting terminated groups crystalline, but upon termination, the highly crystalline polymer forming catalyst site is once again available for reinitiation of polymer formation. The initially formed polymer is therefore another highly crystalline

polymer segment. Accordingly, both ends of the resulting multi-block copolymer are preferentially highly crystalline.
[106] The ethylene α-olefininterpolymers used in the embodiments of the invention are preferably interpolymers of ethylene with at least one C3-C20 a-olefin. Copolymers of ethylene and a C3-C2O α-olefinare especially preferred. The interpolymers may further comprise C4-C18 diolefin and/or alkenylbenzene. Suitable unsaturated comonomers useful
for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes, etc. Examples of such comonomers include C3-C20 a -olefins such as propylene, isobutylene, 1-butene, 1-hexene,
1-pentene, 4-methyl-l-pentene, 1-heptene, 1-octene, 1-nonene, l-decene, and the like. 1-Butene and 1-octene are especially preferred. Other suitable monomers include styrene, halo-or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics (e.g., cyclopentene, cyclohexene and cyclooctene).
1107] While ethylene/α-olefininterpolymers are preferred polymers, other
ethylene/olefin polymers may also be used. Olefins as used herein refer to a family of unsaturated hydrocarbon-based compounds with at least one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention. Preferably, suitable olefins are C3-C20 aliphatic and aromatic compounds
containing vinylic unsaturation, as well as cyclic compounds, such as cyclobutene, cyclopentene, dicyclopentadiene, and norbornene, including but not limited to, norbomene substituted in the 5 and 6 position with C1-C2O hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefin compounds.
[108] Examples of olefin monomers include, but are not limited to propylene, isobutylene, I-butene, 1-pentene. 1-hexene, 1-heptenc, 1-octene, 1-nonene, 1-decene. and 1-dodecene, l-tctradecene, 1-hcxadecene, 1-octadeccne, l-cicosene, 3-methyl-1-butene, 3-methyl- l-pentene, 4-methyl-l-pentene, 4,6-dimethyl- 1-heptene, 4-vinylcyclohexene, vinylcyclohexane, norbomadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C4-C40 dienes, including but not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C4-C4oa-olefins, and the like. In certain embodiments, the α-olefinis propylene,!-butene, 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 monomer becomes too high.
[109] 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 styrene, t-butylstyrene, and the like. In particular, interpolymers comprising ethylene and styrene can be prepared by following the teachings herein. Optionally, copolymers comprising ethylene, styrene and a C3-C20 alpha olefin, optionally comprising a C4-C20 dicne, having improved properties can be prepared.
[110] 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 limited 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-raethyM,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-l,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,l)-hepta-2,5-diene; alkenyl, aikylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-rnethylene-2-norbomene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbomene, S-cyclohexylidene-2-norbornene, S-vinyl-2-norbomene, and norbomadienc. Of the dienes typically used to prepare EPDMs, the particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbomene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). The especially preferred dienes are 5-ethylidene-2-norbomene (ENB) and 1,4-hexadiene (HD).
[Ill] One class of desirable polymers that can be made in accordance with embodiments of the invention are elastomeric interpolymers of ethylene, a C3-C20 a-olefin, especially propylene, and optionally one or more diene monomers. Preferred a-olefins for use in this embodiment of the present invention are designated by the formula CH2=CHR*.

where R* is a linear or branched alkyl group of from 1 to 12 carbon atoms. Examples of suitable a-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, l-hexene, 4-methyl-l-pentene, and 1-octene. A particularly preferred α-olefinis 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 polycyclic- dienes comprising from 4 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norborncne, dicyclopcntadiene, cyclohexadiene, and 5-butylidene-2-norbomene. A particularly preferred diene is 5-ethylidene-2-norbornene.
[112] Because the diene containing polymers comprise alternating segments or blocks containing greater or lesser quantities of the diene (including none) and α-olefin(including none), die total quantity of diene and α-olefinmay be reduced without loss of subsequent polymer properties. That is, because the diene and α-olefinmonomers are preferentially incorporated into one type of block of the polymer rather than uniformly or randomly 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 strength and better elastic recovery.
[113] In some embodiments, the inventive interpolymers made with two catalysts incorporating differing quantities of comonomer have a weight ratio of blocks formed thereby from 95:5 to 5:95. The elastomeric polymers desirably have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefincontent of from 10 to 80 percent, based on the total weight of the polymer. Further preferably, the multi-block elastomeric polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefincontent of from 10 to 40 percent, based on the total weight of the polymer. Preferred polymers are high molecular weight polymers, having a weight average molecular weight (Mw) from 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20.000 to 350,000, and a polydispersity less than 3.5, more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125°C.) from 1 to 250. More preferably, such polymers have an ethylene content from 65 to 75 percent, a diene content from 0 to 6 percent, and an α-olefincontent from 20 to 35 percent.

[114] The ethylene/α-olefininterpolymers can be functionaiized by incorporating at least one functional group in its polymer structure. Exemplary functional groups may include, for example, ethylenically unsaturated mono- and di-functional carboxylic acids, ethylenically unsaturated mono- and di-functional carboxylic acid anhydrides, salts thereof and esters thereof. Such functional groups may be grafted to an ethylene/ a -olefin interpolymer, 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 polyediylene are described for example in U.S. Patents Nos. 4,762,890,4,927,888, and 4,950,541, die disclosures of these patents are incorporated herein by reference in their entirety. One particularly useful functional group is malic anhydride.
[115] The amount of the functional group present in the functional interpolymer can
vary. The functional group can typically be present in a copolymer-type functionaiized interpolymer in an amount 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 functionaiized 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
[116] In the examples that follow, the following analytical techniques are employed:
GPC Method for Samples 1-4 and A-C
[117] An automated liquid-handling robot equipped with a heated needle set to 160°C is used to add enough 1,2,4-trichlorobenzene stabilized with 300 ppm 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 polymer solution is then diluted to 1 mg/ml using the automated liquid-handling robot and the heated needle set to 160°C.
[118] A Symyx Rapid GPC system is used to determine the molecular weight data for each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is used to pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm lonol as the mobile phase dirough three

Plgel 10 micrometer (urn) Mixed B 300mm x 7.5mm columns placed in series and heated to 160°C. A Polymer Labs ELS 1000 Detector is used with the Evaporator set to 250°C» the Nebulizer set to 165°C, and the nitrogen flow rate set to 1.8 SLM at a pressure of 60-80 psi (400-600 kPa) N2. The polymer samples are heated to 160°C and each sample injected into a 25011I loop using the liquid-handling robot and a heated needle. Serial analysis of the polymer samples using two switched loops and overlapping injections are used. The sample data is collected and analyzed using Symyx Epoch™ software. Peaks are manually integrated and the molecular weight information reported uncorrected against a polystyrene standard calibration curve.
Standard CRYSTAF Method
[119] Branching distributions are determined by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from PolymeiChar, Valencia, Spain. The samples are dissolved in 1,2,4 trichlorobenzene at 160°C (0.66 mg/raL) for 1 hr and stabilized at 95°C for 45 minutes. The sampling temperatures range from 95 to 30°C at a cooling rate of 0.2°C/min. An infrared detector is used to measure the polymer solution concentrations. The cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased. The analytical derivative of the cumulative profile reflects die short chain branching distribution of the polymer.
[120] The CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF Software (Version 2001 .b, PolymerChar, Valencia, Spain). The CRYSTAF peak finding routine identifies a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either 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 parameters above the temperature limit of 0.1, and below the temperature limit of 0.3.
DSC Standard Method (Excluding Samples 1-4 and A-C)
[121] Differential Scanning Calorimetry results are determined using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml/min is used. The sample is pressed into a thin film and melted in the 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 mm diameter disk, accurately weighed, placed in a light aluminum pan (ca 50 mg), and then crimped shut. The thermal behavior of the sample is investigated with the following temperature profile. The sample is rapidly heated to 180°C and held isothermal for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -40°C at 10°C/min cooling rate and held at -40°C for 3 minutes. The sample is then heated to L50°C at 10°C/min. heating rate. The cooling and second heating curves are recorded.
[122] The DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30°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-Q
[123] The gel permeation chromatographic system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The 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 of polymer in SO 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 ml/minute.
[124] Calibration of the GPC column set is performed 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 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80°C with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polvm. ScL Polvm. Let.. 6,621 (1968)):

[125] Polyethylene equivalent molecular weight calculations are performed using ViscotekTriSEC software Version 3.0.
Compression Set
[126] Compression set is measured according to ASTM D 395. The sample is prepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and 0.25 mm thickness until a total thickness of 12.7 mm is reached. The discs are cut from 12.7 cm x 12.7 cm compression molded plaques molded with a hot press under the following conditions: zero pressure for 3 min at 190°C, followed by 86 MPa for 2 min at 190°C, followed by cooling inside the press with cold running water at 86 MPa.
Density
[127] Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B.
Flexural/Secant Modulus/ Storage Modulus
[128] Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790. Storage modulus is measured according to ASTM D 5026-01 or equivalent technique.
Optical properties
[129] Films of 0.4 mm thickness are compression molded using a hot press (Carver Model #4095-4PR1001R). The pellets are placed between polytetrafluoroethylene sheets, heated at 190°C at 55 psi (380 kPa) for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min. The film is then cooled in the press with running cold water at 1.3 MPa for 1 min. The compression molded films are used for optical measurements, tensile behavior, recovery, and stress relaxation.
[130J Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D 1746.
[131] 45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° as specified in ASTM D-2457

where Lo is the load at 50% strain at 0 time and L|2 is the load at 50 percent strain after 12 hours.
[136] Tensile notched tear experiments are carried out on samples having a density of 0.88 g/cc or less using an Instron™ instrument The geometry consists of a gauge section of 76 mm x 13 mm x 0.4 mm with a 2 mm notch cut into the sample at half the specimen length. The sample is stretched at 508 mm min"1 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
[137] Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter x 3.3 mm thick, compression molded discs, formed at 180°C and 10 MPa molding pressure for 5 minutes and then air quenched. The instrument used is a TMA 7, brand available from Perkin-Elmer. In the test, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to the surface of the sample disc with IN force. The temperature is raised at 5°C/min from 25°C. The probe penetration distance is measured as a function of temperature. The experiment ends when the probe has penetrated 1 mm into the sample.
DMA
[138] 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 / min. Testing is conducted using an ARES controlled strain rheometer (TA instruments) equipped with dual cantilever fixtures for torsion testing.
[139] 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 10mm (grip separation AL) and subjected to successive temperature steps from - 100°C to 200°C (5°C per step). At each temperature the torsion modulus Gf is measured at an angular frequency of 10 rad/s, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.
[140] An initial static force of 10 g is maintained (auto-tension mode) to prevent slack in the sample when thermal expansion occurs. As a consequence, the grip separation

AT. increases with the temperature, particularly above the melting or softening point of the polymer sample. The test stops at the maximum temperature or when the gap between the fixtures reaches 65 mm.
Meli Index
[141] Meli index, or h. is measured in accordance with ASTM D 1238, Condition 190°C/2.16 kg. Melt index, or lio is also measured in accordance with ASTM D 1238, Condition 190°C/10 kg.
ATREF
[142] Analytical temperature rising elution fractionation (ATREF) analysis is conducted according to the method described in USP 4,798.081 and Wilde, L.; Rylc, T.R.; Knobeloch, D.C.; Peat, I.R.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20,441-455 (1982), which are incorporated by reference herein in their entirety. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20°C at a cooling rate of 0.1°C/min. The column is equipped with an infrared detector. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120°C at a rate of 1.5°C/min.
13C NMK Analysis
[143] The samples are prepared by adding approximately 3g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 150°C. The data are collected using a JEOL Eclipse™ 400MHz spectrometer or a Varion Unity Plus™ 400MHz spectrometer, corresponding to a l3C resonance frequency of 100.5 MHz. The data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together. The spectral width is 25,000 Hz with a minimum file size of 32K data points. The samples arc 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 (1989), which is incorporated by reference herein in its entirety.
Polymer Fractionation by TREF
[144] Large-scale TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB)by stirring for 4 hours at 16Q°C. The polymer solution is forced by 15 psig (100 kPa) nitrogen onto a 3 inch by 4 foot (7.6 cm x 12 cm) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 jim) spherical, technical quality glass beads (available from Potters Industries, HC 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 minute and held for one hour. Fresh TCB is introduced at about 65 ml/min while the temperature is increased at 0.167°C per minute.
[1451 Approximately 2000 ml portions of eluant from the preparative TREF column are collected in a 16 station, heated fraction collector. The polymer is concentrated in each fraction using a rotary evaporator until about 50 to 100 ml of die polymer solution remains. The concentrated solutions are allowed to stand overnight before adding excess methanol, filtering, and rinsing (approx. 300-500 ml of methanol including the final rinse). The filtration step is performed on a 3 position vacuum assisted filtering station using 5.0 jam polytetrafluoroethylenc coated filter paper (available from Osmonics Inc., Cat# Z50WP04750). The filtrated fractions are dried overnight in a vacuum oven at 60°C and weighed on an analytical balance before further testing.
Melt Strength
[146] Melt Strength (MS) is measured by using a capillary iheometer 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 run at a speed of I inch/minute (2.54 cm/minute). The standard test temperature is 190°C. The sample is drawn uniaxially to a set of accelerating nips located 100 mm below the die with an acceleration of 2.4 mm/sec2. The required tensile force is recorded as a function of the take-up speed of the nip rolls. The 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 centiNewtons
(McN~).
Catalysts
[147] The term "overnight", if used, refers to a time of approximately 16-18 hours, die term "room temperature", refers to a temperature of 20-25 °C, and the term "mixed alkalies" refers to a commercially obtained mixture of C6.9 aliphatic hydrocarbons available under the trade designation Isopar E**t from ExxonMobil Chemical Company. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control. The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and were dried before their use.
[148] MMAO refers to modified methylalumoxane, a triisobutylaluminum modified methylalumoxane available commercially from Akzo-Noble Corporation.
[149] The preparation of catalyst (Bl) is conducted as follows.
a) Preparation of n'methvlethvnf2-hvdroxv-3,5"dift-butvnphenvnmethvlimine
3,5-Di-t-butylsalicylaldehydc (3.00 g) is added to 10 mL of isopropylamine. The solution rapidly turns bright yellow. After stirring at ambient temperature for 3 hours, volatiles are removed under vacuum to yield a bright yellow, crystalline solid (97 percent yield).
b) Preparation of 1.2-bis- methvlethvttimmino)methvl'M2-oxovr) zirconium dibenzyl
A solution of (l-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605 mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution of Zr(CH2Ph)4 (500 mg, 1.1 mmol) in 50 mL toluene. The resulting dark yellow solution is stirred for 30 min. Solvent is removed under reduced pressure to yield the desired product as a reddish-brown solid.
[150] The preparation of catalyst (B2) is conducted as follows.

a) Preparation of (1 ~(2-methvlcyclohexvl)ethvD(2-oxovl-3,3-di(t-butvDphenvlMmine
2-Methylcyclohcxylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25°C for 12 hrs. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x IS mL), and then dried under reduced pressure. The yield is 11.17 g of a yellow solid. *H NMR is consistent with the desired product as a mixture of isomers.
b) Preparation of bts-(l-(2-methvlcvclohex\l)ethvl)(2-oxovl-3.5-dirt-butvl)ohenvn
imminoteirconium dibenzvl
A solution of (l*(2-methylcyclohexyl)ethylX2-oxoyl-3^-di(t-butyl)phenyl)imine (7.63 g. 232 mmol) in 200 mL toluene is slowly added to a solution of Zr(CH2Ph)4 (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting dark yellow solution is stirred for 1 hour at 25°C. The solution is diluted further with 680 mL toluene to give a solution having a concentration of 0.00783 M.
[151] Cocatalyst 1 A mixture of methyldC14-18 alkyl)ammonium salts of tetrakis(pentafluorophenyl)borate (here-in-after armeenium borate), prepared by reaction of a long chain trialkylamine (Armeen™ M2HT, available from Akzo*Nobel, Inc.), HC1 and Li[B(GoF3)4l, substantially as disclosed in USP 5,919,9883, Ex. 2.
[152] Cocatalyst 2 Mixed C14-18 alkyldimethylammonium salt of bis(tris(pentafluorophenyl>alumane)-2-undecylimidazolide, prepared according to USP 6.395,671, Ex. 16.
[153] Shuttling Agents. The shutding agents employed include diethylzinc (DEZ, SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum (TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6), i-butylaluminum bis(dimethyl(t-butyI)siloxane) (SA7), i-butylaluminum bis(di(trimethylsilyl)amide) (SA8), n-octyla!uminum di(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10), i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminum bis(2,6-di-t-butylphenoxide) (SA12), n-octyloluminum di(ethyl( I-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimcdiylsiloxide) (SA14), ethylaluminum di(bis(trimethylsilyl)amide) (SA15), ethylalurninum bis(2,3,617*dibenzo-l-azacycloheptaneamide) (SA16), n-octylaluminum

bis(2,3,6,7-dibeitto-l-azacycloheptaneamide) (SA17), n-octylaluminum bis(dimethyl(t-butyl)siloxide(SA18), ethylzinc (2,6-diphenylphenoxide) (SA19), and ethylzinc (t-butoxide)
(SA20).
Examples 1-4. Comparative A-C
General High Throughput Parallel Polymerization Conditions
[154) Polymerizations are conducted using a high throughput, parallel polymerization reactor (PPR) available from Symyx technologies. Inc. and operated substantially according to USP's 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 present). A series of 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 tube. The working volume in each reactor cell is 6000 pL. Each eel) is temperature and pressure controlled with stirring provided by individual stirring paddles. The 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 mixed alkanes. The order of addition is mixed alkanes solvent (4 ml), ethylene, l-octene comonomer (1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, and catalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts is used, the reagents are premixed in a small vial immediately prior to addition to the reactor. When a reagent is omitted in an experiment, the above order of addition is otherwise maintained. Polymerizations are conducted for approximately 1-2 minutes, until predetermined ethylene consumptions are reached. After quenching with CO, the reactors are cooled and the glass tubes are unloaded. The tubes ore transferred to a centrifuge/vacuum drying unit, and dried for 12 hours at 60°C. The tubes containing dried polymer are weighed and the difference between this weight and the tare weight gives the net yield of polymer. Results are contained in Table I. In Table 1 and elsewhere in the application, comparative compounds are indicated by an asterisk (*).
[155] Examples 1-4 demonstrate the synthesis of linear block copolymers by the present invention as evidenced by the formation of a very narrow MWD, essentially monomodal copolymer when DEZ is present and a bimodal, broad molecular weight

distribution product (a mixture of separately produced polymers) in the absence of DEZ. Due to the fact that Catalyst (Al) is known to incorporate more octene than Catalyst (B I), the different blocks or segments of the resulting copolymers of the invention are distinguishable based on branching or density.

[156] It may be seen the polymers produced according to the invention have a relatively narrow polydispersity (Mw/Mn) and larger block-copolymer content (trimer, tetramer, or larger) than polymers prepared in the absence of the shuttling agent
[157] Further characterizing data for the polymers of Table 1 are determined by reference to the figures. More specifically DSC and ATREF results show the following:
[158] The DSC curve for the polymer of example 1 shows a 115.7°C melting point (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAF curve shows the tallest peak at 34.5°C with a peak area of 52.9 percent. The difference between the DSC Tm and the Tcrystaf is 81.2°C.
[159] The DSC curve for the polymer of example 2 shows a peak with a 109.7°C melting point (Tm) with a heat of fusion of 214.0 J/g. The corresponding CRYSTAF curve shows the tallest peak at 46.2°C with a peak area of 57.0 percent. The difference between the DSC Tm and the Tcrystaf is 63.5°C.
[160] The DSC curve for the polymer of example 3 shows a peak with a 120.7°C melting point (Tm) widi a heat of fusion of 160.1 J/g. The corresponding CRYSTAF curve shows the tallest peak at 66.1 °C with a peak area of 71.8 percent. The difference between the DSC Tm and the Tcrystaf is 54.6°C.

[161] 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 J/g. The corresponding CRYSTAF curve shows the tallest peak at 30 °C with a peak area of 18.2 percent The difference between the DSC Tm and the Tcrystaf is 74.5°C.
[162] The DSC curve for comparative A shows a 90.0°C melting point (Tm) with a heat of fusion of 86.7 J/g. The 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.
[163] 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 with 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 Tcrystaf is 47.4°C.
[164] The DSC curve for comparative C shows a 125.3°C melting point (Tm) with a heat of fusion of 143.0 J/g. The corresponding 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 presence of a high crystalline and a low crystalline polymer. The difference between the DSC Tm and the Tcrystaf is 43.5°C.
Examples 5-19, Comparatives D-F« Continuous Solution Polymerization, Catalyst A1/B2 + DEZ
[165] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E available from ExxonMobil Chemical Company), ethylene at 2.70 lbs/hour (1.22 kg/hour), 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 1 injection lines and the reactor agitator. These flows are measured by 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 hydrogen (where used) and fed to the reactor. A mass flow

controller is used to deliver hydrogen to (he 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 and introduced into the bottom of the reactor. The reactor is run liquid-full at 500 psig (3.4S MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactor. 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 mixer. The product stream is then heated by passing through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer. Process details and results are contained in Table 2. Selected polymer properties are provided in Table 3.





[1661 The resulting polymers are tested by DSC and ATREF as with previous examples. Results are as follows:
[1671 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 CRYSTAF curve shows the tallest peak at 47.6°C with a peak area of 59.5 percent The delta between the DSC Tm and the Tcrystaf is 72.0°C.
[168] The DSC curve for the polymer of example 6 shows a peak with a 115.2°C melting point (Tm) with a heat of fusion of 60.4 J/g. The 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.
[169] The DSC curve for the polymer of example 7 shows a peak with a 121.3°C melting point with a heat of fusion of 69.1 J/g. The corresponding CRYSTAF 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.
[170] The DSC curve for the polymer of example 8 shows a peak with a 123.5°C melting point (Tm) with a heat of fusion of 67.9 J/g. The corresponding CRYSTAF curve shows the tallest peak at 80,1°C with a peak area of 12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4°C.
[171] The DSC curve for the polymer of example 9 shows a peak with a 124.6°C melting point (Tm) with a heat of fusion of 73.5 J/g. The corresponding CRYSTAF curve shows the tallest peak at 80.8°C with a peak area of 16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8°C.
[172] The DSC curve for the polymer of example 10 shows a peak with a 115.6°C melting point (Tm) with a heat of fusion of 60.7 J/g. The corresponding CRYSTAF curve shows the tallest peak at 40.9°C with a peak area of 52.4 percent. The delta between the DSC
Tm and the Tcrystaf is 74.7°C.
[173] The DSC curve for the polymer of example 11 shows a peak with a 113.6°C melting point (Tm) with a heat of fusion of 70.4 J/g. The corresponding CRYSTAF curve

shows the tallest peak at 39.6°C with a peak area of 25.2 percent. The delta between the DSC Tm and the Tcrystaf is 74.1°C.
[174] The DSC curve for the polymer of example 12 shows a peak with a 113.2°C melting point (Tm) with a heat of fusion of 48.9 J/g. The corresponding CRYSTAF curve shows no peak equal to or above 30°C. (Tcrystaf for purposes of further calculation is therefore set at 30°C). The delta between the DSC Tm and the Tcrystaf is 83.2°C.
[175] 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 J/g. The corresponding CRYSTAF curve shows the tallest peak at 33.8°C with a peak area of 7.7 percent The delta between the DSC Tm and the Tcrystaf is 84.4°C.
[176] The DSC for the polymer of example 14 shows a peak with a 120.8°C melting point (Tm) with a heat of fusion of 127.9 J/g. 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 Tcrystaf is 47.9°C.
[177] The DSC curve for the polymer of example 15 shows a peak with a 1143°C melting point (Tm) with a heat of fusion of 36.2 J/g. 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.
[178] The DSC curve For the polymer of example 16 shows a peak with a 116.6°C melting point (Tm) with a heat of fusion of 44.9 J/g. 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.
[179] The DSC curve for the polymer of example 17 shows a peak with a 116.0°C melting point (Tm) with a heat of fusion of 47.0 J/g. The corresponding CRYSTAF curve shows the tallest peak at43.1°C with a peak area of 56.8 percent. The delta between the DSC Tm and the Tcrystaf is 72.9°C.
[180] The DSC curve for the polymer of example 18 shows a peak with a 120.5°C melting point (Tm) with a heat of fusion of 141.8 J/g. 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.
[181J The DSC curve for the polymer of example 19 shows a peak with a 124.8°C melting point (Tm) with a heat of fusion of 174.8 J/g. The corresponding CRYSTAF curve shows the tallest peak at 79.9°C with a peak area of 87.9 percent. The delta between the DSC Tm and the Tcrystaf is 45.0°C.
[182] The DSC curve for the polymer of comparative D shows a peak with a 37.3°C melting point (Tm) with a heat of fusion of 31.6 J/g. The corresponding CRYSTAF curve 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 between the DSC Tm and the Tcrystaf is 7.3°C.
[183] The DSC curve for the polymer of comparative E shows a peak with a 124.0°C melting point (Tm) with a heat of fusion of 179.3 J/g. The corresponding CRYSTAF 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.
[184J The DSC curve for the polymer of comparative F shows a peak with a 124.8°C melting point (Tm) with a heat of fusion 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
[185] Polymer samples are evaluated for physical properties such as high temperature resistance properties, as evidenced by TMA temperature testing, pellet blocking strength, high temperature recovery, high temperature compression set and storage modulus ratio, G'(25°C)/G,(l00oC). Several commercially available polymers are included in the tests: Comparative G* is a substantially linear ethylene/1 -octene copolymer (AFFINITY®, available from The Dow Chemical Company), Comparative H* is an elastomeric, substantially linear ethylene/ 1-octcne copolymer (AFF1N1TYOEG8100, available from The Dow Chemical Company), Comparative I is a substantially linear ethylene/1 -octene

copolymer (AFFIN1TY®PL1840, available from The Dow Chemical Company). Comparative J is a hydrogenated styrene/butadiene/styrene triblock copolymer (KRATON™ G1652, available from KRATON Polymers), Comparative K is a thermoplastic vulcanizate (TPV, a polyolefm blend containing dispersed therein a crosslinked elastomer). Results are presented in Table 4.

[1861 In Table 4, Comparative F (which is a physical blend of the two polymers resulting from simultaneous polymerizations using catalyst Al and B I) has a 1 mm penetration temperature of about 70°C, while Examples 5-9 have a 1 mm penetration temperature of I00°C or greater. Further, examples 10-19 all have a 1 mm penetration temperature of greater than 85°C, with most having 1 mm TMA 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 blend. Comparative J (a commercial SEBS) has a good 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. Thus the exemplified polymers have a unique combination of properties unavailable even in some commercially available, high performance thermoplastic elastomers.
[187] Similarly, Table 4 shows a low (good) storage modulus ratio, G,(25°C)/G*( 100°C), for the inventive polymers of 6 or less, whereas a physical blend (Comparative F) has a storage modulus ratio of 9 and a random ethylene/octene copolymer (Comparative G) of similar density has a storage modulus ratio an order of magnitude 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 unaffected by temperature, and fabricated articles made from such polymers can be usefully employed over a broad temperature range. This feature of low storage modulus ratio and temperature independence is particularly useful in elastomer applications such as in pressure sensitive adhesive formulations.
[188] The data in Table 4 also demonstrate that the polymers of the invention
possess improved pellet blocking strength. In particular. Example 5 has a pellet blocking strength of 0 MPa, meaning it is free flowing 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.
[189] High temperature (70°C) compression set for the inventive polymers is generally 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, H and J all have a 70°C compression set of 100 percent (the maximum possible value, indicating no recovery). Good high temperature compression set (low numerical values) is especially needed for applications such as gaskets, window profiles, o-rings, and the like.



[190] Table 5 shows results for mechanical properties for the new polymers as well
as for various comparison polymers at ambient temperatures. It may be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 nun3, preferably less than about 80 mm3, and especially less than about 50 mm3. In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance.
[191] 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 mJ.
[192] Table 5 also shows that the polymers 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 H 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. 11) to as high as about 1100 kPa (Ex. 17). Polymers having higher than 150 percent retractive stress values would be quite useful for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics. Other applications include diaper, hygiene, and medical garment waistband applications, such as tabs and elastic bands.
[193] Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for the inventive polymers as compared to, for example. Comparative G. Lower stress relaxation means 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.


[194] The optical properties reported in Table 6 are based on compression molded films substantially lacking in orientation. Optical properties of the polymers may be varied over wide ranges, due to variation in crystallite size, resulting from variation in the quantity of chain shuttling agent employed in the polymerization.
Extractions of Multi-Block Copolymers
[195] 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 extraction thimble and fitted into a Kumagawa type extractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flask is then fitted to the extractor. The ether is heated while being stirred. Time is noted when the ether begins to condense into the thimble, and the extraction is allowed to proceed under nitrogen for 24 hours. At this time, heating is stopped and the solution is allowed to cool. Any ether remaining in the extractor is returned to the flask. The ether in the flask is evaporated under vacuum at ambient temperature, and the resulting solids are purged dry with nitrogen. Any residue is transferred to a weighed bottle using successive washes of hexane. The combined hexane washes are then evaporated with another nitrogen purge, and

the residue dried under vacuum overnight at 40°C. Any remaining ether in the extractor is purged dry with nitrogen.
[196] 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 by a nitrogen purge, and the residue is vacuum dried overnight at 40°C
[197] The polymer sample 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 Table 7.

Additional Polymer Examples 19 A-X. Continuous Solution Polymerization. Catalyst A1/B2 + DEZ
For Examples 19A-I
[198] Continuous solution polymerizations are carried out in a computer controlled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ E available from Exxon Mobil, Inc.), ethylene, 1-octene, and hydrogen (where used) are combined and fed to a 27 gallon reactor. The feeds to the reactor are measured by mass-flow controllers. The temperature of the feed stream is controlled by use of a glycol cooled heat exchanger before entering the reactor. The catalyst component solutions are metered using pumps and mass flow meters. The reactor is run liquid-full at approximately 550 psig pressure. Upon exiting the reactor.

water and additive are injected in the polymer solution. The water hydrolyzes the catalysts, and terminates the polymerization reactions. The post reactor solution is then heated in preparation for a two-stage devolatization. The solvent and unreacted monomers are removed during the devolatization process. The polymer melt is pumped to a die for underwater pellet cutting.
For Example 19J
[199] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E available from ExxonMobil, Inc.), ethylene at 2.70 lbs/hour (1.22 kg/hour), 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. These flows are measured by 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 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 catalyst component solutions are metered using pumps and mass flow meters and are combined with 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 reactor. AH 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 mixer. The product stream is then heated by passing through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer.
[200] Process details and results are contained in Table 8. Selected polymer properties are provided in Tables 9A-C.

[201] In Table 9B, inventive examples 19F and 19G show low immediate set of
around 65 - 70 % strain after 500% elongation.







Function alized Ethylene/α-olefinInterpolymers
[202] The multi-block olefin interpolymers disclosed above may be modified by, for example, grafting, hydrogenation, nitrene insertion reactions, or other functionalization reactions such as those known to those skilled in the art. Preferred functionalizations are grafting reactions using a free radical mechanism.
[203] A variety of radically graftable species may be attached to the polymer, either
individually, or as relatively short grafts. These species include unsaturated molecules, each containing at least one hetcroatom. These species include, but are not limited to, maleic anhydride, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, nadic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, and the respective esters, imides, salts, and Diels-Alder adducts of these compounds. These species also include silane compounds.
[204] Radically graftable species of the silane class of materials may be attached to the polymer, either individually, or as relatively short grafts. These species include, but are not limited to, vinylalkoxysilanes, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, and the like. Generally, materials of this class include, but are not limited to, hydrolyzable groups, such as alkoxy, acyloxy, or halide groups, attached to silicon. Materials of this class also include non-hydrolyzable groups, such as alkyl and siloxy groups, attached to silicon.
[205] Other radically graftable species may be attached to the polymer, individually, or as short-to-longer grafts. These species include, but are not limited to, methacrylic acid; acrylic acid; Diels-Alder adducts of acrylic acid; methacrylates including methyl, ethyl, butyl, isobutyl, ethylhexyl, lauryl, stearyl, hydroxyethyl, and dimethylaminoethyl; acrylates including methyl, ethyl, butyl, isobutyl, ethylhexyl, lauryl, stearyl, and hydroxyethyl; glycidyl methacrylate; trialkoxysilane methacrylates, such as 3-(methacryIoxy)propyltrimethoxysiIaneand 3-(methacryloxy)propyl-triethoxysiIane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane; acrylonitrile; 2-isopropenyI-2-oxazoIine; styrene; a-methylstyrene; vinyltoluene; dichlorostyrene; N-

vinylpyrrolidinone, vinyl acetate, methacryloxypropyltrialkoxysilanes, methacryloxymethyltrialkoxysilanes and vinyl chloride.
[206] Mixtures of radically graftable species that comprise at least one of the above species may be used, with styrene/maleic anhydride and styrene/acrylonitrile as illustrative examples.
[207] A thermal grafting process is one method for reaction, however, other grafting processes may be used, such as photo initiation, including different forms of radiation, e-beam, or redox radical generation.
[208] The functionalized interpolymers disclosed herein may also be modified by various chain extending or cross-linking processes, including, but not limited to peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems. A full description of the various cross-linking technologies is described in U.S. Patents No. 5,869,591 and No. 5.977571, both of which are herein incorporated by reference in their entirety.
[209] Suitable curing agents may include peroxides, phenols, azides, aldehyde-amine reaction products, substituted ureas, substituted guanidtnes; substituted xanthates; substituted dithiocarbamates; sulfur- containing compounds, such as thiazoles, imidazoles, sulfenamides, thiuramidisulfides, paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; and combinations thereof. Elemental sulfur may be used as a crosslinking agent for diene containing polymers.
[210] In some systems, for example, in silane grafted systems, crosslinking may be promoted with acrosslinking catalyst, and any catalyst that will provide this function can be used in this invention. These catalysts generally include acids and bases, especially organic bases, carboxylic acids and sulfonic acids, and organometailic compounds including organic titanates, organic zirconates, and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin. Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, cobalt naphthenate, and the like, are examples of suitable crosslinking catalysts.
[211] Rather than employing a chemical crosslinking agent, crosslinking may be effected by use of radiation or by the use of electron beam. Useful radiation types include ultraviolet (UV) or visible radiation, beta ray, gamma rays. X-rays, or neutron rays.

Radiation is believed to effect crosslinking by generating polymer radicals which may combine and crosslink.
[212] Dual cure systems, which use a combination of heat, moisture cure, and radiation steps, may be effectively employed. Dual cure systems are disclosed in U.S. Patents No. 5,911,940 and No. 6,124370, which are incorporated herein by reference in their entirety. For example, it may be desirable to employ peroxide crosslinking agents in conjunction with silane crosslinking agents; peroxide crosslinking agents in conjunction with radiation; or sulfur-containing crosslinking agents in conjunction with silane crosslinking agents.
[213] The functionalization may also occur at the terminal unsaturated group (e.g., vinyl group) or an internal unsaturation group, when such groups are present in the polymer. Such functionalization includes, but is not limited to, hydrogenation, halogenation (such as chlorination), ozonation, hydroxylation, sulfonation, carboxylation, epoxidation, and grafting reactions. Any functional groups, such as halogen, amine, amide, ester, carboxylic acid, ether, silane, siloxane, and so on, or functional unsaturated compounds, such as maleic anhydride, can be added across a terminal or internal unsaturation via known chemistry. Other functionalization methods include those disclosed in the following U.S. Patents: 5,849,828, entitled, "Metalation and Functionalization of Polymers and Copolymers;" 5,814,708, entitled, "Process for Oxidative Functionalization of Polymers Containing Alkylstyrene;" and 5,717,039, entitled, "'Functionalization of Polymers Based on Koch Chemistry and Derivatives Thereof." Each of these patents is incorporated by reference, herein, in its entirety.
Free Radical Initiators Useful for Initiating Grafting Reactions
[214] There are several types of compounds that can initiate grafting reactions by decomposing to form free radicals, including ozo-containing compounds, carboxylic peroxyacids and peroxyesters, alkyl hydroperoxides, and dialkyl and diacyi peroxides, among others. Many of these compounds and their properties have been described (Reference: J. Branderup, E. Immergut, E. Grulke, eds. "Polymer Handbook," 4th ed, Wiley, New York, 1999, Section II, pp. 1-76.). It is preferable for the species that is formed by the decomposition of the initiator to be an oxygen-based free radical. It is more preferable for the initiator to be selected from carboxylic peroxyesters, peroxyketals, dialkyl peroxides, and

diacyl peroxides. Some of the more preferable initiators, commonly used to modify the structure of polymers, are listed below. Also shown below, are the respective chemical structures and the theoretical radical yields. The theoretical radical yield is the theoretical number of free radicals that are generated per mole of initiator.



Maleic Anhydride Functionalized Olefin Interpolymers
[215] The multi-block olefin interpolymers disclosed above may be modified by, for example, grafting with maleic anhydride. The grafted maleic anhydride olefin inteipolymer may or may not contain small amounts of hydrolysis product and/or other derivatives. In one embodiment, the grafted maleic anhydride olefin interpolymers have a molecular weight distribution from about 1 to 7, preferably from 1.5 to 6, and more preferably from 2 to 5. All individual values and subranges from about 1 to 7 are included herein and disclosed herein.
(216] In another embodiment* the grafted maleic anhydride olefin interpolymers have density from 0.855 g/cc to 0.955 g/cc, preferably from 0.86 g/cc to 0.90 g/cc, and more preferably from 0.865 g/cc to 0.895 g/cc. All individual values and subranges from 0.84 g/cc to 0.955 g/cc are included herein and disclosed herein.
(217] In another embodiment, the amount of maleic anhydride used in the grafting
reaction is less than, or equal to, 10 phr (parts per hundred, based on the weight of the olefin interpolymer), preferably less than 5 phr, and more preferably from 0.5 to 10 phr, and even

more preferably from 0.5 to 5 phr. AH individual values and subranges from 0.05 phr to 10 phr are included herein and disclosed herein.
[218] In another embodiment, the amount of initiator used in the grafting reaction is
less than* or equal to, 10 millimoles radicals per 100 grams olefin interpolymer, preferably, less than, or equal to, 6 millimoles radicals per 100 grains olefin interpolymer, and more preferably, less than, or equal to, 3 millimoles radicals per 100 grams olefin interpolymer. All individual values and subranges from 0.01 millimoles to 10 millimoles radicals per 100 grams olefin interpolymer are included herein and disclosed herein.
[219] In another embodiment, the amount of maleic anhydride constituent grafted on the polyolefin chain is greater than 0.05 weight percent (based on the weight of the olefin interpolymer), as determined by titration analysis, FTIR analysis, or any other appropriate method. In a further embodiment, this amount is greater than 0.25 weight percent, and in yet a further embodiment, this amount is greater than 0.5 weight percent. In a preferred embodiment, 0.5 weight percent to 2.0 weight percent of maleic anhydride is grafted All individual values and subranges greater than 0.05 weight percent are considered within the scope of this invention, and are disclosed herein.
[220] The maleic anhydride, as well as many other unsaturated heteroatom containing species, may be grafted to the polymer by any conventional method, typically in the presence of a free radical initiator, for example the peroxide and azo classes of compounds, etc., or by ionizing radiation. Organic initiators are preferred, such as any one of the peroxide initiators, such as, dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, 2,5-dimethyI-2,5-di(tert-butyl peroxy)-3-hexyne, lauryl peroxide, and tert-butyl peracetate. A suitable azo compound Is 2,2'-azobis(isobutyronitrile). The organic initiators have varying reactivities at different temperatures, and may generate different types of free radicals for grafting. One skilled in the art may select the appropriate organic initiator as needed for the grafting conditions.
[221] The amount and type, of initiator, the amount of maleic anhydride, as well as reaction conditions, including temperature, time, shear, environment, additives, diluents, and the like, employed in the grafting process, may impact the final structure of the maleated polymer. For example, the degree of maleic anhydride/succinic anhydride, their oligomers,

and their derivatives, including hydrolysis products, grafted onto the grafted polymer may be influenced by the aforementioned considerations. Additionally, the degree and type of branching, and the amount of cross! inking, may also be influenced by the reaction conditions and concentrations. In general, it is preferred that crosslinking during the maleation process be minimized. The composition of the base olefin interpoiymer may also play a role in the final structure of the maleated polymer. The resulting structure, will in turn, affect the properties and use of the final product Typically, the amount of initiator and maleic anhydride employed will not exceed that, which is determined to provide the desired level of maleation and desired melt flow, each required for the fiinctionalized polymer and its subsequent use.
[222] The grafting reaction should be performed under conditions that maximize grafts onto the polymer backbone, and minimize side reactions, such as the homopolymerization of the grafting agent, which is not grafted to the olefin interpoiymer. It is not unusual that some fraction of the maleic anhydride (and/or its derivatives) does not graft onto the olefin interpoiymer, and it is generally desired that the unreacted grafting agent be minimized. The grafting reaction may be performed in the melt, in solution, in the solid-state, in a swollen-state, and the like. The maleation may be performed in a wide-variety of equipments, such as, but not limited to, twin screw extruders, single screw extruders, Brabenders, batch reactors, and the like.
[223] Additional embodiments of the invention provide for olefin interpolymers grafted with other carbonyl-containing compounds. In one embodiment, these grafted olefin interpolymers may have molecular weight distributions and/or densities the same as, or similar to, those described above for the grafted maleic anhydride olefin interpolymers. In another embodiment, these grafted olefin interpolymers are prepared using the same or similar amounts of grafting compound and initiator as those used for the grafted maleic anhydride olefin interpolymers, as described above. In another embodiment, these grafted olefin interpolymers contain the same or similar levels of grafted compound as for the grafted maleic anhydride, as described above.
[224] Additional carbonyl-containing compounds include, but are not limited to, dibutyl maleate. dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, nadic anhydride, methylnadic anhydride, alkenyisuccinic

anhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, esters thereof, imides thereof, salts thereof, and Diels-Alder adducts thereof.
Silane Functionalizcd Olefin Interpolvmers
[225] The multi-block olefin interpoiymers disclosed above may be modified by, for example, grafting with at least one silane compound. The grafted silane olefin interpolymer may or may not contain small amounts of hydrolysis product and/or other derivatives.
[226] In one embodiment, the silane-grafted olefin interpoiymers have a molecular weight distribution from about 1 to 7, preferably from 1.5 to 6, and more preferably from 2 to 5. All individual values and subranges from about 1 to 7 are included herein and disclosed herein.
[227] In another embodiment, the silane-grafted olefin interpoiymers have density from 0.855 g/cc to 0.955 g/cc, and preferably from 0.86 g/cc to 0.90 g/cc, and more preferably from 0.865 g/cc to 0,895 g/cc. All individual values and subranges from 0.84 g/cc to 0.955 g/cc are included herein and disclosed herein.
[228] In another embodiment, the amount of silane used in the grafting reaction is greater than, or equal to, 0.05 phr (based on the amount of the olefin interpolymer), more preferably, from 0.5 phr to 6 phr, and even more preferably, from 0.5 phr to 4 phr. All individual values and subranges from 0.05 phr to 6 phr are included herein and disclosed herein.
[229] In another embodiment, the amount of amount of initiator used in the grafting reaction is less than, or equal to, 4 millimoles radicals per 100 grams olefin interpolymer, preferably, less than, or equal to, 2 millimoles radicals per 100 grams olefin interpolymer, and more preferably, less than, or equal to, 1 millimoles radicals per 100 grams olefin interpolymer. AH individual values and subranges from 0.01 millimoles to 4 millimoles radicals per 100 grams olefin interpolymer are included herein and disclosed herein.
[230] In another embodiment, the amount of silane constituent grafted on the polyolefm chain is greater than, or equal to, 0.05 weight percent (based on the weight of the olefin interpolymer), as determined by FTIR analysts, or other appropriate method. In a further embodiment, this amount is greater than, or equal to, 0.5 weight percent, and in yet a

further embodiment, this amount is greater than, or equal to, 1.2 weight percent. In a preferred embodiment, the amount silane constituent grafted on the olefin interpolyrner is from 0.5 weight percent to 4.0 weight percent. All individual values and subranges greater than 0.05 weight percent are considered within the scope of this invention, and are disclosed herein.
[231] Suitable silanes include, but are not limited to, those of the general formula (D:
CH2=CR-(COO)x(CIIH2fl)ySiR'3 (I).
[232] In this formula, R is a hydrogen atom or methyl group; x and y are 0 or 1, with the proviso that when x is 1, y is 1; n is an integer from 1 to 12 inclusive, preferably 1 to 4, and each R' independently is an organic group, including, but not limited to, an alkoxy group having from I to 12 carbon atoms (e.g. methoxy, ethoxy, butoxy), an aryloxy group (e.g. phenoxy), an araioxy group (e.g. benzyloxy), an aliphatic or aromatic siloxy group, an aromatic acyloxyl group, an aliphatic acyloxy group having from 1 to 12 carbon atoms (e.g. formyloxy, acetyioxy, propanoyloxy), amino or substituted amino groups (alkylamino, aryiamino), or a lower alky] group having 1 to 6 carbon atoms.
[233] In one embodiment, the silane compound is selected from vinyltrialkoxysilanes, vinyltriacyloxysilanes or vinyltrichlorosilane. In addition, any silane, or mixtures of silanes, which will effectively graft to, and/or crosslink, the olefin interpolymers can be used in the practice of this invention. Suitable silanes include unsaturated silanes that comprise both an ethylenicaUy unsaturated hydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or y-(meth)acryIoxy allyl group, and a hydrolyzable group, such as, a hydrocarbyloxy, hydrocarbonyloxy, orhydrocarbylamino group, or a halide. Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, chloro, and alkyl or aryiamino groups. Preferred silanes are the unsaturated alkoxy silanes which can be grafted onto the polymer. These silanes and their method of preparation are more fully described in U.S. Patent No. 5,266,627 to Meverden, et at., which is incorporated herein, in its entirety, by reference. Preferred silanes include vinyUrimethoxysilane, vinyltriethoxysilane, 3-(trimethoxysilyl)propyl rnethacrylate (y-(meth)acryloxypropyl trimethoxysilane), and mixtures thereof.

[234] The siiane can be grafted to the polymer by any conventional method, typically in the presence of a free radical initiator, for example peroxides and azo compounds, etc., or by ionizing radiation. Organic initiators are preferred, such as any one of the peroxide initiators, for example, dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate. benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxyjhexane, lauryl peroxide, and tert-butyl peracetate. A suitable azo compound is 2,2'-azobis(isobutyronitrile).
[235] The amount of initiator and siiane employed will affect the final structure of the siiane grafted polymer, such as, for example, the degree of grafting in the grafted polymer and the degree of crosslinking in the cured polymer. The resulting structure, will in turn, affect the physical and mechanical properties of the final product. Typically, the amount of initiator and siiane employed will not exceed that which is determined to provide the desired level of crosslinking, and the resulting properties in the polymer.
[236] The grafting reaction should be performed under conditions that maximize grafts onto the polymer backbone, and minimize side reactions, such as the homopolymerization of grafting agent, which is not grafted to the polymer. Some siiane agents undergo minimal or ho homopolymerization, due to steric features in the molecular structure, low reactivity and/or other reasons.
[237] Cure (crosslinking) of a silanated graft is promoted with a crosslinking catalyst, and any catalyst that will effectively promote the crosslinking of the particular grafted siiane can be used. These catalysts generally include acids and bases, and organometallic compounds, including organic titanates, organic zirconates, and complexes or carboxylaces of lead, cobalt, iron, nickel, zinc and tin.
[238] Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, cobalt naphthenate, and the like, can be used. The amount of catalyst will depend on the particular system at issue.
[239] In certain embodiments of the claimed invention, dual crosslinking systems, which use a combination of radiation, heat, moisture and crosslinking steps, may be effectively employed. For instance, it may be desirable to employ peroxide crosslinking

agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, or sulfur-containing crosslinking agents in conjunction with silane crosslinking agents. Dual crosslinking systems are disclosed, and claimed in, U.S. Patent Nos. 5,911,940 and 6,124,370, the entire contents of both are herein incorporated by reference.
[240] The silane grafted interpolymers of the present invention are often useful in adhesive compositions. In this regard the functionalizcd interpolymers may be characterized by, for example, a Peel Adhesion Failure Temperature (PAFT) of greater than, or equal to, 110°F (43 °C), or a Shear Adhesion Failure Temperature (SAFT) of greater than, or equal to, 140°F (60°C); or both wherein PAFT and SAFT are measured as follows:
Shear Adhesion Failure Temperature (SAFT)
[241] Shear adhesion failure temperature (SAFT) of each sample was measured
according to ASTM D 4498 with a 500 gram weight in the shear mode. The tests were staned at room temperature (25°C/77°F) and the oven temperature was ramped at an average rate of 0.5°C/minute. The temperature at which the specimen failed was recorded. This measurement was used as an indication of the heat resistance of the composition which is important for shipping.
Peel Adhesion Failure Temperature (PAFT)
[242] Peel adhesion failure temperature (PAFT) was tested according to ASTM D 4498 with a 100 gram weight in the peel mode. The tests were started at room temperature (25°C/77°F) and the temperature was increased at an average rate of 0.5°C/minute.
[243] In addition, if the silane-grafted interpolymer is to be employed in, for
example, an adhesive composition, it is often preferable that the silane-grafted ethylene/a-olefin polymer have a molecular weight distribution (Mw/Mn) from about 1 to about 3.5 and/or a number average molecular weight from 5,000 to 25,000.
Azide Modification
[244] The multi-block olefin interpolymers disclosed above may be modified by, for example, azide modification. Compounds having at least two sulfonyl azide groups capable of C--H iasertion under reaction conditions are referred to herein as coupling agents. For the



We claim:
1. A composition comprising at least one fiinctionalized olefin interpolymer, and
wherein the fiinctionalized olefin interpolymer is formed from an olefin interpolymer having at least one melting point, Tm, in degrees Celsius, and a density, d*. in grams/cubic centimeter, and wherein the numerical values of the variables correspond to the relationship:
Tm > -2002.9 + 4538.5 wherein the olefin interpolymer has a Mw/MD from 1.7 to 3.5.
2. The composition of Claim 1, wherein the olefin interpolymer is fiinctionalized with at least one unsaturated compound containing at least one heteroatom.
3. The composition of Claim 1, wherein the olefin interpolymer is functionalized with at least one carbonyl-containing compound.
4. The composition of Claim 3, wherein the at least one carbonyl-containing compound is selected from the group consisting of maleic anhydride, dibutyl maleate, dicyclohcxyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, nadic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, esters thereof, imides thereof, salts thereof, and Dicls-Alder adducts thereof.
5. The composition of Gaim 1, wherein the olefin interpolymer is functionalized with at least one silane compound.
6. The composition of Claim 5, wherein the at least one silane compound is represented by formula (I):
CHz^R-CCOO^CnH.n^iR'a (I),
wherein, R is a hydrogen atom or methyl group; x and y are 0 or 1, with the proviso that when x is 1, y is 1; n is an integer from 1 to 12; and each R' is independently an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group, an araloxy group, an aromatic

acyloxy group, an aromatic or aliphatic siloxy group, an aliphatic acyloxy group having from 1 to 12 carbon atoms, amino or substituted amino groups, or a lower alkyl group having 1 to 6 carbon atoms.
7. The composition of Claim 5, wherein the at least one silane compound is selected from the group consisting of vinyltrialkoxysilanes, vinyltriacyloxysilanes and vinyltrichlorosilane.
8. The composition of Claim 1, wherein the olefin interpolymer is functionalized with at least one compound selected from the group consisting of methacrylic acid; acrylic acid; Diels-AIder adducts of acrylic acid; methacrylates; acrytates; glycidyl methacrylate; trialkoxysilane methacrylates; acrylonitrile; 2-isopropenyl-2-oxazoline; styrene; a-methylstyrene; vinyltoluene; dichlorostyrene; N-vinylpyrrolidinone, vinyl acetate, methacryloxypropyltrialkoxysilanes, methacryloxymethyltrialkoxysilanes and vinyl chloride.
9. A composition comprising at least one functionalized multi-block interpolymer, and wherein the interpolymer is prepared from a multi-block interpolymer that comprises, in polymerized form, ethylene and one or more copolymerizable comonomers, and wherein said multi-block interpolymer comprises two or more segments, or blocks, differing in comonomer content, crystallinity, density, melting point or glass transition temperature, and
wherein the multi-block interpolymer is functionalized with at least one compound selected from the group consisting of unsaturated compounds containing at least one heteroatom.
10. The composition of Claim 9, wherein the interpolymer is grafted with at least one unsaturated compound, containing at least one heteroatom, and wherein the ratio of "the CH2/CH groups in the multi-block interpolymer" to "the CH-graft/CH-graft groups in the functionalized interpolymer" is greater than, or equal to, 3.
11. The composition of Claim 9, wherein the functionalized multi-block interpolymer is prepared by reacting the multi-block interpolymer with the at least one compound, and at least one initiator, and wherein the at least one initiator generates 0.01 millimoles to 10 millimoles radicals per 100 grams of the multi-block interpolymer, and

wherein the at least one compound is present in an amount from 0.05 to 10 parts per hundred gram of the multi-block interpoiymer.
12. The composition of Claim 11, wherein the at least one compound is present in an amount from 0.05 to 5 parts per hundred gram of the multi-block interpoiymer.
13. The composition of Claim 9, wherein the at least one compound is grafted onto the multi-block interpoiymer, in an amount greater than, or equal to, 0.1 weight percent, based on the weight of the multi-block interpoiymer.
14. The composition of Claim 9, wherein the at least one compound is grafted onto the multi-block mterpolymer, in an amount greater than* or equal to, 1.0 weight percent, based on the weight of the multi-block interpoiymer.
15. A composition comprising at least one silane-grafted ethylene/a-olefin multi-block polymer, and wherein the silane-grafted ethylene/a-olefin multi-block polymer is formed from an olefin interpoiymer having a melt viscosity less than 50,000 cP at 350°F (177°C).
16. The composition of Claim 15 wherein the silane-grafted ethylene/a-olefin multi-block polymer interpoiymer is formed from an olefin interpoiymer having at least one melting point, Tm, in degrees Celsius, and a density, d*. in grams/cubic centimeter, and wherein the numerical values of the variables correspond to the relationship:
Tm > -2002.9 + 4538.5(d*) - 2422.2(d*)2, and
wherein the olefin interpoiymer has a Mw/Mn from 1.7 to 3.5.
17. A composition comprising at least one functionalized ethylene/a-olefin multi-block polymer, and wherein the functionalized ethylene/a-olefin multi-block polymer is formed from an olefin multi-block interpoiymer having a melt viscosity less than 50,000 cP at350°F(l77°C).
18. The composition of Claim 15 or 17, wherein the at least one silane-grafted or functionalized olefin interpoiymer is formed From an olefin interpoiymer having a molecular weight distribution (Mw/Mn) from about 1 to about 3.5.

19. The composition of Claim 15 or 17, wherein the at least one silane-grafted olefin interpolymer is formed from an olefin interpolymer having a number average molecular weight from 5,000 to 25*000.
20. The composition of Claim 15, wherein the at least one silane-grafted ethylene/a-olefin multi-block polymer is present in an amount from 15 to 50 weight percent, based on die total weight of the composition, and the composition further comprises 0 to 40 weight percent of at least one tackifier, based on the total weight of the composition, and 0 to 40 weight percent of at least one oil, based on the total weight of the composition.
21. The composition of claim 20, wherein the silane-grafted ethylene/a-olefin multi-block polymer further comprises a curing catalyst.
22. The composition of claim 21, wherein the composition has been cured.
23. The composition of Claim 22, wherein the composition is characterized by

(a) a Peel Adhesion Failure Temperature (PAFT) of greater than, or equal to, 110°F(43°C)for
(b) a Shear Adhesion Failure Temperature (SAFT) of greater than, or equal to, 140°F(60°C);or
(c) both (a) and (b).

24. The composition of Claim 17, wherein the at least one functionalized ethylene/a-olefin multi-block polymer is present in an amount from 15 to 50 weight percent, based on the total weight of the composition, and the composition further comprises 0 to 40 weight percent of at least one tackifier, based on the total weight of the composition, and 0 to 40 weight percent of at least one oil, based on the total weight of the composition.
25. The composition of Claim 15 or 17, wherein the at least one silane-grafted or functionalized olefin interpolymer is formed from an olefin multi-block interpolymer having a density from about 0.855 g/cc to about 0.93 g/cc.
26. A composition comprising a reaction product formed from the reaction of an ethylene/a-olefin multi-block polymer with at least one silane compound.

27. A composition comprising a reaction product formed from the reaction of an ethylene/a-olefin multi-block polymer with at least one poly(sulfonyl azide) or at least one peroxide.
28. The composition of Claim 27 wherein the viscosity change between the ethylene/a-olefin multi-block polymer and the reaction product is greater than 5 percent at a shear frequency of 0.1 rad/sec.
29. The composition of Claim 27 wherein the ethylene/a-olefin multi-block polymer is reacted with at least 400 ppm of the at least one poly(sulfonyl azide) or at least one peroxide.
30. The composition of Claim 29 wherein the reaction further comprises a co-agent.
31. The composition of Claim 30 wherein the co-agent is a cyanurate.
32. The composition of any one of Claims 27-31 which further comprises polypropylene.
33. The composition of any one of Claims 27-31 wherein the composition has a viscosity ratio (ratio of shear viscosity at 0.1 rad/sec to shear viscosity at 100 rad/sec measured at 190oC) of greater than S.
34. A composition comprising a reaction product formed from the reaction of an *thylene/a-olefin multi-block polymer with at least one maleic anhydride.
35. The composition of Claim 34 wherein the composition has an average Izod impact strength that is greater than a random ethylene/a-olefin interpolymer of similar iensity.
36. A functionalized ethylene/a-olefin interpolymer, wherein the functionalized :thylene/a-olefm interpolymer is the reaction product of at least one unsaturated compound :ontaining at least one heteroatom and an ethylene/a-olefin interpolymer charaterized by one ir more of the following:

(a) 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, 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 > -0.1299(AH) + 62.81 for AH greater than zero and up to 130 J/g,
AT > 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
(b) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured
with a compression-molded film of the ethylene/a-olefin interpolymer, and has a density, d,
in grams/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-linked phase:
Re>1481-1629(d);or
(c) 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 has a melt index, density, and molar comonomer content (based
on the whole polymer) within 10 percent of that of the ethylene/a-olefin interpolymer; or
(d) has 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.S
and up to about 1; or
(e) has 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; or
(0 has 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 in the range of about 1:1 to about 9:1.


Documents:

4034-chenp-2007 other document 29-04-2011.pdf

4034-CHENP-2007 CORRESPONDENCE OTHERS 02-01-2014.pdf

4034-chenp-2007 correspondence others 29-04-2011.pdf

4034-chenp-2007 form-13 29-04-2011.pdf

4034-CHENP-2007 AMENDED CLAIMS 03-09-2014.pdf

4034-CHENP-2007 AMENDED PAGES OF SPECIFICATION 03-09-2014.pdf

4034-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 03-09-2014.pdf

4034-CHENP-2007 FORM-1 03-09-2014.pdf

4034-CHENP-2007 POWER OF ATTORNEY 03-09-2014.pdf

4034-chenp-2007(form18).pdf

4034-chenp-2007-abstract.pdf

4034-chenp-2007-claims.pdf

4034-chenp-2007-correspondnece-others.pdf

4034-chenp-2007-description(complete).pdf

4034-chenp-2007-drawings.pdf

4034-chenp-2007-form 1.pdf

4034-chenp-2007-form 3.pdf

4034-chenp-2007-form 5.pdf

4034-chenp-2007-pct.pdf

Form 3.pdf

Petition for Annexure.pdf


Patent Number 263397
Indian Patent Application Number 4034/CHENP/2007
PG Journal Number 44/2014
Publication Date 31-Oct-2014
Grant Date 27-Oct-2014
Date of Filing 14-Sep-2007
Name of Patentee DOW GLOBAL TECHNOLOGIES LLC
Applicant Address 2040 DOW CENTER, MIDLAND, MICHIGAN 48674
Inventors:
# Inventor's Name Inventor's Address
1 CHEUNG, YUNWA W 104 ROSEMARY LANE, LAKE JACKSON, TX 77566, USA.
2 GUPTA, PANKAJ P 110 LAKE ROAD, APT. 203, LAKE JACKSON, TX 77566, USA.
3 HO, THOI, H 54 ORCHID COURT, LAKE JACKSON, TX 77566, USA.
4 REICHEK, KENNETH, N 115, HONEYSUCKLE STREET, LAKE JACKSON, TX 77566, USA.
5 YALVAC, SELIM 11316 STARLIGHT BAY STREET, PEARLAND, TX 77584, USA.
6 KARJALA, TERESA 56, MANDEVILLA COURT, LAKE JACKSON, TX 77566, USA.
7 ROZENBLAT, BENJAMIN, ROMAN. 2005 TAGGERT DRIVE, BELLE MEAD, NEW JERSEY 08502, USA.
8 RICHEY, CYNTHIA L 315 CARNATION STRESS, LAKE JACKSON, TEXAS 77566, USA.
9 HARRIS, WILLIAM J 216 PLUM CIRCLE, LAKE JACKSON, TX 77566,
10 WEAVER, JOHN, D 122 ANCHUSA STREET, LAKE JACKSON, TX 77566, USA.
11 WALTHER, BRIAN W 309, WILLIAMSBURG, CLUTE, TX 77531, USA
12 HAHN, STEPHEN, F 313 ROSEMARY LANE, LAKE JACKSON, TX 77566, USA.
PCT International Classification Number C08F 295/00
PCT International Application Number PCT/US2006/009591
PCT International Filing date 2006-03-15
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/718,184 2005-09-16 U.S.A.
2 PCT/US05/08917 2005-03-17 U.S.A.