KR20070117595A - Ethylene/alpha-olefins block interpolymers - Google Patents

Abstract

Embodiments of the invention provide a class of ethylene/alpha-olefEn block interpolymers. The ethylene/alpha-olefEn interpolymers are 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 1.3. Preferably, the block index is from about 0.2 to about 1. In addition or alternatively, the block ethylene/alpha-olefin interpolymer is characterized by having at least one fraction obtained by Temperature Rising Elution Fractionation ("TREF"), wherein the fraction has a block index greater than about 0.3 and up to about 1.0 and the ethylene/alpha-olefin interpolymer has a molecular weight distribution, M w/Mn, greater than about 1.3.

Description

Ethylene / α-Olefin Block Interpolymers {ETHYLENE / α-OLEFINS BLOCK INTERPOLYMERS}

The present invention is directed to ethylene / α-olefin block interpolymers and articles made from block interpolymers.

Block copolymers include sequences of the same monomeric units ("blocks") covalently linked to different types of sequences. Blocks may be connected in various ways, such as A-B in a diblock structure and A-B-A in a triblock structure, where A represents one block and B represents another block. In multiblock copolymers, A and B can be linked in many different ways and repeated many times. Multiblock copolymers may further comprise additional blocks of different types. Multiblock copolymers may be linear multiblock polymers or multiblock star polymers, in which all blocks are bound to the same atom or chemical moiety.

Block copolymers are produced when two or more polymer molecules of different chemical composition are covalently bonded in an end-to-end manner. While a wide variety of block copolymer configurations are possible, most block copolymers include covalent bonds of substantially crystalline or glassy rigid plastic blocks to the elastomer blocks forming the thermoplastic elastomer. Other block copolymers such as rubber-rubber (elastomer-elastomer), glass-glass and glass-crystalline block copolymers may also be possible and commercially important.

One way to make the block copolymer is to produce a "living polymer." Unlike typical Ziegler-Natta polymerization processes, living polymerization processes only comprise an initiation step and a growth step, and are essentially free of chain termination side reactions. This allows the synthesis of any desired well controlled structure in the block copolymer. The polymers produced in the “living” system may have a narrow or extremely narrow molecular weight distribution and may be monodisperse in nature (ie, the molecular weight distribution is essentially one). Living catalyst systems are characterized by an onset rate above or above the rate of growth, and the absence of a termination or transfer reaction. In addition, these catalyst systems are characterized by the presence of a single type of active site. In order to produce high yields of block copolymers in the polymerization process, the catalysts must exhibit living properties to a significant extent.

Butadiene-isoprene block copolymers have been synthesized through anionic polymerization using sequential monomer addition techniques. With sequential addition, a certain amount of one monomer is in contact with the catalyst. When all of these first monomers react substantially to form the first block, a certain amount of second monomer or monomer species is introduced and reacted to form the second block. This process can be repeated using the same or different anionic polymerizable monomers. However, ethylene and other α-olefins such as propylene, butene, 1-octene and the like cannot be directly block polymerized by anionic techniques.

Thus, there is a requirement to be achieved for block copolymers based on ethylene and α-olefins. There is also a need for a process for preparing such block copolymers.

<Overview of invention>

The above requirements are met by various aspects of the present invention. In one aspect, the invention comprises polymerized ethylene and α-olefin units, characterized by an average block index greater than 0 and up to about 1.0 and an molecular weight distribution (M _w / M _n ) greater than about 1.3. Olefin interpolymers. In another aspect, the invention comprises polymerized ethylene and α-olefin units, having an average block index greater than 0 and less than about 0.4 and an molecular weight distribution (M _w / M _n ) greater than about 1.3. Olefin interpolymers. Preferably, the interpolymer is a linear multiblock copolymer having at least 3 blocks. Also preferably, the ethylene content in the interpolymer is at least 50 mol%.

In some embodiments, the average block index of the interpolymer is in the range of about 0.1 to about 0.3, about 0.4 to about 1.0, about 0.3 to about 0.7, about 0.6 to about 0.9, or about 0.5 to about 0.7. In other embodiments, the interpolymer has a density of less than about 0.91 g / cc, such as from about 0.86 g / cc to about 0.91 g / cc. In some embodiments, the α-olefin of the ethylene / α-olefin interpolymer is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1 , 5-hexadiene, or a combination thereof. In other embodiments, the molecular weight distribution (M _w / M _n ) is greater than about 1.5 or greater than about 2.0. The molecular weight distribution may range from about 2.0 to about 8 or from about 1.7 to about 3.5.

In another aspect, the invention comprises polymerized ethylene and α-olefin units and has one or more fractions having a block index greater than about 0.3 and up to about 1.0, obtained by temperature rise eluting fractionation (“TREF”), Ethylene / α-olefin interpolymers, characterized in that the distribution (M _w / M _n ) is greater than about 1.3. In another aspect, the present invention has a molecular weight distribution (M _w / M _n ) comprising polymerized ethylene and α-olefin units and having at least one fraction obtained by TREF having a block index greater than about 0 and up to about 0.4 or less. Ethylene / α-olefin interpolymers, characterized in that is greater than about 1.3. In some embodiments, the block index of the fraction is greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than about 0.7, greater than about 0.8, or greater than about 0.9.

The interpolymer includes one or more hard segments and one or more soft segments. Preferably, the hard segment comprises at least 98 weight percent ethylene and the soft segment comprises less than 95 weight percent, preferably less than 50 weight percent ethylene. In some embodiments, the hard segments are present in an amount from about 5% to about 85% by weight of the interpolymer. In other embodiments, the interpolymers comprise at least 5 or at least 10 hard and soft segments that are linked in a linear manner to form a linear chain. Preferably, the hard and soft segments are randomly distributed along the chain. In some embodiments, both the soft and hard segments do not include tip segments (different segments and chemical composition).

Also provided herein are methods of making the interpolymers. Further aspects of the present invention and the features and characteristics of various embodiments of the present invention will become apparent from the following description.

FIG. 1 shows the melting point / density relationship of the polymer of the present invention (indicated by diamond) compared to conventional random copolymers (indicated by circles) and Ziegler-Natta copolymers (indicated by triangles).

2 shows a plot of delta DSC-CRYSTAF as a function of DSC melt enthalpy for various polymers. Diamonds are random ethylene / octene copolymers; Squares are polymers Examples 1-4; Triangles are polymers Examples 5-9; Circles represent Polymer Examples 10-19. The symbol "X" represents Polymer Examples A ^* to F ^* .

FIG. 3 shows the elastic recovery for non-oriented films made from the inventive interpolymers (represented by squares and circles) and conventional copolymers (Dow AFFINITY® polymers, represented by triangles). It shows the effect of density on. Squares represent ethylene / butene copolymers of the present invention, and circles represent ethylene / octene copolymers of the present invention.

FIG. 4 shows TREF fractionated ethylene / 1 for the temperature rising elution fractionation (“TREF”) elution temperature of the polymer fraction of Example 5 (shown as circles) and the comparative polymer E and F fractions (shown with the symbol “X”). Plot of the octene content of the octene copolymer fraction. Diamonds represent conventional random ethylene / octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionated ethylene / 1-octene copolymer fractions versus ATREF elution temperatures of the polymer fraction of Example 5 and the polymer fraction of Comparative Example F ^* . Squares represent Polymer Example F ^* and triangles represent Polymer Example 5. The ATREF temperature distribution for Example 5 (Curve 1) and Comparative Example F ^* (Curve 2) is also shown.

6 shows an embodiment of the invention prepared using comparative ethylene / 1-octene copolymer (curve 2) and propylene / ethylene copolymer (curve 3) and different amounts of chain shuttling agent It is a graph of log storage modulus as a function of temperature for two ethylene / 1-octene block copolymers (curve 1).

FIG. 7 shows a plot of thermomechanical analysis (“TMA”) (1 mm) for flexural modulus for some polymers of the present invention (represented by diamond) compared to some known polymers. Triangles represent Dow VERSIFY® polymers, circles represent random ethylene / styrene copolymers, and squares represent Dow Affinity® polymers.

8 is a plot of the natural log ethylene mole fraction for a random ethylene / α-olefin copolymer as the inverse of the DSC peak melting temperature or ATREF peak temperature. Solid squares represent data points obtained from random ethylene / α-olefin copolymers homogeneously branched in ATREF, and hollow squares represent data points obtained from random ethylene / α-olefin copolymers homogeneously branched in DSC. "P" is the ethylene mole fraction and "T" is the Kelvin temperature.

9 is a plot constructed based on the Flory equation of a random ethylene / α-olefin copolymer to illustrate the definition of “block index”. "A" denotes a wholly complete random copolymer, "B" denotes a pure "hard segment" and "C" denotes a wholly complete block copolymer having the same comonomer content as "A". A, B, and C define a triangular region in which most TREF fractions are included.

10 is a plot of the block index calculated for each TREF fraction for the four polymers. Diamonds represent polymer F ^* with an average block index of 0, triangles represent polymer 5 with an average block index of 0.53, squares represent polymer 8 with an average block index of 0.59, and “X” represent polymer 20 with an average block index of 0.20. Indicates.

FIG. 11 is a plot of the block index calculated for each TREF fraction for the two polymers of the invention, with solid bars representing polymer 18B and hollow bars representing polymer 5. FIG.

FIG. 12 is a plot of average block index calculated for nine different polymers as a function of diethyl zinc concentration during polymerization for “[Zn / C ₂ H ₄ ] * 1000”. "x" represents the ethylene / propylene block copolymer of the present invention (polymer 23), two triangles represent the two ethylene / butene block copolymers of the present invention (polymer 21 and polymer 22), and the squares (any di Ethylene / octene copolymers made from different levels of diethyl zinc (including those made without ethyl zinc) are shown.

FIG. 13 is a plot of the square root of the second moment with respect to the average weight average block index as a function of “[Zn / C ₂ H ₄ ] * 1000”.

14 shows a standard DSC profile for the polymer of the present invention.

FIG. 15 is a weighted DSC profile obtained by converting FIG. 14.

16 is a ¹³ C NMR spectrum of Polymer 19A.

General definition

"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The general term "polymer" encompasses the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer".

"Interpolymer" means a polymer prepared by polymerizing two or more different types of monomers. The general term "interpolymer" refers to the term "copolymer" (commonly used to refer to a polymer made from two different monomers) and the term "terpolymer" (a polymer made from three different types of monomers) Commonly used). Interpolymers also encompass polymers made by polymerizing four or more monomers.

The term “ethylene / α-olefin interpolymer” generally refers to a polymer comprising ethylene and an α-olefin having at least 3 carbon atoms. Preferably, ethylene comprises most of the mole fraction of the total polymer, ie ethylene comprises at least about 50 mol% of the total polymer. More preferably, ethylene comprises at least about 60 mol%, at least about 70 mol%, or at least about 80 mol%, with the substantial remainder of the entire polymer being preferably an α-olefin having 3 or more carbon atoms. At least one other comonomer. For many ethylene / octene copolymers, preferred compositions have an ethylene content of greater than about 80 mol% of the total polymer and an octene content of about 10 to about 15 mol%, preferably about 15 to about 20 mol% of the total polymer. Include. In some embodiments, the ethylene / α-olefin interpolymers do not include those produced in low yield or in small amounts or as a byproduct of a chemical process. The ethylene / α-olefin interpolymers may be blended with one or more polymers, but the resulting ethylene / α-olefin interpolymers are substantially pure and are often included as a major component of the reaction product of the polymerization process.

The term “crystalline”, when used, refers to a polymer or segment having a primary transition temperature or crystal melting point (Tm), measured by differential scanning calorimetry (DSC) or equivalent technique. This term may be used interchangeably with the term "semicrystalline". The term “amorphous” refers to a polymer having no crystalline melting point measured by differential scanning calorimetry (DSC) or equivalent technique.

The term "multiblock copolymer" or "segmented copolymer" is preferably a polymer comprising two or more chemically distinct regions or segments (also referred to as "blocks"), ie pendant or grafted, connected in a linear manner. Rather than a manner, it refers to a polymer comprising chemically differentiated units that are end-to-end linked to a polymerized ethylene functional group. In a preferred embodiment, the block comprises the amount or type of comonomer incorporated therein, the density, the amount of crystallization, the microcrystalline size attributable to the polymer of this composition, the type or degree of tacticity (isotactic or syn Different amounts, homogeneity, or any other chemical or physical property of branching, including diotactic), regio-regular or site-irregularity, long chain branching or hyper-branching. Multiblock copolymers are characterized by the distribution of specific polydispersity indices (PDI or M _w / M _n ), block length distribution and / or block number distribution due to specific copolymer preparation methods. More specifically, when produced in a continuous process, the polymer is about 1.7 to about 8, preferably about 1.7 to about 3.5, more preferably about 1.7 to about 2.5, most preferably about 1.8 to about 2.5 or It preferably has a PDI of about 1.8 to about 2.1. When produced in a batch or semi-batch method, the polymer is about 1.0 to about 2.9, preferably about 1.3 to about 2.5, more preferably about 1.4 to about 2.0, most preferably about 1.4 to about 1.8 Has a PDI. Note that “block (s)” and “segment (s)” are used interchangeably herein.

In the following description, all values disclosed herein are approximations whether or not the term "about" or "approximately" is used in this regard. They may vary by 1%, 2%, 5%, or sometimes 10-20%. When a numerical range having a lower limit (R ^L ) and an upper limit (R ^U ) is disclosed, any numerical value included in the range is specifically disclosed. Specifically, the following numerical values within the range are specifically disclosed: R = R ^L + k * (R ^U -R ^L ) where k is a variable ranging from 1% to 100% in 1% increments, ie k Is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99% or 100% being). In addition, any numerical range defined by two R values as defined above is also specifically disclosed.

Embodiments of the present invention provide a new class of ethylene / α-olefin block interpolymers (hereinafter “polymers of the invention”, “ethylene / α-olefin interpolymers” or variants thereof). Ethylene / α-olefin interpolymers comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form and feature multiple blocks or segments having two or more polymerized monomer units that differ in chemical or physical properties. It is done. In other words, the ethylene / α-olefin interpolymers are block interpolymers, preferably multiblock interpolymers or copolymers. The terms "interpolymer" and "copolymer" are used interchangeably herein. In some embodiments, the multiblock copolymer can be represented by the formula:

(AB) _n

Wherein n is an integer greater than or equal to 1, preferably greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, A and B are connected in a linear fashion rather than in a branched or star fashion. A "hard" segment refers to a block of polymerized units in which ethylene is present in an amount greater than 95% by weight, preferably greater than 98% by weight. That is, the comonomer content in the hard segments is less than 5% by weight, preferably less than 2% by weight. In some embodiments, the hard segments are all or substantially all composed of ethylene. On the other hand, a "soft" segment represents a block of polymerized units having a comonomer content of greater than 5%, preferably greater than 8%, greater than 10% or greater than 15% by weight. In some embodiments, the comonomer content in the soft segment is greater than 20 weight percent, greater than 25 weight percent, greater than 30 weight percent, greater than 35 weight percent, greater than 40 weight percent, greater than 45 weight percent, greater than 50 weight percent, or 60 weight percent. May be in excess.

In some embodiments, A blocks and B blocks are randomly distributed along the polymer chain. That is, the block copolymer typically does not have a structure such as AAA-AA-BBB-BB.

In other embodiments, the block copolymers typically do not have a third type of block. In another embodiment, block A and block B each have monomers or comonomers randomly distributed within the block. That is, block A and block B both do not include two or more segments (or sub-blocks) with different compositions, such as tip segments having a different composition than the remaining blocks.

The ethylene / α-olefin interpolymers are characterized by an average block index (ABI) of greater than 0 and up to about 1.0, and a molecular weight distribution (M _w / M _n ) of greater than about 1.3. The average block index (ABI) is the fractionation of the polymer by preparative TREF (i.e. temperature rising elution fractionation) at 20 ° C to 110 ° C in 5 ° C increments (other temperature increments such as 1 ° C, 2 ° C, 10 ° C may be used). ) Is the weight average of the block index ("BI") of each polymer fraction obtained.

Wherein BI _i is the block index for the i-th fraction of the ethylene / α-olefin interpolymers of the invention obtained in the preparative TREF and w _i is the weight percent of the i-th fraction. Similarly, the square root of the second moment with respect to the mean value (hereinafter referred to as the second moment weight average block index) may be defined as follows.

Wherein N is defined as the number of fractions with BI _i greater than zero. Referring to FIG. 9, for each polymer fraction, BI is defined by one of the following two equations (both give the same BI value).

Wherein T _X is the ATREF (ie analytical TREF) elution temperature (preferably expressed in Kelvin) for the i th fraction, and P _X is the i th fraction that can be measured by NMR or IR as follows: Ethylene mole fraction. P _AB is the ethylene mole fraction of the total ethylene / α-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. T _A and P _A are the ATREF elution temperature and ethylene mole fraction for pure “hard segments” (referring to the crystalline segments of the interpolymer). Approximately, or for polymers that do not know the "hard segment" composition, the T _A and P _A values are set to the values for the high density polyethylene homopolymer.

T _AB is the ATREF elution temperature for the random copolymer having the same composition (ethylene mole fraction is P _AB ) and molecular weight as the copolymer of the present invention. T _AB can be calculated from the mole fraction of ethylene (measured by NMR) using the following equation.

Ln P _AB = α / T _AB + β

Wherein α and β are two constants that can be determined by correcting using a number of well characterized preparative TREF fractions for a wide range of random copolymers and / or a well characterized random ethylene copolymer of narrow composition. It should be noted that α and β may vary from instrument to instrument. In addition, using the appropriate molecular weight range and comonomer type for the random copolymer and / or preparative TREF fraction used to obtain the calibration curve, it is necessary to obtain the appropriate calibration curve by the polymer composition of interest. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, this effect is essentially negligible. In some embodiments as shown in FIG. 8, the random ethylene copolymer and / or preparative TREF fractions satisfy the following relationship.

Ln P = -237.83 / T _ATREF + 0.639

The correction equation _relates to the molar fraction (P) of ethylene with respect to the TREF fraction for the preparation of the random copolymer of wide composition and / or the analytical TREF elution temperature (T _ATREF ) of the narrow copolymer of narrow composition. T _XO is the ATREF temperature for a random copolymer having the same composition (ie, the same comonomer type and content) and the same molecular weight and whose ethylene mole fraction is P _X. T _XO can be calculated from LnP _X = α / T _XO + β by the P _X mole fraction measurement. Conversely, P _XO is the ethylene mole fraction for a random copolymer having the same composition (ie, the same comonomer type and content) and the same molecular weight, and the ATREF temperature is T _X , which is determined using the T _X measurement using Ln P _XO = It can be calculated from α / T _X + β.

Once the block index (BI) for each preparative TREF fraction is obtained, the weight average block index (ABI) for the entire polymer can be calculated. In some embodiments, ABI is greater than zero but less than about 0.4, or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.4 and up to about 1.0. Preferably, the ABI should range from about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some embodiments, ABI ranges from about 0.3 to about 0.9, about 0.3 to about 0.8, about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, ABI ranges from about 0.4 to about 1.0, about 0.5 to about 1.0, about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.

Another feature of the ethylene / α-olefin interpolymers of the present invention is that the ethylene / α-olefin interpolymers of the present invention have at least one polymer fraction having a block index greater than about 0.1 and up to about 1.0, which can be obtained by preparative TREF. Wherein the molecular weight distribution (M _w / M _n ) of the polymer is 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 another embodiment, 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 another embodiment, 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.

In addition to the average block index and the individual fraction block index, the ethylene / α-olefin interpolymers are characterized by one or more of the following characteristics.

In one aspect, the ethylene / α-olefin interpolymers used in embodiments of the present invention have an M _w / M _n of about 1.7 to about 3.5, and at least one melting point (T _m ) (degrees C) and density (d) ( g / cm ³ ), and the values of these variables correspond to the following relations.

T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ,

Preferably T _m ≧ −6288.1 + 13141 (d) -6720.3 (d) ² ,

More preferably T _m ≥ 858.91-1825.3 (d) + 1112.8 (d) ² .

This melting point / density relationship is shown in FIG. 1. Unlike typical random copolymers of ethylene / α-olefins, which have a lower melting point with decreasing density, the interpolymers of the present invention (denoted as diamonds), especially when the density is from about 0.87 g / cc to about 0.95 g / cc It shows a melting point that is substantially independent of density. For example, the melting point of such polymers ranges from about 110 ° C. to about 130 ° C. when the density is between 0.875 g / cc and about 0.945 g / cc. In some embodiments, the melting point of such polymers range from about 115 ° C. to about 125 ° C. when the density ranges from 0.875 g / cc to about 0.945 g / cc.

In another aspect, the ethylene / α-olefin interpolymers comprise ethylene and one or more α-olefins in polymerized form, wherein the temperature of the maximum differential scanning calorimetry (“DSC”) peak—the highest crystallization analysis fractionation (“CRYSTAF ΔT (degrees Celsius), defined as the temperature of the peak, and the heat of fusion ΔH (J / g), wherein ΔT and ΔH are the following relations for ΔH of 130 J / g or less: To satisfy.

ΔT> -0.1299 (ΔH) + 62.81,

Preferably ΔT ≧ −0.1299 (ΔH) +64.38,

More preferably ΔT ≧ −0.1299 (ΔH) +65.95.

In addition, when (DELTA) H exceeds 130 J / g, (DELTA) T is 48 degreeC or more. CRYSTAF peaks are measured using at least 5% of the cumulative polymer (ie, peaks must represent at least 5% of the cumulative polymer), and if less than 5% of the polymers have an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C. And ΔH are numerical values of heat of fusion (J / g). More preferably, the highest CRYSTAF peak contains at least 10% of the cumulative polymer. 2 shows the data plotted for the polymers of the invention as well as the comparative examples. The integral peak area and peak temperature are calculated with a computerized drawing program provided by the instrument manufacturer. The diagonal line shown for the random ethylene octene comparison polymer corresponds to the equation ΔT = −0.1299 (ΔH) +62.81.

In another aspect, the ethylene / α-olefin interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using temperature eluting fractionation (“TREF”), which fractions elute at the same temperature range. Characterized by having a comonomer molar content higher than the comonomer molar content of the comparative random ethylene interpolymer fraction, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer Contains the same comonomer (s) as the blocked interpolymer and has a melt index, density and comonomer molar content (based on total polymer) within 10% of the block interpolymer. Preferably, M _w / M _n of the comparative interpolymer is also within 10% of M _w / M _n of the block interpolymer, and / or the total comonomer content of the comparative interpolymer is within 10% by weight of the block interpolymer. to be.

In another aspect, the ethylene / α-olefin interpolymers are characterized by 300% strain and elastic recovery in one cycle (Re) (%) as measured on compression molded films of ethylene / α-olefin interpolymers, Having a density (d) (g / cm ³ ), wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers do not substantially comprise a crosslinked phase.

Re> 1481-1629 (d);

Preferably Re ≧ 1491-1629 (d);

More preferably Re ≧ 1501-1629 (d);

Even more preferably Re ≧ 1511-1629 (d).

3 shows the effect of density on elastic recovery for non-oriented films made from certain interpolymers and conventional random copolymers of the present invention. At the same density, the inventive interpolymers have substantially higher elastic recovery.

In some embodiments, the ethylene / α-olefin interpolymer has a tensile strength of greater than 10 MPa, preferably of at least 11 MPa, more preferably of at least 13 MPa, and / or of 11 cm / min crosshead It has a breaking elongation of at least 600%, more preferably at least 700%, very preferably at least 800% and most very preferably at least 900% at the separation rate.

In another embodiment, the ethylene / α-olefin interpolymer has (1) a storage modulus ratio G ′ (25 ° C.) / G ′ (100 ° C.) of 1 to 50, preferably 1 to 20, more preferably 1 To 10 and / or; (2) 70 ° C. Compression set is less than 80%, preferably less than 70%, especially less than 60%, less than 50%, or less than 40% to 0%.

In another embodiment, the ethylene / α-olefin interpolymer has a 70 ° C. compression set of less than 80%, less than 70%, less than 60%, or less than 50%. Preferably, the 70 ° C. compression set of the interpolymer is less than 40%, less than 30%, less than 20% and can be reduced to about 0%.

In some embodiments, the ethylene / α-olefin interpolymer has a heat of fusion less than 85 J / g, and / or 100 lb / ft ² (4800 Pa) or less, preferably 50 lb / ft ² (2400 Pa) or less , In particular, has a pellet blocking strength of less than 5 lb / ft ² (240 Pa) and also as low as 0 lb / ft ² (0 Pa).

In other embodiments, the ethylene / α-olefin interpolymers comprise at least 50 mol% ethylene in polymerized form and have a 70 ° C. compression set of less than 80%, preferably less than 70%, or less than 60%, most Preferably it is less than 40-50% and decreases to near 0%.

In some embodiments, the multiblock copolymer has a PDI that fits the Schultz-Flory distribution rather than the Poisson distribution. The copolymer has both a polydisperse block distribution and a polydisperse block size distribution, and is also characterized by having the most possible block length distribution. Preferred multiblock copolymers are copolymers containing four or more blocks or segments, including terminal blocks. More preferably, the copolymer comprises 5, 10 or 20 or more blocks or segments, including end blocks.

In addition, the block interpolymers of the present invention have additional features or characteristics. In one aspect, the interpolymers, preferably comprising polymerized forms of ethylene and at least one copolymerizable comonomer, are a plurality of blocks or segments, most preferably having two or more polymerized monomer units that differ in chemical or physical properties. Is characterized by a multiblock copolymer (blocked interpolymer), wherein the block interpolymer has molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF, and the fractions are eluted at the same temperature range. Characterized in that it has a comonomer molar content higher than the comonomer molar content of the random ethylene interpolymer fraction, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer 10 of the blocked interpolymer containing the same comonomer (s) as the blocked interpolymer A melt index, density, and molar comonomer content within has a (total polymer basis). Preferably, M _w / M _n of the comparative interpolymer is also within 10% of M _w / M _n of the blocked interpolymer, and / or the total comonomer content of the comparative interpolymer is 10 weight of the blocked interpolymer. It is within%.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred. In addition, in the case of polymers or blends of polymers having a relatively wide TREF curve, first the TREF is used to fractionate the polymers into fractions each having an elution 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, the block interpolymers have one or more fractions having a higher comonomer molar content than the corresponding fractions of the comparative interpolymers.

In another aspect, the polymer of the present invention preferably comprises a plurality of blocks comprising two or more polymerized monomer units, preferably comprising polymerized forms of ethylene and one or more copolymerizable comonomers and having different chemical or physical properties ( That is, olefin interpolymers (blocked interpolymers) characterized by two or more blocks) or segments, most preferably multiblock copolymers, which block elution (individual fractions) which elute at 40 ° C. to 130 ° C. Collected and / or not isolated) peaks (not molecular fractions only), which peaks have a comonomer content predicted by infrared spectroscopy at development using a full width at half maximum (FWHM) area calculation, and a full width at half maximum (FWHM) ) Higher than the average comonomer molar content of the comparative random ethylene interpolymer peak at the same elution temperature developed using area calculation. Preferably at least 5% higher, more preferably at least 10% higher average comonomer molar content, wherein the comparative random ethylene interpolymer has the same comonomer (s) as the blocked interpolymer Melt index, density and comonomer molar content (based on total polymer) within 10% of block interpolymers. Preferably, M _w / M _n of the comparative interpolymer is also within 10% of M _w / M _n of the blocked interpolymer, and / or the total comonomer content of the comparative interpolymer is 10% by weight of the block interpolymer. Within. The full width at half maximum (FWHM) calculation is based on the ratio of methyl to methylene reaction area [CH ₃ / CH ₂ ] from the ATREF infrared detector, where the highest (maximum) peak is identified from the baseline and thus the FWHM area is determined. In the distribution measured using the ATREF peak, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T ₁ and T ₂ are horizontal lines to the baseline after dividing the ATREF peak height by 2 (ATREF Traversing the left and right sides of the curve) to determine the left and right sides of the ATREF peak. A calibration curve for comonomer content is obtained by plotting the FWHM area ratio of comonomer content from NMR to TREF peak using a random ethylene / α-olefin copolymer. In this infrared method, a calibration curve is obtained for the same comonomer type of interest. The comonomer content of the TREF peak of the polymers of the present invention can be measured with reference to such calibration curves using the FWHM methyl: methylene area ratio [CH ₃ / CH ₂ ] of its TREF peak.

Comonomer content can be measured using any suitable technique using techniques based on preferred nuclear magnetic resonance (NMR) spectroscopy. Using this technique, the blocked interpolymers have a higher comonomer molar content than the corresponding comparative interpolymers.

Preferably, in the interpolymers of ethylene and 1-octene, the block interpolymers have a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. of at least (-0.2013) T + 20.07, more preferably (- Greater than or equal to 0.2013) T + 21.07 (where T is the value of the peak elution temperature of the compared TREF fraction, measured in ° C.).

FIG. 4 graphically illustrates embodiments of block interpolymers of ethylene and 1-octene and plots of comonomer content versus TREF elution temperature for various comparative ethylene / 1-octene interpolymers (random copolymers). (-0.2013) fitted to the line (solid line) representing T + 20.07. The line of Equation (-0.2013) T + 21.07 is shown as a dotted line. Also shown is the comonomer content for the fractions of ethylene / 1-octene block interpolymers according to embodiments of the present invention. All block interpolymer fractions had significantly higher 1-octene content compared to the line at equivalent elution temperatures. These results are characteristic of the interpolymers of the present invention, which are believed to be due to the presence of differentiated blocks in the polymer chain having both crystalline and amorphous properties.

FIG. 5 graphically illustrates the TREF curve and comonomer content for the polymer fractions of Example 5 and Comparative Example F, discussed below. Peaks eluting at 40 ° C. to 130 ° C., preferably 60 ° C. to 95 ° C., for the two polymers were fractionated in 5 ° C. increments. Actual data for three of the fractions of Example 5 are shown as triangles. Those skilled in the art will appreciate that appropriate calibration curves for interpolymers can be constructed while varying comonomer content to match the ATREF temperature value. Preferably, this calibration curve is obtained using a comparative interpolymer having the same monomer, preferably a random copolymer made using metallocene or other homogeneous catalyst composition. The interpolymers of the present invention are characterized by a comonomer molar content of greater than, preferably at least 5% and more preferably at least 10% greater than the value measured from the calibration curve at the same ATREF elution temperature.

In addition to the foregoing aspects and properties described herein, the polymers of the present invention may be characterized as having one or more additional features. In one aspect, the polymer of the invention preferably comprises a plurality of blocks or segments comprising two or more polymerized monomer units, preferably in polymerized form, comprising ethylene and one or more copolymerizable comonomers in different chemical or physical properties. Olefin interpolymers (blocked interpolymers), most preferably multiblock copolymers, characterized in that the block interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments. Is a comonomer mole higher than the comonomer mole content of the comparative random ethylene interpolymer fraction eluting in the same temperature range, preferably at least 5% higher, more preferably at least 10%, 15%, 20% or 25% higher. Content, wherein the comparative random ethylene interpolymer is the same as the blocked interpolymer Including a comonomer (s) and, preferably, has the same comonomer (s), and a mixed blocked less than 10% the melt index, density, and molar comonomer content of the polymer (based on total polymer). Preferably, M _w / M _n of the comparative interpolymer is also within 10% of M _w / M _n of the blocked interpolymer, and / or the total comonomer content of the comparative interpolymer is 10 weight of the blocked interpolymer. It is within%.

Preferably, the interpolymer has, in particular, a total polymer density of from about 0.855 to about 0.935 g / cm ³ , more particularly the polymer has more than about 1 mol% comonomer, and the blocked interpolymer is from 40 ° C. to The comonomer content of the TREF fraction eluted at 130 ° C. is greater than or equal to (-0.1356) T + 13.89, more preferably greater than or equal to (−0.1356) T + 14.93, most preferably greater than or equal to (-0.2013) T + 21.07. A quantity of at least an interpolymer of ethylene and at least one α-olefin, where T is the value of the peak ATREF elution temperature of the compared TREF fraction, measured in degrees Celsius.

In another aspect, the polymer of the invention preferably comprises a plurality of blocks comprising two or more polymerized monomer units, preferably in polymerized form, comprising ethylene and one or more copolymerizable comonomers in different chemical or physical properties, or Olefin interpolymers (blocked interpolymers) characterized by segments, most preferably multiblock copolymers, said block interpolymers having molecular fractions which elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, All fractions having a comonomer content of at least about 6 mol% have a melting point above about 100 ° C. For fractions having a comonomer content of about 3 mol% to about 6 mol%, all fractions have a DSC melting point of about 110 ° C. or greater. More preferably, the polymer fraction having at least 1 mol% comonomer has a DSC melting point corresponding to the following formula.

Tm ≥ (-5.5926) (mol% of comonomer in the fraction) + 135.90

In another aspect, the polymer of the invention preferably comprises a plurality of blocks comprising two or more polymerized monomer units, preferably in polymerized form, comprising ethylene and one or more copolymerizable comonomers in different chemical or physical properties, or Olefin interpolymers (blocked interpolymers) characterized by segments, most preferably multiblock copolymers, said block interpolymers having molecular fractions which elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, All fractions having an ATREF elution temperature above about 76 ° C. are characterized by having a melting enthalpy (heat of fusion) corresponding to the following equation as determined by DSC.

Heat of fusion (J / g) ≤ (3.1718) (ATREF elution temperature (Celsius))-136.58

The block interpolymers of the present invention have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, and all fractions having ATREF elution temperatures of 40 ° C. to less than about 76 ° C. It is characterized by having a melting enthalpy (heat of fusion) corresponding to the equation.

Heat of fusion (J / g) ≤ (1.1312) (ATREF elution temperature (Celsius)) + 22.97

Measured by an infrared detector ATREF  peak Comonomer  Furtherance

The comonomer composition of the TREF peak can be measured using an IR4 infrared detector available from Polymer Char (Valencia, Spain) ( http://www.polymerchar.com/ ).

The "composition mode" of the detector is equipped with a measuring sensor (CH ₂ ) and a composition sensor (CH ₃ ) (fixed narrow band infrared filter in the region of 2800 to 3000 cm ^-1 ). The measurement sensor detects methylene (CH ₂ ) carbon on the polymer, which is directly related to the polymer concentration in solution, and the composition sensor detects the methyl (CH ₃ ) group of the polymer. The mathematical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH ₂ ) is sensitive to the comonomer content of the polymer in the measured solution and its response is corrected by known ethylene alpha-olefin copolymer standards.

The detector, when used with an ATREF instrument, provides both the concentration (CH ₂ ) and composition (CH ₃ ) signal response of the polymer eluted during the TREF process. Polymer specific correction can be obtained by measuring the area ratio of CH ₃ to CH ₂ to the polymer by known comonomer content (preferably determined by NMR). The comonomer content of the ATREF peak of the polymer can be predicted by applying a baseline correction of the area ratio for the individual CH ₃ and CH ₂ reactions (ie, area ratio CH ₃ / CH ₂ to comonomer content).

The area of the peak can be calculated using the full width at half maximum (FWHM) calculation after integrating the individual signal responses from the TREF chromatogram using the appropriate baseline. The full width at half maximum is based on the ratio of methyl to methylene reaction area [CH ₃ / CH ₂ ] from the ATREF infrared detector, where the highest (maximum) peak is identified from the baseline and thus the FWHM area is determined. In the distribution measured using the ATREF peak, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T ₁ and T ₂ are horizontal lines to the baseline after dividing the ATREF peak height by 2 (ATREF Traversing the left and right sides of the curve) to determine the left and right sides of the ATREF peak.

The application of infrared spectroscopy to determine the comonomer content of polymers in this ATREF-infrared method is in principle similar to that of the GPC / FTIR system 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-FTIR)", Polymer (2002), 43, 59-170.] Introduced for reference).

It should be noted that while in the above description the TREF fraction is obtained in 5 ° C. increments, other temperature increments are possible. For example, the TREF fraction can be obtained in 4 ° C. increments, 3 ° C. increments, 2 ° C. increments, or 1 ° C. increments.

For the copolymer of ethylene and an α-olefin, the polymer of the present invention is preferably (1) 1.3 or more, more preferably 1.5 or more, 1.7 or more, or 2.0 or more, most preferably 2.6 or more, maximum 5.0 or less, More preferably a PDI of at most 3.5, in particular at most 2.7; (2) heat of fusion of up to 80 J / g; (3) an ethylene content of at least 50% by weight; (4) has a glass transition temperature (Tg) of less than -25 ° C, more preferably less than -30 ° C, and / or (5) one, also a single, T _m .

In addition, the polymers of the present invention have a storage modulus (G ′) at a temperature of 100 ° C. of which log (G ′) is at least 400 kPa, preferably at least 1.0 MPa, alone or in combination with any other properties. Can be. In addition, the polymers of the present invention have a relatively uniform storage modulus as a function of temperature in the range of 0 to 100 ° C. (shown in FIG. 6), which is a property of the block copolymer, which is characterized in that at least one of olefin copolymers, in particular ethylene, for C _{3 -8} aliphatic copolymers of α- olefin is unknown up to now. (In this context, the term "relatively uniform" means that the log G '(Pa) is reduced to less than one digit range at 50 to 100 ° C, preferably 0 to 100 ° C.)

The interpolymers of the present invention may be further characterized by a thermomechanical analysis penetration depth of 1 mm and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa) at temperatures above 90 ° C. Alternatively, the inventive interpolymers can have a thermomechanical analysis penetration depth of 1 mm and a flexural modulus of at least 3 kpsi (20 MPa) at temperatures of 104 ° C. or higher. They are characterized by having a wear resistance (volume loss) of less than 90 mm ³ . 7 shows the TMA (1 mm) for the flexural modulus of the polymers of the present invention compared to other known polymers. The polymers of the present invention have a significantly better flexibility-heat resistance balance than other polymers.

In addition, the ethylene / α-olefin interpolymers may be used in an amount of 0.01 to 2000 g / 10 minutes, preferably 0.01 to 1000 g / 10 minutes, more preferably 0.01 to 500 g / 10 minutes, especially 0.01 to 100 g / 10 minutes. May have a melt index (I ₂ ). In certain embodiments, the ethylene / α-olefin interpolymer has 0.01 to 10 g / 10 minutes, 0.5 to 50 g / 10 minutes, 1 to 30 g / 10 minutes, 1 to 6 g / 10 minutes, or 0.3 to 10 g Melt index (I ₂ ) of 10 minutes. In certain embodiments, the melt index of the ethylene / α-olefin polymer is 1 g / 10 minutes, 3 g / 10 minutes or 5 g / 10 minutes.

The polymer has a molecular weight (M) of 1,000 g / mol to 5,000,000 g / mol, preferably 1000 g / mol to 1,000,000, more preferably 10,000 g / mol to 500,000 g / mol, in particular 10,000 g / mol to 300,000 g / mol _w ). The density of the polymer of the present invention may be 0.80 to 0.99 g / cm ³ , preferably 0.85 g / cm ³ to 0.97 g / cm ³ for ethylene containing polymers. In certain embodiments, the density of the ethylene / α-olefin polymer is in the range of 0.860 to 0.925 g / cm ³ or 0.867 to 0.910 g / cm ³ .

Methods of making polymers are disclosed in the following patent applications: US Provisional Application No. 60 / 553,906, filed March 17, 2004; 60 / 662,937, filed March 17, 2005; 60 / 662,939, filed March 17, 2005; 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 / US2005 / 008917, filed March 17, 2005, all of which are incorporated herein by reference in their entirety. For example, one such method involves the process of adding ethylene and optionally one or more addition polymerizable monomers other than ethylene under addition polymerization conditions,

(A) a first olefin polymerization catalyst having a high comonomer incorporation index,

(B) a second olefin polymerization catalyst having a comonomer incorporation index of less than 90%, preferably less than 50%, most preferably less than 5% of the comonomer incorporation index of catalyst (A), and

(C) mixtures or reaction products formed by combining chain transfer agents

It comprises contacting with a catalyst composition comprising a.

Representative catalysts and chain transfer agents are as follows.

Catalyst (A1) : [N- (2,6-di (1-methylethyl) phenyl) amido prepared according to the teachings of WO 03/40195, US Pat. Nos. 6,953,764 and 6,960,635, and WO 04/24740. (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A2) : [N- (2,6-di (1-methylethyl) phenyl) amido prepared according to the teachings of WO 03/40195, US Pat. Nos. 6,953,764 and 6,960,635, and WO 04/24740. (2-methylphenyl) (1,2-phenylene- (6-pyridine-2-diyl) methane)] hafnium dimethyl.

Catalyst (A3) : Bis [N, N '"-(2,4,6-tri (methylphenyl) amido) ethylenediamine] hafnium dibenzyl.

Catalyst (A4) : Bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2- substantially prepared according to the teachings of US Pat. No. 6,897,276 Phenoxymethyl) cyclohexane-1,2-diyl zirconium (IV) dibenzyl.

Catalyst (B1) : 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl .

Catalyst (B2): 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (2-methylcyclohexyl) -imino) methyl) (2-oxoyl) zirconium Dibenzyl.

Catalyst ( C1 ) : (t-butylamido) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a-η-inden-1-yl substantially prepared according to the teachings of US Pat. No. 6,268,444 Silantitanium dimethyl.

Catalyst ( C2 ) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a-η-indene-1 substantially prepared according to the teachings of US Pat. No. 6,825,295 -Yl) silanetitanium dimethyl.

Catalyst ( C3 ) : substantially (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a-η-s-, prepared according to the teachings of US Pat. No. 6,825,295 Sen-1-yl) silanetitanium dimethyl.

Catalyst ( D1 ) : Bis (dimethyldisiloxane) (inden-1-yl) zirconium dichloride available from Sigma-Aldrich.

Transfer agent : The transfer agent used was diethylzinc, di (i-butyl) zinc, di (n-hexyl) zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum bis (dimethyl (t-butyl) Siloxane), i-butylaluminum bis (di (trimethylsilyl) amide), n-octylaluminum di (pyridine-2-methoxide), bis (n-octadecyl) i-butylaluminum, i-butylaluminum bis (di (n-pentyl) amide), n-octyl aluminum bis (2,6-di-t-butylphenoxide, n-octyl aluminum di (ethyl (1-naphthyl) amide), ethyl aluminum bis (t-butyldimethyl Siloxide), ethylaluminum di (bis (trimethylsilyl) amide), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis (2,3,6 , 7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis (dimethyl (t-butyl) siloxide, ethylzinc (2,6-diphenylphenoxide) and ethylzinc (t-butoxide) It includes.

Preferably, the method includes using a plurality of catalysts that can not be interconversion of block copolymers, especially multi-block copolymer, preferably two or more monomers, more especially ethylene and a C _{3 -20} olefin or cycloolefin, and most specially it takes the form of a continuous solution process for the production of ethylene and C _{4 -20} linear multi-block of the α- olefin copolymer. That is, the catalyst is chemically different. Under continuous solution polymerization conditions, the process is ideally suited for the polymerization of monomer mixtures of high monomer conversion. Under these polymerization conditions, the transfer from the chain transfer agent to the catalyst is favored over the chain growth, so that multiblock copolymers, especially linear multiblock copolymers, are formed with high efficiency.

The interpolymers of the present invention can be differentiated from conventional random copolymers, physical blends of polymers and block copolymers prepared by sequential monomer addition, flow catalysts, anionic or cationic living polymerization techniques. In particular, compared to random copolymers having the same monomer and monomer content at equivalent crystallinity or modulus, the inventive interpolymers have better (higher) heat resistance (measured by melting point), higher TMA penetration temperature, higher hot tension Strength and / or high hot torsional storage modulus (measured by dynamic mechanical analysis). Compared to random copolymers having the same monomers and monomer content, the interpolymers of the invention have lower compression set, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, especially at elevated temperatures, Faster set-up due to higher crystallization (solidification) temperature, higher recovery rate (especially at elevated temperatures), better wear resistance, higher shrinkage, and better oil and filler tolerance.

The interpolymers of the present invention also exhibit specific crystallization and branching distribution relationships. That is, the interpolymers of the present invention are CRYSTAF as a function of heat of fusion, in particular compared to random copolymers or physical blends of polymers containing the same monomers and monomer concentrations, such as blends of high density polymers and low density copolymers at equivalent overall density and There is a relatively large difference between the highest peak temperatures measured using DSC. This particular feature of the inventive interpolymers is due to the unique comonomer distribution in the blocks in the polymer backbone. In particular, the interpolymers of the present invention may include alternating blocks (including homopolymer blocks) having different comonomer contents. The interpolymers of the present invention may comprise a distribution that is a Schultz-Florie distribution in the number and / or block size of polymer blocks having different densities or comonomer contents. In addition, the inventive interpolymers also have specific peak melting points and crystallization temperatures that are substantially independent of polymer density, modulus, and shape. In a preferred embodiment, the order of the microcrystals of the polymer exhibits characteristic spherulite and lamella, even distinguishable from random or block copolymers, even at PDI values of less than 1.7, or less than 1.5 and also less than 1.3.

In addition, the interpolymers of the present invention can be prepared using techniques that affect the degree or level of blocking. That is, the length and amount of comonomers of each polymer block and segment can be varied by controlling the ratio and type of catalyst and transfer agent as well as the polymerization temperature, and other polymerization parameters. A surprising advantage of this phenomenon is the discovery that as the degree of blocking increases, the optical properties, tear strength and high temperature recovery properties of the resulting polymers improve. In particular, as the average number of blocks in the polymer increases, the haze decreases with increasing transparency, tear strength and high temperature recovery properties. By selecting a combination of a catalyst and a transfer agent having the desired chain transfer capacity (high transfer rate at low chain termination), other forms of polymer termination are effectively suppressed. Thus, the polymerization of ethylene / α-olefin comonomer mixtures according to embodiments of the present invention results in very little β-hydride removal, even when present, and the resulting crystalline blocks have little or no long chain branching and are very or substantially Completely linear.

Polymers with highly crystalline chain ends can optionally be prepared in accordance with embodiments of the present invention. In elastomer applications, reducing the relative amount of polymer terminated by amorphous blocks reduces the effect of intermolecular dilution on crystalline regions. These results can be obtained by selecting chain transfer agents and catalysts having an appropriate reaction with hydrogen or other chain terminators. Specifically, catalysts that produce highly crystalline polymers (such as by the use of hydrogen, for example) in comparison to catalysts that produce polymer segments that are less crystalline (e.g., by large comonomer incorporation, site-error or atactic polymer formation). If more susceptible to chain termination, the highly crystalline polymer segment occupies the terminal portion of the polymer. Not only are the resulting end groups crystalline, but upon termination, a highly crystalline polymer forming catalyst site is available for resumption of polymer formation once again. Thus, the initially formed polymer is another highly crystalline polymer segment. Thus, both ends of the resulting multiblock copolymer are predominantly highly crystalline.

The ethylene / α-olefin interpolymers used in the embodiments of the present invention are preferably interpolymers of ethylene and at least one C ₃ -C ₂₀ α-olefin. Particular preference is given to copolymers of ethylene and C ₃ -C ₂₀ α-olefins. The interpolymers may further comprise C ₄ -C ₁₈ diolefins and / or alkenylbenzenes. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes and the like. Examples of such comonomers are C ₃ -C ₂₀ α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene , 1-nonene, 1-decene and the like. Particular preference is given to 1-butene and 1-octene. Other suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene and naphthenic components (eg cyclopentene, cyclohexene and Cyclooctene).

Although ethylene / α-olefin interpolymers are preferred polymers, other ethylene / olefin polymers may be used. Olefin as used herein refers to a group of unsaturated hydrocarbon-based compounds having at least one carbon-carbon double bond. Depending on the choice of catalyst, any olefin can be used in embodiments of the present invention. Preferably, suitable olefins are C ₃ -C ₂₀ aliphatic and aromatic compounds containing vinylic unsaturated groups, and cyclic compounds such as cyclobutene, cyclopentene, dicyclopentadiene and norbornene (positions 5 and 6) To norbornene substituted with a C ₁ -C ₂₀ hydrocarbyl or cyclohydrocarbyl group). Mixtures of the olefins as well as mixtures of C ₄ -C ₄₀ diolefin compounds with the olefins are included.

Examples of olefin monomers include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4 Vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C ₄ -C ₄₀ diene (1,3-butadiene, 1,3 -Pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene), other C ₄ -C ₄₀ α- Olefins and the like, but are not limited thereto. In certain embodiments, the α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or a combination thereof. Any hydrocarbon containing a vinyl group may be used in embodiments of the present invention, but as the molecular weight of the monomers becomes too high, practical problems such as monomer availability, cost, and the ability to conveniently remove unreacted monomers from the resulting polymers are further increased. It can be a problem.

The polymerization process described herein is well suited for the preparation of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butyl styrene and the like. In particular, interpolymers comprising ethylene and styrene can be prepared according to the teachings herein. Optionally, copolymers comprising optionally C ₄ -C ₂₀ dienes, including ethylene, styrene and C ₃ -C ₂₀ alpha olefins with improved properties can be prepared.

Suitable nonconjugated diene monomers may be straight, branched or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable nonconjugated dienes include 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 -Methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyriene and dihydrooxyene, monocyclic alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and multicyclic alicyclic conjugated and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- ( 2,2,1) -hepta-2,5-diene; Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene Butene, 5-vinyl-2-norbornene and norbornadiene. Among the dienes typically used for EPDM preparation, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB ), 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of preferred polymers that can be prepared according to the invention are elastomeric interpolymers of ethylene, C ₃ -C ₂₀ α-olefins, in particular propylene, and optionally one or more diene monomers. Preferred α-olefins for use in this embodiment of the invention are represented by the formula CH ₂ = CHR ^{* wherein} R ^* is a linear or branched alkyl group having from 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularly preferred α-olefins are propylene. Propylene based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in preparing such polymers, especially multiblock EPDM type polymers, include conjugated or nonconjugated, straight or branched chain, cyclic or polycyclic dienes comprising 4 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene and 5-butylidene-2-norbornene Include. Particularly preferred dienes are 5-ethylidene-2-norbornene.

Diene-containing polymers contain alternating segments or blocks containing more or less amounts of dienes (including if not present) and α-olefins (including if not present), thereby reducing diene without subsequent loss of polymer properties. And the total amount of α-olefins can be reduced. That is, since dienes and α-olefin monomers are predominantly incorporated into one type of polymer block rather than uniformly or randomly incorporated throughout the polymer, they are used more effectively, and the crosslinking density of the polymer can then be better controlled. . Such crosslinkable elastomers and cured products have advantageous properties, including higher tensile strength and better elastic recovery.

In some embodiments, interpolymers of the invention prepared by two catalysts incorporating different amounts of comonomer have a weight ratio of the blocks formed thereby from 95: 5 to 5:95. The elastomeric polymer preferably has 20 to 90% ethylene content, 0.1 to 10% diene content and 10 to 80% α-olefin content, based on the total weight of the polymer. More preferably, the multiblock elastomeric polymer has an ethylene content of 60 to 90%, a diene content of 0.1 to 10% and an α-olefin content of 10 to 40% based on the total weight of the polymer. Preferred polymers have a weight average molecular weight (M _w ) of 10,000 to about 2,500,000, preferably 20,000 to 500,000, more preferably 20,000 to 350,000, a polydispersity of less than 3.5, more preferably less than 3.0, Mooney) high molecular weight polymer having a viscosity (ML (1 + 4) 125 ° C.) of 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75%, a diene content of 0 to 6% and an α-olefin content of 20 to 35%.

Ethylene / α-olefin interpolymers can be functionalized by incorporating one or more functional groups into their polymer structure. Examples of functional groups may include, for example, ethylenically unsaturated monofunctional and difunctional carboxylic acids, ethylenically unsaturated monofunctional and difunctional carboxylic anhydrides, salts thereof and esters thereof. Such functional groups may be grafted onto ethylene / α-olefin interpolymers or copolymerized with ethylene and any additional comonomers to form interpolymers of ethylene, functional comonomers and optionally other comonomer (s). Can be. Means for grafting functional groups onto polyethylene are described, for example, in US Pat. Nos. 4,762,890, 4,927,888 and 4,950,541, the disclosures of which are incorporated herein by reference in their entirety. One particularly useful group is maleic anhydride.

The amount of functional groups present in the functional interpolymer can vary. The functional group may typically be present in the copolymerized functionalized interpolymer in an amount of at least about 1.0 wt%, preferably at least about 5 wt%, more preferably at least about 7 wt%. The functional group is typically present in the copolymerized functionalized interpolymer in an amount of less than about 40 weight percent, preferably less than about 30 weight percent, more preferably less than about 25 weight percent.

Additional explanation of block index

The random copolymer satisfies the following relationship. See P. All. J. Flory, Trans. Faraday Soc., 51, 848 (1955).

<Equation 1>

In Equation 1, the mole fraction (P) of the crystallizable monomer is related to the melting temperature (T _m ) of the copolymer and the melting temperature (T _m ⁰ ) of the pure crystallizable homopolymer. The equation is similar to the relationship to the natural logarithm of the mole fraction of ethylene as the inverse function of ATREF elution temperature (° K) as shown in FIG. 8 for various copolymers of ethylene and olefins that are uniformly branched.

As shown in FIG. 8, the relationship between the ethylene mole fraction, ATREF peak elution temperature and DSC melting temperature for various uniformly branched copolymers is similar to the Flori's equation. Similarly, almost all random copolymers and preparative TREF fractions of random copolymer blends are also included in this trend except for small molecular weight effects.

According to Flory, if the mole fraction (P) of ethylene is equal to the conditional probability that one ethylene unit precedes or follows another ethylene unit, the polymer is a random polymer. On the other hand, if the conditional probability that any two ethylene units appear sequentially is greater than P, the copolymer is a block copolymer. Alternate copolymers are provided where the conditional probability is less than P.

The mole fraction of ethylene in the random copolymer primarily determines the specific distribution of ethylene segments where the crystallinity behavior is governed by the minimum equilibrium crystal thickness at a given temperature. Thus, the copolymer melting and TREF crystallization temperatures of the block copolymers of the present invention are related to the degree of departure from the random relationship in FIG. 8, which indicates that a given TREF fraction is added to its random equivalent copolymer (or random equivalent TREF fraction). It is a useful way to quantify how "blocky" it is. The term "blocking" refers to the extent to which a particular polymer fraction or polymer comprises blocks of polymerized monomers or comonomers. There are two random equivalents, one corresponding to a constant temperature and one corresponding to a constant mole fraction of ethylene. These form the side of a right triangle as shown in FIG. 9 which shows the definition of a block index.

In FIG. 9, points (T _X , P _X ) represent preparative TREF fractions, where ATREF elution temperature (T _X ) and NMR ethylene mole fraction (P _X ) are the measurements. The ethylene mole fraction (P _AB ) of the entire polymer is also measured by NMR. The “hard segment” elution temperature and molar fraction (T _A , P _A ) can be set or predicted to the value of the ethylene homopolymer relative to the ethylene copolymer. The T _AB value corresponds to the calculation of random copolymer equivalent ATREF elution temperature based on P _AB measurements. From the measurements of the ATREF elution temperature (T _X ), the corresponding random ethylene mole fraction (P _X0 ) can also be calculated. The square of the block index is defined as the ratio of the area of the (P _X , T _X ) triangle and the (T _A , P _AB ) triangle. Since the right triangles are similar, the area ratio is also the square ratio of the distance from (T _A , P _AB ) and (T _X , P _X ) to a random line. Also, the similarity of the right triangle means that the ratio of the length of the corresponding side can be used instead of the area.

The most complete block distribution corresponds to the entire polymer having a single elution fraction at points (T _A , P _AB ), which maintains the ethylene segment distribution within the "hard segment" but contains all available octene (possibly It should be noted that this is almost the same as that produced by the soft segment catalyst). In most cases, "soft segments" do not crystallize in ATREF (or prefabricated TREF).

Application and end use

The ethylene / α-olefin block interpolymers of the present invention can be used in various conventional thermoplastic resin fabrication processes to produce objects comprising one or more film layers, such as monolayer films, or cast, blown, calendering or extrusion coating processes. At least one layer of the multilayer film produced by the; Molded articles, such as blow molded, injection molded or rotomolded articles; Extrudate; fiber; And useful articles, including wovens or nonwovens. Thermoplastic compositions comprising the polymers of the present invention include blends with other natural or synthetic polymers, additives, reinforcing agents, flame retardant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, foaming agents, and plasticizers. Particularly useful are multicomponent fibers such as core / sheath fibers having an outer surface layer at least partially comprising one or more polymers according to embodiments of the invention.

Fibers that can be made from the polymers or blends of the present invention include staple fibers, tow fibers, multicomponent fibers, sheath / core fibers, twisted fibers, and monofilament fibers. Suitable fiber making methods include spunbonded, melt blown techniques (disclosed in US Pat. Nos. 4,430,563, 4,663,220, 4,668,566 and 4,322,027), and gel spun fibers (US Pat. 4,413,110), fabrics and nonwovens (disclosed in US Pat. No. 3,485,706), or structures, thermoforms, including blends with other fibers, such as polyester, nylon, or cotton, made from the fibers, Extrusion moldings (including profile extrusion and coextrusion), calendaring articles, and stretched, twisted or crimped yarns or fibers. The novel polymers described herein are also useful for sheet extrusion and molded article manufacturing (including injection molding, blow molding processes or rotomolding processes) for wire and cable coating operations as well as vacuum forming operations. Compositions comprising olefin polymers may also be molded into processed articles such as those described above using conventional polyolefin processing techniques known to those skilled in the art of polyolefin processing.

In addition, both the aqueous and non-aqueous dispersions can be prepared using the polymers of the invention or combinations comprising the same. In addition, foamed foams comprising the polymers of the present invention can be prepared as disclosed in PCT Application PCT / US2004 / 027593 (filed Aug. 25, 2004) and published as WO2005 / 021622. The polymer may be crosslinked by any known means, such as using peroxides, electron beams, silanes, azide or other crosslinking techniques. The polymer may also be chemically modified by, for example, grafting (eg, using maleic anhydride (MAH), silanes or other grafting agents), halogenation, amination, sulfonation or other chemical modifications.

Additives and auxiliaries can be included in any combination comprising the polymers of the invention. Suitable additives include fillers such as organic and inorganic particles such as clays, talc, titanium dioxide, zeolites, powder metals, organic or inorganic fibers such as carbon fibers, silicon nitride fibers, steel wires or meshes, and nylons or Polyester cording, nano-sized particles, clays, and the like; Tackifiers, oil extenders such as paraffinic or naphthenic oils; And other natural and synthetic polymers, such as other polymers according to embodiments of the present invention.

Suitable polymers for blending with the polymers according to embodiments of the invention include thermoplastic and non-thermoplastic polymers, including natural and synthetic polymers. Examples of polymers for blending include polypropylene, (including impact modulating polypropylene, isotactic polypropylene, atactic polypropylene and random ethylene / propylene copolymers), various types of polyethylene, for example high pressure, free-radical LDPE , Ziegler-Natta LLDPE, metallocene PE, for example multi-reactor PE (products disclosed in US Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575 and 6,448,341. "In reactor" blends of Ziegler-Natta PE and metallocene PE), ethylene-vinyl acetate (EVA), ethylene / vinyl alcohol copolymers, polystyrene, impact controlled polystyrene, ABS, styrene / Butadiene block copolymers and their hydrogenated derivatives (SBS and SEBS), and thermoplastic polyurethanes. In addition, homogeneous polymers such as olefin plastomers and elastomers, copolymers based on ethylene and propylene (e.g., also available under the tradename Versipy® from The Dow Chemical Company, also exonmobiles) Polymers available under the tradename VISTAMAXX® from Chemical Company, ExxonMobil Chemical Company, may be useful as components in blends comprising the polymers of the present invention.

Suitable end uses for the product include elastic films and fibers; Soft touch products such as toothbrush handles and tool handles; Gaskets and profiles; Adhesives (including hot melt adhesives and pressure sensitive adhesives); Shoes (including shoe soles and shoe insoles); Automotive interior parts and profiles; Foam products (both continuous and independent cells); Impact modifiers for other thermoplastic polymers such as high density polyethylene, isotactic polypropylene or other olefin polymers; Coated fabric; hose; tube; Weather stripping; Cap liners; Flooring; And viscosity index regulators (also known as pour point regulators) for lubricants.

In some embodiments, thermoplastic compositions comprising thermoplastic matrix polymers, in particular isotactic polypropylene, and elastomeric multiblock copolymers of ethylene and copolymerizable comonomers according to embodiments of the invention, are specifically designed around the closed domain of the hard polymer. It is possible to form core-shell like particles with hard crystalline or semicrystalline blocks in the form of cores surrounded by soft or elastomeric blocks forming a “shell”. These particles are formed and dispersed in the matrix polymer by forces generated during melt blending or blending. This highly desirable shape is due to the specific properties of the multiblock copolymers that allow compatible polymer regions, such as the matrix of the multiblock copolymer and elastomeric regions of higher comonomer content, to self-assemble into the melt by thermodynamic forces. It is believed to be due. It is believed that the shear force during compounding results in the formation of discrete regions of the matrix polymer surrounded by the elastomer. These regions become closed elastomer particles casing in the polymer matrix as they solidify.

Particularly preferred blends are thermoplastic polyolefin blends (TPO), thermoplastic elastomer blends (TPE), thermoplastic vulcanizates (TPV) and styrene polymer blends. TPE and TPV blends are prepared by combining the multiblock polymers of the present invention (including their functionalized or unsaturated derivatives) with any rubber (including conventional block copolymers, especially SBS block copolymers) and optionally crosslinking or vulcanizing agents. It can manufacture. TPO blends are generally prepared by blending the multiblock copolymers of the invention with polyolefins and optionally with crosslinkers or vulcanizing agents. The blend can be used to prepare moldings and optionally to crosslink the formed moldings. Similar procedures using different components were previously disclosed in US Pat. No. 6,797,779.

Suitable conventional block copolymers for this use preferably have a Mooney viscosity (ML 1 + 4 @ 100 ° C.) of 10 to 135, more preferably 25 to 100 and most preferably 30 to 80. Suitable polyolefins include, in particular, linear or low density polyethylene, polypropylene (including atactic, isotactic, syndiotactic and impact controlled forms thereof) and poly (4-methyl-1-pentene). Suitable styrene polymers include polystyrene, rubber modified polystyrene (HIPS), styrene / acrylonitrile copolymer (SAN), rubber modified SAN (ABS or AES) and styrene maleic anhydride copolymers.

Blends can be prepared by mixing or kneading each component at or near the melting point temperature of one or both components. In most multiblock copolymers, the temperature is above 130 ° C., most generally above 145 ° C., most preferably above 150 ° C. Typical polymer mixing or kneading apparatus can be used that can reach the desired temperature and can melt plasticize the mixture. These include mills, kneaders, extruders (including both single and twin screw extruders), Banbury mixers, calenders and the like. Mixing order and method may vary depending on the final composition. Combinations of Banbury batch mixers and continuous mixers may be used, such as Banbury mixers, then wheat mixers, and then extruders. Typically, TPE or TPV compositions have a higher amount of crosslinkable polymers (typically conventional block copolymers containing unsaturated groups) compared to TPO compositions. Generally, in TPE and TPV compositions, the weight ratio of block copolymer to multiblock copolymer is about 90:10 to 10:90, more preferably 80:20 to 20:80, most preferably 75:25 to 25. May be 75. For TPO applications, the weight ratio of the multiblock copolymer to polyolefin may be about 49:51 to about 5:95, more preferably 35:65 to about 10:90. For modified styrene polymer applications, the weight ratio of the multiblock copolymer to polyolefin may also be about 49:51 to about 5:95, more preferably 35:65 to about 10:90. The said ratio can be changed by changing the viscosity ratio of various components. There are many documents that can be consulted by those skilled in the art, if necessary, that describe techniques for changing phase continuity by varying the viscosity ratio of the components of the blend.

The blend composition may contain a processing oil, a plasticizer and a processing aid. Both rubber processing oils with specific ASTM designations and paraffinic, naphthenic or aromatic processing oils are suitable for use. Generally, from 0 to 150 parts, more preferably from 0 to 100 parts and most preferably from 0 to 50 parts of oil are used per 100 parts of the total polymer. Higher amounts of oil may tend to improve the processing of the product while lowering some physical properties. Further processing aids are conventional waxes, fatty acids such as calcium stearate or zinc stearate, (poly) alcohols such as glycols, (poly) alcohol ethers such as glycol ethers, (poly) esters, eg (Poly) glycol esters, and metal salts, in particular Group 1 or 2 metal salts or zinc salts, and derivatives thereof.

Non-hydrogenated rubbers (hereinafter, diene rubbers), such as those comprising polymerized forms of butadiene or isoprene, including block copolymers, have lower UV, ozone, and oxidation resistance compared to most or highly saturated rubbers. It is known. In applications such as tires made from compositions containing high concentrations of diene based rubber, it is known to incorporate carbon black with anti-ozonating additives and antioxidants to improve rubber stability. Multiblock copolymers according to the invention with extremely low unsaturation have particular use as weather resistant films or protective surface layers (coated, coextruded or laminated) adhered to articles formed from conventional diene elastomer modified polymer compositions.

In conventional TPO, TPV and TPE applications, carbon black has been selected as an additive for UV absorption and stabilization properties. Representative examples of carbon black include ASTM N11O, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. The carbon black has an average pore volume of iodine absorption, and 10 to 150 cm ^3/100 g range from 9 to 145 g / kg range. In general, carbon black having a smaller particle size is used to an acceptable level in consideration of cost. In many of these applications, the multiblock copolymers and blends thereof of the present invention require little or no carbon black, thereby allowing considerable design freedom, including alternative pigments or no pigments. One possibility is a tire that matches the color of the vehicle or a multi-coloured tire.

Compositions comprising thermoplastic blends according to embodiments of the invention may also contain antioxidants or antioxidants known to those skilled in the rubber chemistry art. Antiozonants may be physical protective agents, such as wax materials that protect components from oxygen or ozone at the surface, or may be chemical protective agents that react with oxygen or ozone. Suitable chemical protectants include butylated reaction products of styrenated phenol, butylated octylated phenol, butylated di (dimethylbenzyl) phenol, p-phenylenediamine, p-cresol and dicyclopentadiene (DCPD), polyphenols Antioxidants, hydroquinone derivatives, quinoline, diphenylene antioxidants, thioester antioxidants, and blends thereof. Some representative trade names for these products are Wingstay S antioxidant, Polystay 100 antioxidant, Polystay 100 AZ antioxidant, Polystay 200 antioxidant, wing Stay ™ L Antioxidant, Wingstay® LHLS Antioxidant, Wingstay® K Antioxidant, Wingstay® 29 Antioxidant, Wingstay® SN-1 Antioxidant, and Irganox (Irganox, trade name) Antioxidant. In some applications, the antioxidants and antiozonants used are preferably non-stainable and non-mobile.

To provide additional stability to UV radiation, hindered amine light stabilizers (HALS) and UV absorbers may be used. Suitable examples include Tinuvin 123, Tinuvin 144, Tinuvin 622, Tinuvin 765, Tinuvin (trade name) available from Ciba Specialty Chemicals. ) 770 and Tinuvin® 780, and Chemisorb (trade name) T944 available from Cytex Plastics (Houston, Texas, USA). As disclosed in US Pat. No. 6,051,681, Lewis acids may further be included with HALS compounds to achieve good surface quality.

In some compositions, additional mixing processes may be used to predisperse the antioxidants, antiozonants, carbon blacks, UV absorbers, and / or light stabilizers to form masterbatches, from which polymer blends may be prepared.

Crosslinking agents (also referred to as curing or vulcanizing agents) suitable for use herein include sulfur based, peroxide based or phenol based compounds. Examples of the material include U.S. Patent Nos. 3,758,643, 3,806,558, 5,051,478, 4,104,210, 4,130,535, 4,202,801, 4,271,049, 4,340,684, 4,250,273 Nos. 4,927,882, 4,311,628 and 5,248,729 are known in the art.

When using a sulfur based curing agent, accelerators and curing activators may also be used. Accelerators are used to control the time and / or temperature required for dynamic vulcanization and to improve the properties of the resulting crosslinked product. In one embodiment, a single promoter or first promoter is used. The first promoter (s) can be used in total amounts ranging from about 0.5 to about 4, preferably from about 0.8 to about 1.5 phr, based on the total composition weight. In another embodiment, a combination of first and second promoters can be used, where the second promoter is used in small amounts, such as about 0.05 to about 3 phr, to activate and improve the properties of the cured product. Combinations of promoters generally provide articles with properties that are somewhat better than those provided by the use of a single promoter. It is also possible to use delay action accelerators which provide satisfactory curing at normal vulcanization temperatures without being affected by normal processing temperatures. Vulcanization retardants can also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. Preferably, the first promoter is sulfenamide. When using a second promoter, the second promoter is preferably a guanidine, dithiocarbamate or thiuram compound. Certain processing aids and cure activators such as stearic acid and ZnO can also be used. When using a peroxide based curing agent, co-activators or cooperative agents can be used in combination. Suitable co-agents include, in particular, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC). The use of peroxide crosslinkers, and any cooperative agents used for partial or complete dynamic vulcanization, is known in the art and described, for example, in "Peroxide Vulcanization of Elastomer", Vol. 74, No 3, July-August 2001.

If the multiblock copolymer containing composition is at least partially crosslinked, the degree of crosslinking can be measured by dissolving the composition in a solvent for a certain period of time and calculating the percentage of gel or non-extractable components. Gel percentages typically increase as the degree of crosslinking increases. In the cured product according to an embodiment of the present invention, the gel content (%) is preferably in the range of 5 to 100%.

Multiblock copolymers, as well as blends thereof, according to embodiments of the present invention have improved processability compared to prior art compositions, which are believed to be due to lower melt viscosity. Thus, the compositions or blends of the present invention exhibit an improved surface appearance, especially when molded into molded or extruded articles. At the same time, the compositions of the present invention and their blends specifically have improved melt strength properties, whereby the multiblock copolymers and blends thereof, in particular TPO blends, are useful in foams and thermoforming applications where current melt strength is inadequate. Can be used.

Thermoplastic compositions according to embodiments of the invention may comprise inorganic or organic fillers, or starches, talc, calcium carbonate, glass fibers, polymer fibers (including nylon, rayon, cotton, polyester and polyaramid), metal fibers, plaques or particles , Foamed laminated silicates, phosphates or carbonates such as clays, mica, silica, alumina, aluminosilicates or aluminophosphates, carbon whiskers, carbon fibers, nanotubes with nanoparticles, wollastonite, graphite, zeolites and ceramics such as carbonization It may also contain other additives such as silicon, silicon nitride or titania. Silane based coupling agents or other coupling agents may be used for better filler bonding.

Thermoplastic compositions (including the blends) according to embodiments of the present invention can be processed by conventional molding techniques such as injection molding, extrusion molding, thermoforming, slush molding, over molding, insert molding, blow molding and other techniques. have. Films, including multilayer films, can be prepared by cast or tentering processes (including blown film processes).

In addition to the foregoing, the ethylene / α-olefin block interpolymers may be used in the manner described in the following U.S. provisional applications (the disclosures of these and their continuous, split and partial continuous applications are incorporated herein by reference in their entirety). .

1) "Impact-Modification of Thermoplastics with Ethylene / α-Olefins", US Application 60 / 717,928, filed September 16, 2005;

2) “Three Dimensional Random Looped Structures Made from Interpolymers of Ethylene / α-Olefins and Uses Thereof”, US Application No. 60 / 718,130, filed Sep. 16, 2005;

3) “Polymer Blends from Interpolymer of Ethylene / α-Olefin”, US Application No. 60 / 717,825, filed Sep. 16, 2005;

4) “Viscosity Index Improver for Lubricant Compositions”, US Application No. 60 / 718,129, filed September 16, 2005;

5) “Fibers Made from Copolymers of Ethylene / α-Olefins”, US Application No. 60 / 718,197, filed Sep. 16, 2005;

6) “Fibers Made from Copolymers of Propylene / α-Olefins”, US Application No. 60 / 717,863, filed Sep. 16, 2005;

7) "Adhesive and Marking Compositions Made from Interpolymers of Ethylene / α- Olefins", US Application 60 / 718,000, filed September 16, 2005;

8) "Compositions of Ethylene / α-Olefin Multi-Block Interpolymers Suitable For Films", US Application No. 60 / 718,198, filed Sep. 16, 2005;

9) “Rheology Modification of Interpolymers of Ethylene / α-Olefins and Articles Made Therefrom”, US Application No. 60 / 718,036, filed Sep. 16, 2005;

10) “Soft Foams Made From Interpolymers of Ethylene / α-Olefins”, US Application No. 60 / 717,893, filed Sep. 16, 2005;

11) “Low Molecular Weight Ethylene / α-Olefin Interpolymer as Base Lubricant Oil”, US Application No. 60 / 717,875, filed Sep. 16, 2005;

12) “Foams Made From Interpolymers of Ethylene / α-Olefins”, US Application No. 60 / 717,860, filed September 16, 2005;

13) "Compositions of Ethylene / α-Olefin Multi-Block Interpolymer For Blown Films with High Hot Tack", US Application 60 / 717,982, filed September 16, 2005;

14) “Cap Liners, Closures and Gaskets From Multi-Block Polymers”, US Application 60 / 717,824, filed September 16, 2005;

15) "Polymer Blends From Interpolymers of Ethylene / α-Olefins", US Application 60 / 718,245, filed September 16, 2005;

16) “Anti-Blocking Compositions Comprising Interpolymers of Ethylene / α-Olefins”, US Application No. 60 / 717,588, filed Sep. 16, 2005;

17) “Interpolymers of Ethylene / α-Olefins Blends and Profiles and Gaskets Made Therefrom”, US Application 60 / 718,165, filed September 16, 2005;

18) “Filled Polymer Compositions Made from Interpolymers of Ethylene / α-Olefins and Uses Thereof, US Application No. 60 / 717,587, filed Sep. 16, 2005;

19) “Compositions of Ethylene / α-Olefin Multi-Block Interpolymer For Elastic Films and Laminates”, US Application 60 / 718,081, filed September 16, 2005;

20) “Thermoplastic Vulcanizate Comprising Interpolymers of Ethylene / α-Olefins”, US Application No. 60 / 718,186, filed Sep. 16, 2005;

21) "Multi-Layer, Elastic Articles", US Application No. 60 / 754,087, filed December 27, 2005; And

22) “Functionalized Olefin Interpolymers, Compositions and Articles Prepared Therefrom, and Methods for Making the Same”, US Application No. 60 / 718,184, filed September 16, 2005.

The following examples are provided to illustrate the synthesis of the polymers of the invention. Certain comparative examples were made using some existing polymers. The examples are provided to illustrate embodiments of the invention and are not intended to limit the invention to the specific embodiments described. Unless otherwise stated, all parts and percentages are by weight. All figures are approximate. If a numerical range is provided, it should be understood that embodiments outside the stated range are also included within the scope of the present invention. The specific details described in each example should not be intended as essential features of the invention.

Test method

In the following examples, the following analytical techniques were used.

For samples 1-4 and A-C GPC  Way

Using an automated liquid-handling robot equipped with a heated needle set at 160 ° C., sufficient 1,2,4-trichlorobenzene stabilized by 300 ppm Ionol was added to each dried polymer sample by 30 A final concentration of mg / mL was obtained. A small glass stir bar was placed in each tube and the sample was heated to 160 ° C. for 3 hours in a heated rotary shaker rotating at 250 rpm. The polymer concentrate was then diluted to 1 mg / ml using an automated liquid-handling robot and a heated needle set at 160 ° C.

Molecular weight data for each sample was measured using the Symyx Rapid GPC system. Helium purged 1,2-dichlorobenzene stabilized with 300 ppm ionol, using a Gilson 350 pump set at a flow rate of 2.0 ml / min, was placed in series with three Plgel 10 micrometers (μm) Pumped as a mobile phase through a Mixed-B 300 mm × 7.5 mm column and heated to 160 ° C. The Polymer Labs ELS 1000 Detector was placed at an evaporator set at 250 ° C., a nebulizer set at 165 ° C., and at a pressure of 60 to 80 psi (400 to 600 kPa) N ₂ . Used with nitrogen flow rate set to 1.8 SLM. The polymer samples were heated to 160 ° C. and each sample was injected into a 250 μl loop using a liquid-handling robot and heated needle. A series of polymer sample analyzes and duplicate injections using two switched loops were used. Sample data was collected and analyzed using Symyx Epoch (tradename) software. Peaks were manually integrated and molecular weight information was recorded uncorrected against the polystyrene standard calibration curve.

Standard CRYSTAF  Way

Branching distribution was measured by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from Polymer Char (Valencia, Spain). The sample was dissolved in 1,2,4-trichlorobenzene at 160 ° C. for 1 hour (0.66 mg / mL) and stabilized at 95 ° C. for 45 minutes. Sampling temperatures ranged from 95 to 30 ° C. at a cooling rate of 0.2 ° C./min. The polymer solution concentration was measured using an infrared detector. The cumulative soluble concentration was measured when the polymer crystallized with decreasing temperature. Analytical derivatives of the cumulative profile reflect the short chain branching distribution of the polymer.

CRYSTAF peak temperature and area were confirmed by the peak analysis module included in the CRYSTAF software (version 2001.b, Polymer Char, Valencia, Spain). The CRYSTAF peak identification routine confirmed the area between the peak temperature as the maximum in the dW / dT curve, and the maximum amount of bend on each side of the peak identified in the derivative curve. To calculate the CRYSTAF curve, a preferred processing parameter is to perform parameter planarization above the temperature limit of 0.1 and below the temperature limit of 0.3 with a temperature limit of 70 ° C.

DSC  Standard method (except samples 1-4 and A-C)

The results of the differential scanning calorimetry were measured using a TAI model Q10OO DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml / min was used. The sample was pressed into a thin film and melted in a press at about 175 ° C. and then air cooled to room temperature (25 ° C.). Subsequently, 3-10 mg of material was cut into 6 mm diameter disks, accurately weighed, placed in a lightweight aluminum pan (about 50 mg) and then crimped off. The thermal behavior of the samples was investigated with the following temperature profiles. The sample was rapidly heated to 180 ° C. and kept isothermal for 3 minutes to remove any previous thermal history. The sample was then cooled to −40 ° C. at a cooling rate of 10 ° C./min and held at −40 ° C. for 3 minutes. The sample was then heated to 150 ° C. at a heating rate of 10 ° C./min. Cooling and second heating curves were recorded.

The DSC melt peak was measured as the maximum of heat flow rate (W / g) with respect to the linear baseline shown between −30 ° C. and the melting end point. The heat of fusion was measured as the area under the melting curve between −30 ° C. and the melting end point using a linear baseline.

The calibration of the DSC was performed as follows. First, a baseline was obtained by performing DSC from −90 ° C. without any sample in an aluminum DSC pan. The 7 milligrams of fresh indium sample is then heated to 180 ° C., the sample is cooled to 140 ° C. at a cooling rate of 10 ° C./min, and the sample is isothermally held at 140 ° C. for 1 minute, and then the sample is 10 ° C. The analysis was carried out by heating from 140 ° C. to 180 ° C. at a heating rate of min. The heat of fusion and the onset of melting of the indium sample were confirmed, and checked to be within 0.5 ° C from 156.6 ° C for melting initiation and to within 0.5 J / g from 28.71 J / g for melting. Deionized water was then analyzed by cooling a small drop of fresh sample from 25 ° C. to −30 ° C. at a cooling rate of 10 ° C./min. The sample was kept isothermal at −30 ° C. for 2 minutes and heated to 30 ° C. at a heating rate of 10 ° C./min. Melting start was confirmed and checked so that it might be within 0.5 degreeC from 0 degreeC.

GPC  Method (except Samples 1-4 and A-C)

The gel permeation chromatography system consisted of a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments were operated at 140 ° C. Three polymer Laboratories 10-micrometer Mixed-B columns were used. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples were prepared by gently stirring at 160 ° C. for 2 hours. The injection volume used was 100 microliters and the flow rate was 1.0 ml / min.

Calibration of the set of GPC columns is carried out by 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures separated from each other by at least 10 individual molecular weights. It was. Standards were purchased from Polymer Laboratories, Shropshire, UK. Polystyrene standards were prepared in 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standard was dissolved at 80 ° C. with gentle stirring for 30 minutes. Narrow standard mixtures were run first and then in decreasing order from the highest molecular weight component to minimize degradation. Equation: _Polyethylene standard peak molecular weight was converted to polyethylene molecular weight using M _polyethylene = 0.431 (M _polystyrene ) (Williams and Ward, J. Poym. Sci., Polym. Let., 6, 621 (1968)). Listed).

Polyethylene equivalent molecular weight was calculated using Viscotek TriSEC software version 3.0.

Compression set

Compression set was measured according to ASTM D 395. Samples were prepared by laminating circular discs of diameter 25.4 mm with a thickness of 3.2 mm, 2.0 mm and 0.25 mm until the total thickness reached 12.7 mm. The discs were cut from 12.7 cm x 12.7 cm compression molded plaques formed by hot press under the following conditions. The pressure was cooled at 190 ° C. for 3 minutes, then at 190 ° C. for 2 minutes at 86 MPa, then at 86 MPa for cooling in the press.

density

Samples for density measurement were prepared according to ASTM D 1928. Measurements were made within 1 hour of sample compression using ASTM D792, Method B.

curve/ secant Modulus /Save Modulus

Samples were compression molded using ASTM D 1928. Flexural and 2% secant modulus were measured according to ASTM D-790. Storage modulus was measured according to ASTM D 5026-01 or equivalent technique.

Optical properties

A 0.4 mm thick film was compression molded using a hot press (Carver model # 4095-4PR1001R). The pellet was placed between polytetrafluoroethylene sheets and heated at 190 ° C. for 3 minutes at 55 psi (380 kPa) then 3 minutes at 1.3 MPa and then 3 minutes at 2.6 MPa. The film was then cooled in a press by flowing cooling water at 1.3 MPa for 1 minute. Compression molded films were used for optical measurements, tensile behavior, recovery and stress relaxation rates.

Transparency was measured using BYK Gardner Haze-gard as specified in ASTM D 1746.

45 ° gloss was measured using BYK Gardner Glossmeter Microgloss 45 ° as specified in ASTM D-2457.

Internal haze was measured using a BYK Gardner Haze-Guard based on ASTM D 1003 Procedure A. Mineral oil was applied to the film surface to remove surface scratches.

Mechanical properties-tensile, Hysteresis ( Hysteresis ) And Tear

The stress-strain behavior at uniaxial tension was measured using ASTM D 1708 microtensile test specimens. Samples were stretched by Instron at 500C / min at 21 ° C. Tensile strength and elongation at break were recorded from the average of five test pieces.

100% and 300% hysteresis was measured from cyclic loading for 100% and 300% strain using an ASTM D 1708 microtensile test specimen by an Instron ™ instrument. Samples were loaded and unloaded at 21 ° C. at 267% / min for 3 cycles. Circulation experiments were performed at 300% and 80 ° C using an environmental chamber. In the 80 ° C. experiment, the samples were equilibrated for 45 minutes at the test temperature before testing. In a 21 ° C., 300% strain cycling experiment, shrinkage stress at 150% strain from the first unloading cycle was recorded. The percent recovery in all experiments was calculated from the first unloading cycle using the strain at which loading returned to baseline. Recovery rate (%) is defined as follows.

Where ε _f is the strain obtained for cyclic loading and ε _s is the strain at which the loading returns to the baseline during the first unloading cycle.

Stress relief was measured at 50% strain and 12 hours at 37 ° C. using an Instron ™ instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37 ° C. for 45 minutes in an environmental chamber, the sample was stretched to 50% strain at 333% / min. The stress was recorded as a function of time for 12 hours. The stress relaxation rate (%) was calculated after 12 hours using the following equation.

In the formula, L ₀ is loading at 50% strain at 0 hours and L ₁₂ is loading at 50% strain after 12 hours.

Tensile notched tear experiments were performed with samples having a density of 0.88 g / cc or less using an Instron ™ instrument. The geometry consisted of a 76 mm x 13 mm x 0.4 mm gauge region with a 2 mm notch cut into the sample at half the test piece length. The sample was stretched to 508 mm / min at 21 ° C. until it broke. Tear energy was calculated as the area under the stress-elongation curve up to strain at maximum loading. The average of three or more test pieces was recorded.

TMA

Thermomechanical analysis (penetration temperature) was performed on compression molded discs of 30 mm diameter x 3.3 mm thickness, which were formed at 180 ° C. and 10 MPa molding pressure for 5 minutes and then air quenched. The instrument used was TMA 7 (trademark available from Perkin-Elmer). In the test, a probe with a radius of 1.5 mm (P / N N519-0416) was applied to the surface of the sample disc with a force of 1 N. The temperature was raised from 25 ° C. to 5 ° C./min. Probe penetration distance was measured as a function of temperature. The experiment was terminated when the probe had penetrated 1 mm into the sample.

DMA

Dynamic mechanical analysis (DMA) was performed on a compression molded disc that was formed in a hot press for 5 minutes at 180 ° C. and 10 MPa pressure and then water cooled to 90 ° C./min in the press. The test was performed using an ARES controlled strain rheometer (TA instrument) equipped with a double cantilever fixture for torsion testing.

1.5 mm plaques were pressed and cut into bars measuring 32 x 12 mm. Samples were clamped both ends between fixtures at 10 mm intervals (grip spacing (ΔL)) and a subsequent temperature step (5 ° C. per step) from −100 ° C. to 200 ° C. was performed. At each temperature, the torsional modulus (G ') was measured at each frequency of 10 rad / s, and the strain amplitude was maintained between 0.1% and 4% to ensure that the torque was sufficient and the measurement was maintained in a linear manner.

An initial static force of 10 g was maintained (automatic tension mode) to prevent sagging in the sample when thermal expansion occurred. As a result, the grip spacing (ΔL) increased with temperature, especially at temperatures above the melting or softening point of the polymer sample. The test was stopped at the maximum temperature or when the gap between the fixtures reached 65 mm.

Melt index

Melt index or I ₂ was measured according to ASTM D 1238, Condition 190 ° C./2.16 kg. In addition, the melt index or I ₁₀ was measured according to ASTM D 1238, condition 190 ° C./10 kg.

ATREF

US Pat. No. 4,798,081 and Wilde, L .; Ryle, T. R .; Knobeloch, D. C .; Peat, I. R .; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982), performed analytical temperature rising elution fractionation (ATREF) analysis. The composition to be analyzed was dissolved in trichlorobenzene and crystallized in a column containing an inert support (stainless steel shot) by slowly decreasing the temperature to 20 ° C. at a cooling rate of 0.1 ° C./min. The column was equipped with an infrared detector. The crystallized polymer sample was then eluted from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 ° C. to 120 ° C. at a rate of 1.5 ° C./min to obtain an ATREF chromatogram curve.

¹³ C NMR  analysis

Samples were prepared by adding approximately 3 g of 50/50 mixture of tetrachloroethane-d ² / orthodichlorobenzene to 0.4 g of sample in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150 ° C. Data was collected using a JEOL Eclipse 400 MHz spectrometer or a Varian Unity Plus 400 MHz spectrometer, corresponding to a ¹³ C resonance frequency of 100.5 MHz. Data was acquired using 4000 transients per data file with a 6 second pulse repetition delay. To obtain the minimum signal-to-noise for quantitative analysis, multiple data files were added together. At a minimum file size of 32K data points, the spectral width was 25,000 Hz. Samples were analyzed at 130 ° C. in a 10 mm wide band probe. Randall's Randall's triad method (Randall, JC; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989)), which is hereby incorporated by reference in its entirety. Comonomer incorporation was measured.

TREF  (Also for manufacturing TREF Polymer fractionation)

Large scale TREF fractionation was performed by dissolving 15-20 g of polymer at 160 ° C. for 4 hours and dissolving in 2 liters of 1,2,4-trichlorobenzene (TCB). The polymer solution is 30-40 mesh (600-425 μm) spherical industrial glass beads (available from Potters Industries, Brownwood HC 30 Box 20, 76801, USA) and diameter 0.028 "(0.7) mm) packed in a 60:40 (v: v) mixture of cut steel shorted stainless steel (available from Pellets, Inc., Industrial Drive 63, North Towanda, NY, USA 14120). Was added with 15 psig (100 kPa) of nitrogen on a 3 inch by 4 foot (7.6 cm x 12 cm) steel column, which was deposited into a thermally controlled oil jacket and initially set at 160 ° C. The column was first cooled rapidly to 125 ° C. and then slowly cooled to 0.04 ° C./min to 20 ° C. and held for 1 h.The temperature was increased to 0.167 ° C./min and fresh TCB was introduced at about 65 ml / min.

Approximately 2000 ml portions of the eluate from the preparative TREF column were collected in 16 zones of heated fraction collector. The polymer was concentrated in each fraction using a rotary evaporator until about 50-100 ml of polymer solution remained. After the concentrate was left overnight, excess methanol was added, filtered and rinsed (approximately 300-500 ml of methanol, including the final rinse). The filtration step was performed in a three position vacuum assisted filtration zone using a 5.0 μm polytetrafluoroethylene coated filter paper (available from Osmonics Inc., Cat # Z50WP04750). The filtered fractions were dried overnight in a vacuum oven at 60 ° C., weighed on an analytical balance and then further tested. Further information on suitable methods can be found in Wilde, L .; Ryle, T. R .; Knobeloch, D. C .; Peat, I. R .; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982).

Melt strength

Melt strength (MS) was measured using a capillary rheometer with a diameter of 2.1 mm and a 20: 1 die with an inlet angle of approximately 45 degrees. After equilibrating the sample at 190 ° C. for 10 minutes, the piston was run at a speed of 1 inch / minute (2.54 cm / minute). Standard test temperature was 190 ° C. Samples were uniaxially stretched with a set of acceleration nips located 100 mm below the die with an acceleration of 2.4 mm / sec ² . The required tensile force was recorded as a function of the winding speed of the nip rolls. The maximum tensile force achieved during the test is defined as the melt strength. When the polymer melt exhibits stretching resonance, the tensile force before the start of the stretching resonance is taken as the melt strength. Melt strength was reported in centinewtons (“cN”).

catalyst

When the term “overnight” is used, it refers to a time of approximately 16 to 18 hours, the term “room temperature” refers to a temperature of 20 to 25 ° C., and the term “mixed alkanes” is the trade name Iso from ExxonMobil Chemical Company. refers to a Parr (Isopar) E (R), available C _{6 -9} commercially available mixture of aliphatic hydrocarbons. If a compound name does not match its structural representation herein, the structural representation is governed. Synthesis of all metal complexes and preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box technology. All solvents used were HPLC grade and they were used after drying.

MMAO refers to modified methylalumoxane, triisobutylaluminum modified methylalumoxane, commercially available from Akzo-Noble Corporation.

Preparation of the catalyst (B1) was carried out as follows.

a) (1- Methylethyl ) (2-hydroxy-3,5- Di (t-butyl) phenyl ) Methylimine  Produce

3,5-di-t-butylsalicylaldehyde (3.00 g) was added to 10 mL of isopropylamine. The solution rapidly turned bright yellow. After stirring for 3 hours at ambient temperature, the volatiles were removed under vacuum to yield a light yellow crystalline solid (yield 97%).

b) 1,2- Vis -(3,5-di-t- Butylphenylene ) (1- (N- (1- Methylethyl ) Imino ) methyl )(2- Oxoyl Zirconium Dibenzyl  Produce

A solution of (1-methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) imine (605 mg, 2.2 mmol) in 5 mL toluene was added Zr (CH ₂ Ph) ₄ in 50 mL toluene. (500 mg, 1.1 mmol) was added slowly to the solution. The resulting dark yellow solution was stirred for 30 minutes. Removal of solvent under reduced pressure gave the desired product as a reddish brown solid.

Preparation of the catalyst (B2) was carried out as follows.

a) (1- (2- Methylcyclohexyl ) Ethyl) (2- Oxoyl -3,5- Di (t-butyl) phenyl Production of immigration

2-methylcyclohexylamine (8.44 mL, 64.0 mmol) was dissolved in methanol (90 mL) and di-t-butylsalicylaldehyde (10.00 g, 42.67 mmol) was added. The reaction mixture was stirred for 3 hours and then cooled to -25 ° C for 12 hours. The resulting yellow solid precipitate was collected by filtration, washed with cold methanol (2 × 15 mL) and then dried under reduced pressure. 11.17 g of a yellow solid were obtained. ¹ H NMR was consistent with the desired product as an isomer mixture.

b) Vis -(1- (2- Methylcyclohexyl ) Ethyl) (2- Oxoyl -3,5- Di (t-butyl) phenyl ) Imino )zirconium Dibenzyl  Produce

Zr in 600 mL toluene with a solution of (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imine (7.63 g, 23.2 mmol) in 200 mL toluene To the solution of (CH ₂ Ph) ₄ (5.28 g, 11.6 mmol) was added slowly. The resulting dark yellow solution was stirred at 25 ° C. for 1 hour. The solution was further diluted with 680 mL toluene to give a solution with a concentration of 0.00783 M.

Cocatalyst 1: Substantially long-chain trialkylamines (Armeen® M2HT, Liquid-Nobel, Inc.), as disclosed in US Pat. No. 5,919,983, Example 2. Available from)), methyldi (C _14-18 alkyl) ammonium salt of tetrakis (pentafluorophenyl) borate (hereafter aluminum borate), prepared by reacting HCl and Li [B (C ₆ F ₅ ) ₄ ] ) Mixture.

Co-catalyst 2: U.S. Patent No. 6,395,671, Example 16 prepared according to, bis (tris (pentafluorophenyl) - aluminate only) -2-undecyl-mixing of the microporous Jolly DE C _{14 -18-alkyl} dimethyl ammonium salts.

Transfer agent : The transfer agent used was 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-butyl) siloxane) (SA7), i-butylaluminum bis (di (trimethylsilyl) amide) (SA8), n-octylaluminum 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-octylaluminum di (ethyl (1-naphthyl) amide) (SA13), ethylaluminum bis (t-butyldimethylsiloxide) (SA14) , Ethylaluminum di (bis (trimethylsilyl) amide) (SA15), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide) (SA16), n-octylaluminum bis (2, 3,6,7-dibenzo-1-azacycloheptanamide) (SA17), n-octylaluminum bis (dimethyl (t-butyl) Include hydroxide (SA18), ethyl zinc (2,6-diphenyl-phenoxide) (SA19), and zinc acetate (t- butoxide) (SA20).

Example  1 to 4, Comparative example  A to C

General high throughput parallel polymerization conditions

The polymerization is carried out using a high throughput parallel polymerization reactor (PPR) available from Simyx Technologies, Inc., and is substantially US Pat. No. 6,248,540, 6,030,917, 6,362,309. Work was performed in accordance with US Pat. No. 6,306,658 and 6,316,663. Ethylene copolymerization was carried out at 130 ° C. and 200 psi (1.4 MPa) with the required ethylene using 1.2 equivalents of cocatalyst 1 (1.1 equivalents when MMAO was present) based on the total catalyst used. A series of polymerizations was carried out in a parallel pressure reactor (PPR) containing 48 individual reactor cells in a 6 × 8 array in which pre-weighed glass tubes were fixed. The working volume in each reactor cell was 6000 μl. Each cell was stirred by a separate stirring paddle and temperature and pressure controlled. The monomer gas and the quench gas were plumbed directly into the PPR unit and controlled by an automatic valve. Liquid reagent was robotically added to each reactor cell by syringe, and the reservoir solvent was mixed alkanes. The order of addition was mixed alkane solvent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst 1 / MMAO mixture, transfer agent, and catalyst or catalyst mixture. When using a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts, the premix was premixed in small vials just prior to adding the reagents to the reactor. If reagents were omitted from the experiment, the order of addition was maintained in a different way. The polymerization was carried out for approximately 1 to 2 minutes until the desired ethylene consumption was reached. After quenching with CO, the reactor was cooled and the glass tube was unloaded. The tube was transferred to a centrifuge / vacuum drying unit and dried at 60 ° C. for 12 hours. The tube containing the dried polymer was weighed and the net yield of the polymer was obtained from the difference between this weight and the container weight. The results are shown in Table 1. In Table 1 and elsewhere herein, the comparative compound is indicated by an asterisk (*).

Examples 1 to 4 show the products of a very narrow MWD, in particular monomodal copolymers, and also a broad molecular weight distribution of bimodal in the absence of DEZ (mixture of separately prepared polymers) in the presence of DEZ The synthesis of the linear block copolymers according to the invention, as evidenced by the formation of, is indicated. Due to the fact that catalyst (A1) is known to introduce more octenes compared to catalyst (B1), different blocks or segments of the resulting copolymers according to embodiments of the present invention are based on branching or density It is distinguishable.

¹ per 1000 carbon C _6, or higher chain content

² Bimodal Molecular Weight Distribution

Polymers prepared according to embodiments of the invention have a relatively narrow polydispersity (M _w / M _n ) and higher block-copolymer content (trimers, tetramers or more) compared to polymers prepared in the absence of transfer agents. It can be seen that

Further characterization data for the polymers in Table 1 were determined with reference to the figures. More specifically, the DSC and ATREF results are shown below.

The DSC curve for the polymer of Example 1 showed a heat of fusion of 158.1 J / g and a melting point (Tm) of 115.7 ° C. The corresponding CRYSTAF curve shows the tallest peak at 34.5 ° C. and a peak area of 52.9%. The difference between the DSC Tm and the Tcrystaf was 81.2 ° C.

The DSC curve for the polymer of Example 2 showed a peak with a heat of fusion of 214.0 J / g and a melting point (Tm) of 109.7 ° C. The corresponding CRYSTAF curve shows the tallest peak at 46.2 ° C. and a peak area of 57.0%. The difference between the DSC Tm and the Tcrystaf was 63.5 ° C.

The DSC curve for the polymer of Example 3 showed a peak with a heat of fusion of 160.1 J / g and a melting point (Tm) of 120.7 ° C. The corresponding CRYSTAF curve shows the tallest peak at 66.1 ° C. and a peak area of 71.8%. The difference between the DSC Tm and the Tcrystaf was 54.6 ° C.

The DSC curve for the polymer of Example 4 showed a peak with a heat of fusion of 170.7 J / g and a melting point (Tm) of 104.5 ° C. The corresponding CRYSTAF curve shows the tallest peak at 30 ° C. and a peak area of 18.2%. The difference between the DSC Tm and the Tcrystaf was 74.5 ° C.

The DSC curve for Comparative Example A showed a heat of fusion of 86.7 J / g and a melting point (Tm) of 90.0 ° C. The corresponding CRYSTAF curve shows the tallest peak at 48.5 ° C. and the peak area of 29.4%. Both of these values were consistent with low density resins. The difference between the DSC Tm and the Tcrystaf was 41.8 ° C.

The DSC curve for Comparative Example B showed a heat of fusion of 237.0 J / g and a melting point (Tm) of 129.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 82.4 ° C. and the peak area of 83.7%. Both of these values were consistent with high density resins. The difference between the DSC Tm and the Tcrystaf was 47.4 ° C.

The DSC curve for Comparative Example C showed a heat of fusion of 143.0 J / g and a melting point (Tm) of 125.3 ° C. The corresponding CRYSTAF curve shows the highest peak at 81.8 ° C. and the peak area of 34.7% as well as the lower crystal peak at 52.4 ° C. The spacing between the two peaks was consistent with the presence of high and low crystalline polymers. The difference between DSC Tm and Tcrystaf was 43.5 ° C.

Example  5 to 19, Comparative example  D to F, continuous solution polymerization, catalyst A1 / B2 + DEZ

Continuous solution polymerization was carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkane solvent (Isopar ™ E) available from ExxonMobil Chemical Company, 2.70 lbs / hr (1.22 kg / hr) of ethylene, 1-octene and hydrogen (if used) were internal thermocouple and temperature It was fed to a 3.8 L reactor equipped with a control jacket. Solvent feed to the reactor was measured by a mass flow controller. A variable speed diaphragm pump was used to control the solvent flow rate and pressure into the reactor. On pump discharge, side flow was taken to provide flush flow for the catalyst and cocatalyst 1 injection line and reactor stirrer. These flows were measured by a Micro-Motion mass flow meter and adjusted by a control valve or by manual adjustment of the needle valve. The remaining solvent was combined with 1-octene, ethylene and hydrogen (if used) and fed to the reactor. If necessary, a mass flow controller was used to deliver hydrogen to the reactor. The temperature of the solvent / monomer solution was adjusted using a heat exchanger and then introduced into the reactor. The stream was introduced at the bottom of the reactor. The catalyst component solution was metered, combined with the catalyst flush solvent and introduced into the bottom of the reactor using a pump and a mass flow meter. Liquid filling was performed at 500 psig (3.45 MPa) with vigorous stirring in the reactor. Product was removed through the outlet line at the top of the reactor. All outlet lines from the reactor were vapor traced and insulated. A small amount of water was added to the outlet line with any stabilizer or other additives and the polymerization was stopped by passing the mixture through a static mixer. The product stream was then heated through a heat exchanger and then devolatilized. The polymer product was recovered by extrusion using a devolatilization extruder and a water cooled pelletizer. Process details and results are listed in Table 2. Selected polymer properties are listed in Table 3.

^* Comparative Example (not an embodiment of the present invention)

¹ standard cm ³ / min

² [N- (2,6-di (1-methylethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dimethyl

³ bis- (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

⁴ molar ratio in reactor

⁵ Polymer Producing Rate

⁶ % conversion of ethylene in the reactor

⁷ Efficiency, kg polymer / g M (where g M = g Hf + g Zr)

The resulting polymer was tested by DSC and ATREF as in the above examples. The results are as follows.

The DSC curve for the polymer of Example 5 showed a peak with a heat of fusion of 60.0 J / g and a melting point (Tm) of 119.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 47.6 ° C. and a peak area of 59.5%. The delta between the DSC Tm and the Tcrystaf was 72.0 ° C.

The DSC curve for the polymer of Example 6 showed a peak with a heat of fusion of 60.4 J / g and a melting point (Tm) of 115.2 ° C. The corresponding CRYSTAF curve shows the tallest peak at 44.2 ° C. and the peak area of 62.7%. The delta between the DSC Tm and the Tcrystaf was 71.0 ° C.

The DSC curve for the polymer of Example 7 showed a peak with a heat of fusion of 69.1 J / g and a melting point of 121.3 ° C. The corresponding CRYSTAF curve shows the tallest peak at 49.2 ° C. and the peak area of 29.4%. The delta between the DSC Tm and the Tcrystaf was 72.1 ° C.

The DSC curve for the polymer of Example 8 showed a peak with a heat of fusion of 67.9 J / g and a melting point (Tm) of 123.5 ° C. The corresponding CRYSTAF curve shows the tallest peak at 80.1 ° C. and the peak area of 12.7%. The delta between the DSC Tm and the Tcrystaf was 43.4 ° C.

The DSC curve for the polymer of Example 9 showed a peak with a heat of fusion of 73.5 J / g and a melting point (Tm) of 124.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 80.8 ° C. and the peak area of 16.0%. The delta between the DSC Tm and the Tcrystaf was 43.8 ° C.

The DSC curve for the polymer of Example 10 showed a peak with a heat of fusion of 60.7 J / g and a melting point (Tm) of 115.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 40.9 ° C. and a peak area of 52.4%. The delta between the DSC Tm and the Tcrystaf was 74.7 ° C.

The DSC curve for the polymer of Example 11 showed a peak with a heat of fusion of 70.4 J / g and a melting point (Tm) of 113.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 39.6 ° C. and the peak area of 25.2%. The delta between the DSC Tm and the Tcrystaf was 74.1 ° C.

The DSC curve for the polymer of Example 12 showed a peak with a heat of fusion of 48.9 J / g and a melting point (Tm) of 113.2 ° C. The corresponding CRYSTAF curve did not show a peak above 30 ° C. (Thus, Tcrystaf was set to 30 ° C. for further calculation.) The delta between the DSC Tm and Tcrystaf was 83.2 ° C.

The DSC curve for the polymer of Example 13 showed a peak with a heat of fusion of 49.4 J / g and a melting point (Tm) of 114.4 ° C. The corresponding CRYSTAF curve shows the tallest peak at 33.8 ° C. and the peak area of 7.7%. The delta between the DSC Tm and the Tcrystaf was 84.4 ° C.

The DSC curve for the polymer of Example 14 showed a peak with a heat of fusion of 127.9 J / g and a melting point (Tm) of 120.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 72.9 ° C. and a peak area of 92.2%. The delta between the DSC Tm and the Tcrystaf was 47.9 ° C.

The DSC curve for the polymer of Example 15 showed a peak with a heat of fusion of 36.2 J / g and a melting point (Tm) of 114.3 ° C. The corresponding CRYSTAF curve shows the tallest peak at 32.3 ° C. and the peak area of 9.8%. The delta between the DSC Tm and the Tcrystaf was 82.0 ° C.

The DSC curve for the polymer of Example 16 showed a peak with a heat of fusion of 44.9 J / g and a melting point (Tm) of 116.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 48.0 ° C. and a peak area of 65.0%. The delta between the DSC Tm and the Tcrystaf was 68.6 ° C.

The DSC curve for the polymer of Example 17 showed a peak with a heat of fusion of 47.0 J / g and a melting point (Tm) of 116.0 ° C. The corresponding CRYSTAF curve shows the tallest peak at 43.1 ° C. and a peak area of 56.8%. The delta between the DSC Tm and the Tcrystaf was 72.9 ° C.

The DSC curve for the polymer of Example 18 showed a peak with a heat of fusion of 141.8 J / g and a melting point (Tm) of 120.5 ° C. The corresponding CRYSTAF curve shows the tallest peak at 70.0 ° C. and the peak area of 94.0%. The delta between the DSC Tm and the Tcrystaf was 50.5 ° C.

The DSC curve for the polymer of Example 19 showed a peak with a heat of fusion of 174.8 J / g and a melting point (Tm) of 124.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 79.9 ° C. and a peak area of 87.9%. The delta between the DSC Tm and the Tcrystaf was 45.0 ° C.

The DSC curve for the polymer of Comparative Example D showed a peak with a heat of fusion of 31.6 J / g and a melting point (Tm) of 37.3 ° C. The corresponding CRYSTAF curve did not show a peak above 30 ° C. Both of these values were consistent with low density resins. The delta between the DSC Tm and the Tcrystaf was 7.3 ° C.

The DSC curve for the polymer of Comparative Example E showed a peak with a heat of fusion of 179.3 J / g and a melting point (Tm) of 124.0 ° C. The corresponding CRYSTAF curve shows the tallest peak at 79.3 ° C. and a peak area of 94.6%. Both of these values were consistent with high density resins. The delta between the DSC Tm and the Tcrystaf was 44.6 ° C.

The DSC curve for Comparative Example F showed a peak with a heat of fusion of 90.4 J / g and a melting point (Tm) of 124.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 77.6 ° C. and the peak area of 19.5%. The spacing between the two peaks was consistent with the presence of both high and low crystalline polymers. The delta between the DSC Tm and the Tcrystaf was 47.2 ° C.

Property test

The polymer samples were evaluated for physical properties such as TMA temperature test, pellet block strength, hot recovery rate, hot compressive strain and storage modulus ratio (G '(25 ° C.) / G' (100 ° C.)). . Several commercial polymers were included in the test. Comparative Example G ^* was a substantially linear ethylene / 1-octene copolymer (Affinity® available from The Dow Chemical Company), and Comparative Example H ^* was a substantially linear ethylene / 1-octene elastomer air Coalescence (Affinity® EG8100 available from The Dow Chemical Company) and Comparative Example I was a substantially linear ethylene / 1-octene copolymer (Affinity® available from The Dow Chemical Company). PL1840), Comparative Example J was hydrogenated styrene / butadiene / styrene triblock copolymer (KRATON® G1652 available from KRATON Polymers), and Comparative Example K was a thermoplastic vulcanizate ( TPV, polyolefin blend with crosslinked elastomer dispersed therein). The results are shown in Table 4.

In Table 4, Comparative Example F (which is a physical blend of two polymers resulting from co-polymerization with Catalysts A1 and B1) has a 1 mm penetration temperature of about 70 ° C., while Examples 5-9 are 100 ° C. Had a penetration temperature of at least 1 mm. In addition, Examples 10-19 all had a 1 mm penetration temperature above 85 ° C., mostly with 1 mm TMA temperatures above 90 ° C. or even above 100 ° C. This shows that the new polymers have better dimensional stability at higher temperatures compared to the physical blends. Comparative Example J (commercial SEBS) had a good 1 mm TMA temperature of about 107 ° C., but had a very poor (high temperature 70 ° C.) compression set of about 100%, which also recovers 300% strain at high temperature (80 ° C.). Recovery failed (sample failure). Thus, the polymers exemplified had a unique combination of properties that could not be obtained even with some commercially available high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio (G ′ (25 ° C.) / G ′ (100 ° C.)) of 6 or less for the polymers of the present invention, while the physical blend (Comparative Example F) The storage modulus ratio is 9 and similar density random ethylene / octene copolymers (Comparative Example G) show that the storage modulus ratio 89 is as large as the single-digit range. The storage modulus ratio of the polymer is preferably as close to 1 as possible. Such polymers are relatively unaffected by temperature, and articles made from such polymers can be usefully used over a wide temperature range. This low storage modulus ratio and temperature independence feature is particularly useful in elastomer applications such as pressure sensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers according to embodiments of the invention have improved pellet blocking strength. In particular, Example 5 has a pelletized block strength of 0 MPa, which means free flow under test conditions compared to Comparative Examples F and G, which show significant blocking. Blocking strength is important because bulk transport of polymers with large blocking strength can result in cohesion or adhesion of the product with storage or dropping, resulting in poor handling.

The high temperature (70 ° C.) compression set of the polymers of the present invention is generally good, meaning that it is generally less than about 80%, preferably less than about 70%, in particular less than about 60%. In contrast, Comparative Examples F, G, H and J all had a 70 ° C. compression set of 100% (maximum possible, indicating no recovery). Good high temperature compression set (low values) is particularly necessary for applications such as gaskets, window profiles, o-rings, and the like.

^1. Tested at 51 cm / min.

^2. Measured at 38 ° C. for 12 hours.

Table 5 shows the results for the mechanical properties at ambient temperatures of the various polymers as well as the new polymers. It can be seen that the polymers of the invention have very good wear resistance when tested according to ISO 4649, which generally exhibits a volume loss of less than about 90 mm ³ , preferably less than about 80 mm ³ , in particular less than about 50 mm ^3. have. In this test, high values indicate high volume loss, and consequently low wear resistance.

As shown in Table 5, the tear strength measured by the tensile notch tear strength of the polymer of the present invention was generally 1000 mJ or more. The tear strength of the polymers of the invention can be as high as 3000 mJ, even as high as 5000 mJ. Comparative polymers generally had a tear strength of 750 mJ or less.

Table 5 also shows that the polymers according to embodiments of the invention have better shrinkage stress at 150% strain (represented by higher shrinkage stress values) compared to some comparative samples. Comparative Examples F, G and H have a shrinkage stress value of 400 kPa or less at 150% strain, whereas the polymer of the present invention has a shrinkage stress value of 500 kPa (Example 11) to about 1100 kPa at 150% strain (Example 17). Polymers with higher 150% shrinkage stress values are very useful for elastic applications such as elastic fibers and fabrics, especially nonwovens. Other uses include diapers, hygiene and medical garment waistband articles such as tabs and elastic bands.

Table 5 also shows that the polymers of the present invention have an improved (lower) stress relaxation rate (at 50% strain) compared to Comparative Example G, for example. Low stress relaxation rate means that the polymer has a better effect in applications such as diapers and other garments where long term retention of elasticity at body temperature is desired.

Optical testing

The optical properties reported in Table 6 are based on compression molded films that are not substantially oriented. The optical properties of the polymer can vary over a wide range due to microcrystalline size changes resulting from changes in the amount of chain transfer agent used in the polymerization.

Extraction of Multiblock Copolymers

Extraction studies for the polymers of Examples 5, 7 and Comparative Example E were performed. In this experiment, polymer samples were weighed into a glass frit extraction thimble and placed in a Kumagawa type extractor. The extractor with sample was purged with nitrogen and a 50 mL round bottom flask was charged with 350 mL of diethyl ether. The flask was then fixed to the extractor. The ether was heated with stirring. The time at which the ether began to condense into the thimble was recorded and the extraction was run under nitrogen for 24 hours. At this time, heating was stopped and the solution was cooled. Any ether remaining in the extractor was returned to the flask. The ether in the flask was evaporated in vacuo at ambient temperature and the resulting solids were nitrogen purged dried. Any residue was transferred to a weighed bottle using hexane continuous wash. The combined hexane washes were then evaporated by further nitrogen purge and the residue was dried at 40 ° C. under vacuum overnight. Any ether remaining in the extractor was nitrogen purged dried.

Then, a second transparent round bottom flask filled with 35 mL of hexane was connected to the extractor. Hexane was stirred and heated to reflux and held at reflux for 24 h after hexane was first observed to condense into the thimble. The heating was then stopped and the flask was cooled. Any hexane remaining in the extractor was transferred back to the flask. Hexane was removed by evaporation under vacuum at ambient temperature and any residue remaining in the flask was transferred to a weighed bottle using hexane continuous wash. Hexane in the flask was evaporated by nitrogen purge and the residue was vacuum dried at 40 ° C. overnight.

The polymer sample remaining in the thimble after extraction was transferred from the thimble to a weighed bottle and vacuum dried overnight at 40 ° C. The results are shown in Table 7.

Additional polymers Example  19A-J, continuous solution polymerization, catalyst A1 / B2 + DEZ

Examples 19A-I : Continuous solution polymerization was carried out in a computer controlled well mixed reactor. Purified mixed alkane solvent (Isopar ™ E) available from ExxonMobil Chemical Company, ethylene, 1-octene and hydrogen (if used) were combined and fed to a 27 gallon reactor. The feed to the reactor was measured by a mass flow controller. The temperature of the feed stream was controlled using a glycol cooled heat exchanger and then introduced to the reactor. The catalyst component solution was metered using a pump and a mass flow meter. Liquid filling was performed at approximately 550 psig in the reactor. Drained from the reactor, water and additives were injected into the polymer solution. The polymerization was terminated by hydrolysis of the catalyst with water. The post reactor solution was then heated to prepare for two stage devolatilization. The solvent and unreacted monomers were removed during the devolatilization process. The polymer melt was pumped into a die for cutting pellets underwater.

Example 19J : Continuous solution polymerization was carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar® E) available from ExxonMobil Chemical Company, 2.70 lb / hr (1.22 kg / hr) of ethylene, 1-octene and hydrogen (if used) were subjected to a temperature control jacket and It was fed to a 3.8 L reactor equipped with an internal thermocouple. Solvent feed to the reactor was measured by a mass flow controller. Variable speed diaphragm pumps controlled the solvent flow rate and pressure to the reactor. On pump discharge, side flow was taken to provide flush flow for catalyst and cocatalyst injection lines and reactor stirrers. These flows were measured by a micro-motion mass flow meter and controlled by a control valve or by manual adjustment of the needle valve. The remaining solvent was combined with 1-octene, ethylene and hydrogen (if used) and fed to the reactor. If necessary, a mass flow controller was used to deliver hydrogen to the reactor. The temperature of the solvent / monomer solution was adjusted using a heat exchanger and then introduced into the reactor. The stream was introduced at the bottom of the reactor. The catalyst component solution was metered, combined with the catalyst flush solvent and introduced into the bottom of the reactor using a pump and a mass flow meter. Liquid filling was performed at 500 psig (3.45 MPa) with vigorous stirring in the reactor. Product was removed through the outlet line at the top of the reactor. All outlet lines from the reactor were vapor traced and insulated. A small amount of water was added to the outlet line with any stabilizer or other additives and the polymerization was stopped by passing the mixture through a static mixer. The product stream was then heated through a heat exchanger and then devolatilized. The polymer product was recovered by extrusion using a devolatilization extruder and a water cooled pelletizer.

Polymer Examples 20-23 were prepared using a procedure similar to that described above. Process details and results are listed in Tables 8A-8C. Selected polymer properties are listed in Tables 9A-9B. Table 9C shows the block index for various polymers measured and calculated according to the method described above. In the calculations performed herein, T _A was 372 ° K and P _A was 1.

¹ standard cm ³ / min

² [N- (2,6-di (1-methylethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dimethyl

³ bis- (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dimethyl

⁴ ppm in the final product calculated by mass balance

⁵ Polymer Producing Rate

⁶ conversion of ethylene in the reactor (% by weight)

⁷ Molar ratio in the reactor, Zn / C ₂ * 1000 = (Zn feed flow rate * Mw of Zn concentration / 1000000 / Zn) (total ethylene feed flow rate * (1- fraction ethylene conversion) / M _{w of} ethylene) * 1000. Note that "Zn" in "Zn / C ₂ * 1000" represents the amount of zinc in diethyl zinc ("DEZ") used in the polymerization process, and "C ₂ " represents the amount of ethylene used in the polymerization process. box.

⁸ molar ratio in reactor

⁹ Efficiency, lb polymer / lb M (where lb M = lb Hf + lb Zr)

^* "Co." stands for "comonomer".

^{1. The} standard cm ³ / min.

^2. [N- (2,6-di (1-methylethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridine-2-diyl) methane)] hafnium dimethyl

^3. Bis- (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

^4. molar ratio in the reactor; Zn / C ₂ * 1000 = (Zn feed flow rate * M _w of Zn concentration / 1000000 / Zn) (total ethylene feed flow rate * (1- fractional ethylene conversion) / M _{w of} ethylene) * 1000. Note that "Zn" in "Zn / C ₂ * 1000" represents the amount of zinc in diethyl zinc ("DEZ") used in the polymerization process, and "C ₂ " represents the amount of ethylene used in the polymerization process. box.

^5. Molar ratio in the reactor

^6. Polymer produce rate

^7. Ethylene Conversion in Reactor (%)

^8. Efficiency, kg polymer / g M (where g M = g Hf + g Zr)

1) L ^* is an ultra low density polyethylene made by Ziegler-Natta catalysis, available under the trade name ATTENE 4203 from The Dow Chemical Company.

2) M ^* is a polyethylene copolymer prepared by constrained geometry catalysis (ie, a single-position catalyst) and is available from The Dow Chemical Company under the tradename Affinity® PL1880G.

As shown in Table 9C, the polymers of the invention all have a weight average block index of greater than zero, while the random copolymers (polymers F ^* , L ^*, and M ^* ) are all zero or substantially zero (such as 0.01). Had a block index.

10 shows the block index distribution as a function of ATREF temperature for Polymer F ^* , Polymer 20, Polymer 8, and Polymer 5. FIG. For polymer F ^* , the block index for all ATREF fractions was zero or substantially zero (ie ≦ 0.01). Polymer 20 was made with relatively low concentration of diethyl zinc ("DEZ"). The weight average block index for all polymers was about 0.2 and the polymer had four fractions with a block index of about 0.7 to about 0.9. For Polymers 5 and 8, their weight average block indexes did not differ significantly (0.52 vs. 0.59) and the DEZ concentrations were considered to be about four times different. In addition, most of their fractions had a block index of about 0.6 or greater. Similar results were seen between Polymer 5 and Polymer 19B, which is shown in FIG. 11. However, there were some notable differences in the block index of fractions eluting at about 70 ° C to about 90 ° C. Polymer 19B was made with DEZ at a higher concentration (about 4 times higher concentration) than polymer 5. However, Polymer 5 had more fractions with higher block indices. This is believed to suggest that there may be an optimal DEZ concentration for the preparation of fractions with a higher block index (ie greater than about 0.6).

The effect of DEZ concentration levels on the mean block index of some polymers of Table 9C is shown in FIG. 12. The plot is believed to suggest that the average block index increases as DEZ initially increases. If Zn / C ₂ H ₄ * 1000 exceeds about 0.5, the average block index appears to be even, and can be reduced even if too much DEZ is used.

FIG. 13 is a plot of the square root of the second moment with respect to the average weight average block index as a function of [Zn / C ₂ H ₄ ] * 1000. This was found to decrease with increasing DEZ. This indicates that the distribution of the block index of the fraction is narrower (ie more uniform).

TREF  And NMR Data

Tables 10-14 list TREF, DSC, IR, and NMR data for Polymers 5, 8, 14, and 19 and various comparative polymers.

Infrared detector calibration: octene Mol% = 133.38 (FWHM CH ₃ / CH ₂ area)-100.8

N ^* is an ethylene homopolymer.

O ^* is an ethylene / octene copolymer available as Affinity® HF1030 from The Dow Chemical Company.

P ^* is an ethylene / octene copolymer available as Affinity® PL1880 from The Dow Chemical Company.

Q ^* is an ethylene / octene copolymer available as Affinity® VP8770 from The Dow Chemical Company.

Calculation of block index

Referring to Figures 8-9, the calculation of the block index is illustrated for Polymer 5. In this calculation, the following correction equation was used.

Ln P = -237.8341 / T _ATREF + 0.6390

In the formula, P is an ethylene mole fraction and T _ATREF is an ATREF elution temperature. In addition, the following parameters were used.

parameter value Explanation T _A 372.15 Analytical TREF elution temperature for hard segments (° K) P _A 1.000 Ethylene mole fraction of hard segments P _AB 0.892 Ethylene mole fraction of all polymers T _AB 315.722 Equivalent analytical TREF elution temperature (° K) calculated from total polymer ethylene content

Table 15 details the calculations for Polymer 5. The weighted average block index (ABI) for Polymer 5 was 0.531 and the square root of the sum of weighted squared deviations for the weighted average was 0.136. The weight subtotal with fraction BI greater than 0 (see note 2 below) was 0.835.

Note 1: Fraction # 1 was not crystallized in the analytical ATREF, with BI _i = 0.

Note 2: Only BI _i > 0 is used for the weighted squared deviation from the weighted mean.

Hard and soft Segment  Weight percent measurement

As discussed above, block interpolymers include hard segments and soft segments. The soft segment is, in the block interpolymer, from about 1% to about 99%, preferably from about 5% to about 95%, from about 10% to about 90%, about 15% by weight of the total weight of the block copolymer. % To about 85%, about 20% to about 80%, about 25% to about 75%, about 30% to about 70%, about 35% to about 65%, about 40% % To about 60% by weight, or about 45% to about 55% by weight. On the other hand, the hard segment may exist in a range similar to that described above. Soft segment weight percent (and thus hard segment weight percent) can be measured by DSC or NMR.

DSC Hardness measured by Segment  Weight fraction

For block polymers having hard and soft segments, the density (p _total ) of the entire block polymer satisfies the following relationship.

Where ρ _hard and ρ _soft are the theoretical densities of the hard and soft segments, respectively. χ _hard and χ _soft are the weight fractions of the hard segment and the soft segment, respectively, and their sum is one. Assuming the ρ _hard is equal to the density of the ethylene homopolymer, i.e., 0.96 g / cc, binomial of the above equation gives the following equation for the weight fraction of the hard segment.

In the above equation, the _total p can be measured from the block polymer. Thus, if ρ _soft is known, the hard segment weight fraction can be calculated accordingly. In general, the soft segment density has a linear relationship with the soft segment melt temperature, which can be measured by DSC over a certain range.

ρ _soft = A * T _m + B

Wherein A and B are constants and T _m is the soft segment melting temperature (Celsius). A and B can be determined by performing DSC on various copolymers with known densities to obtain calibration curves. It is desirable to create a soft segment calibration curve over a range of compositions (both comonomer type and content) present in the block copolymer. In some embodiments, the calibration curve satisfies the following relationship.

ρ _soft = 0.00049 * T _m + 0.84990

Thus, if T _m (Celsius) is known, the soft segment density can be calculated using the above equation.

For some block copolymers, there is an identifiable peak in the DSC associated with melting of the soft segments. In this case, it is relatively simple to measure the T _m of the soft segment. By measuring T _m (Celsius) from DSC, the soft segment density, and thus the hard segment weight fraction, can be calculated.

For other block copolymers, the peaks associated with melting of the soft segments are in the form of small humps (or bumps) above the baseline, or sometimes invisible as shown in FIG. This difficulty can be overcome by converting the normal DSC profile into a weighted DSC profile as shown in FIG. 15. The following method converts a normal DSC profile to a weighted DSC profile.

In DSC, the heat flow rate depends on the amount of material that melts at a particular temperature as well as the temperature dependent specific heat capacity. Due to the temperature dependence of the specific heat capacity in the melting mode of linear low density polyethylene, the heat of fusion increases as the comonomer content decreases. That is, the heat of fusion is gradually lowered as the crystallinity decreases with increasing comonomer content. Wild, L. Chang, S .; Shankernarayanan, MJ. Improved method for compositional analysis of polyolefins by DSC. Polym. Prep 1990; 31: 270-1.

At a given point in the DSC curve (defined by heat flux (watts / gram) and temperature (degrees Celsius)), the ratio of the heat of fusion prediction of the linear copolymer to the temperature dependent heat of fusion (ΔH (T)) By obtaining, the DSC curve can be converted into a weight dependency distribution curve.

The temperature dependent heat of fusion curve can be calculated from the sum of the integrated heat flow rates between the two consecutive data points and thus can be represented entirely by the cumulative enthalpy curve.

The predicted relationship of heat of fusion for a linear ethylene / octene copolymer at a given temperature is represented by the heat of fusion versus melting temperature curve. Using a random ethylene / octene copolymer, the following relationship can be obtained.

Melt Enthalpy (J / g) = 0.0072 * T _m ² (° C) + 0.3138 * T _m (° C) + 8.9767

For each integrated data point at a given temperature, the weight fraction can be assigned to each point of the DSC curve by obtaining the ratio of enthalpy from the cumulative enthalpy curve to the heat of fusion predicted linear copolymer at that temperature. .

In this method, it should be noted that the weighted DSC calculates in the range from 0 ° C. to the end of the melt. This method is applicable to ethylene / octene copolymers but can also be adapted to other polymers.

The method was applied to various polymers to calculate the weight percent of hard and soft segments, which are listed in Table 16. It should be noted that due to the fact that hard segments may contain small amounts of comonomers, it is sometimes desirable to specify 0.94 g / cc as the theoretical hard segment density instead of using a density for homopolyethylene.

NMR Hardness measured by Segment  weight%

¹³ C NMR spectroscopy is one of many techniques known in the art for measuring comonomer incorporation into a polymer. One example of such a technique is described in Randall (Journal of Macromolecular Science, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3), 201-317 (1989)), which is hereby incorporated by reference in its entirety. The comonomer content determinations for α-olefin copolymers are described. The basic procedure for measuring comonomer content of ethylene / olefin interpolymers involves obtaining ¹³ C NMR spectra under conditions in which the intensity of peaks corresponding to different carbons in the sample is directly proportional to the total number of contributing nuclei in the sample. Methods to ensure this proportion are known in the art and include the use of sufficient time for post-pulse relaxation, gated-decoupling techniques, the use of emollients and the like. The relative intensities of the peaks or groups of peaks are actually obtained from their integration obtained from the computer. After obtaining the spectrum and integrating the peaks, the peaks associated with the comonomers are designated. Such assignments can be made by reference to known spectra or literature, or by the synthesis and analysis of model compounds, or by the use of isotopically labeled comonomers. The comonomer mol% can be determined by the ratio of the integral corresponding to the number of moles of comonomer to the integral corresponding to the number of moles of all monomers in the interpolymer, as described in Randall's literature.

Since hard segments generally have less than about 2.0% comonomer, the main contribution to their spectrum is only for integration at about 30 ppm. Hard segment contributions to peaks other than 30 ppm are assumed to be negligible at the start of the assay. Thus, at the beginning, it is assumed that integration of peaks other than 30 ppm is obtained only from the soft segment. These integrations are fitted to the first Markovian statistical model of comonomers using linear least squares minimization, and thus fit parameters (ie octenes) used to calculate the soft segment contribution to the 30 ppm peak. The probability of post octene insertion (P _oo ) and the probability of post octene insertion (P _eo ) are obtained. The difference between the total measurement of the 30 ppm peak integration and the calculated value of the soft segment integration contribution to the 30 ppm peak is the contribution from the hard segment. Thus, the spectral experiment is now deconvoluted into two integral lists describing each of the soft and hard segments. The calculation of the weight percentage of the hard segment is simple, which is calculated by the ratio of the sum of the integrals of the hard segment spectra to the integral sum of the whole spectra.

From the deconvoluted soft segment integration list, the comonomer composition can be calculated, for example according to Randall's method. From the comonomer composition of the full spectrum and the comonomer composition of the soft segments, the mass equilibrium can be used to calculate the comonomer composition of the hard segments. From the comonomer composition of the hard segments, Bernoullian statistics are used to calculate the contribution of the hard segments to the integration of peaks other than 30 ppm. Bernoulli statistic is a valid and robust approximation because there is usually very little octene in the hard segments, typically from about 0 to about 1 mol%. These contributions are then subtracted from the experimental integration of peaks other than 30 ppm. The peak integration other than 30 ppm obtained is then adapted to the first Markovian statistical model for the copolymer as described in the paragraph above. The iteration process is carried out in the following manner. After fitting all peaks other than 30 ppm, the soft segment contribution to the 30 ppm peak is calculated; The soft / hard segment splits are then calculated and the hard segment contributions to peaks other than 30 ppm are calculated; The hard segment contributions to peaks other than 30 ppm are then corrected and the peaks other than 30 ppm obtained are fitted. This is repeated until the values for soft / hard segmentation converge to the minimum error function. Record the final comonomer composition for each segment.

Verification of the measurement is achieved by analysis of several in situ polymer blends. By design of polymerization and catalyst concentration, split predictions are compared to NMR split measurements. The soft / hard catalyst concentration is set at 74% / 26%. The measure of soft / hard segment split is 78% / 22%. Table 17 shows the assignment of chemical shifts for ethylene octene polymers.

The following experimental procedure was used. Samples were prepared by adding 0.25 g in a 10 mm NMR tube with 2.5 mL of stock solvent. The mother solvent was prepared by dissolving 1 g of deuterated 1,4-dichlorobenzene together with 0.025 M chromium acetylacetonate (releasing agent) in 30 mL of ortho-dichlorobenzene. The headspace of the tube was oxygen purged by pure nitrogen substitution. The sample tube was then heated in a set of heating blocks set at 150 ° C. The sample tube was repeatedly swirled and heated until the solution flowed steadily from the top of the solution column to the bottom. The sample tube was then left in the heating block for at least 24 hours to achieve optimal sample homogeneity.

¹³ C NMR data was collected using a Varian Inova Unity 400 MHz system with a probe temperature set at 125 ° C. The center of the excitation bandwidth was set at 32.5 ppm and the spectral width was set at 250 ppm. Acquisition parameters were optimized for quantification including 90 ° pulses, inverse gate ¹ H decoupling, 1.3 seconds acquisition time, 6 seconds delay time and 8192 scans for data average. The magnetic field was carefully calibrated to obtain a line shape of less than 1 Hz at full width at half maximum for solvent peaks prior to data acquisition. The raw data file was processed using NUTS processing software (available from Acorn NMR, Inc., Livermore, Calif.) To obtain an integral list.

Polymer 19A of the present invention was analyzed for soft / hard segment split and soft / hard comonomer composition. The list of integrations for this polymer is shown below. The NMR spectrum of polymer 19A is shown in FIG. 16.

Using Randall's three-way method, the total octene weight percentage in the sample was determined to be 34.6%. By fitting to the first Markovian statistical model using all of the integrations except 30.3 to 29.0 ppm integration, the values of P _oo and P _eo were determined to be 0.08389 and 0.2051, respectively. Using these two parameters, the calculation of the integral contribution from the soft segment to the 30 ppm peak was 602.586. By subtracting 602.586 from the total integral found 1177.893 for the 30 ppm peak, the contribution of the hard segment to the 30 ppm peak was obtained at 576.307. By using 576.307 as the integral for the hard segments, the weight percentage of the hard segments was determined to be 26%. Accordingly, the soft segment weight percentage was 100-26 = 74%. Using the values of P ₀₀ and P _eo , the octene weight percentage of the soft segment was determined to be 47%. Using not only the total octene weight percent and the octene weight percent of the soft segment but also the soft segment weight percent, the octene weight percent in the hard segment was calculated to be -2 weight percent. This value is within the measurement error range. Thus, there is no need to repeat again to calculate hard segment contributions to peaks other than 30 ppm. Table 18 summarizes the calculation results for polymers 19A, B, F and G.

As demonstrated above, embodiments of the present invention provide a new class of ethylene and α-olefin block interpolymers. The block interpolymers are characterized by an average block index of greater than zero, preferably greater than 0.2. The block interpolymers have unique properties or combinations of features that are not seen in other ethylene / α-olefin copolymers due to the block structure. The block interpolymers also include various fractions with different block indices. This distribution of block indices affects the overall physical properties of the block interpolymers. It is possible to obtain the ability to tailor the desired polymer by adjusting the polymerization conditions to change the block index distribution. Such block interpolymers have many end use applications. For example, block interpolymers can be used to prepare polymer blends, fibers, films, molded articles, lubricants, base oils, and the like. Other advantages and features will be apparent to those skilled in the art.

Although the present invention has been described with respect to a limited number of embodiments, certain features of one embodiment should not be applied to other embodiments of the invention as well. There is no single embodiment that is representative of all aspects of the invention. In some embodiments, a composition or method may comprise many of the compounds or steps mentioned herein. In other embodiments, the compositions or methods do not comprise or substantially comprise any compound or step listed herein. There are variations and modifications from the described embodiments. The process for preparing the resin is described as including many acts or steps. These steps or actions may be executed in any order or order unless otherwise noted. Finally, any numerical value disclosed herein should be intended to mean an approximation, regardless of whether the term “about” or “approximately” is used in describing the numerical value. It is intended that the appended claims cover all such modifications and variations as fall within the scope of the present invention.

Claims (36)

Ethylene / α-olefin interpolymer comprising polymerized ethylene and α-olefin units, characterized in that the average block index is greater than 0 and less than or equal to about 1.0 and the molecular weight distribution (M _w / M _n ) is greater than about 1.3. Ethylene / α-olefin interpolymers comprising polymerized ethylene and α-olefin units, characterized in that the average block index is greater than 0 and less than about 0.4 and the molecular weight distribution (M _w / M _n ) is greater than about 1.3. The ethylene / α-olefin interpolymer of claim 1 or 2, wherein the average block index is in the range of about 0.1 to about 0.3. The ethylene / α-olefin interpolymer of claim 1 wherein the average block index is in the range of about 0.4 to about 1.0. The ethylene / α-olefin interpolymer of claim 1 wherein the average block index is in the range of about 0.3 to about 0.7. The ethylene / α-olefin interpolymer of claim 1 wherein the average block index is in the range of about 0.6 to about 0.9. The ethylene / α-olefin interpolymer of claim 1 wherein the average block index is in the range of about 0.5 to about 0.7. The ethylene / α-olefin interpolymer of claim 1 or 2 having a density of less than about 0.91 g / cc. The ethylene / α-olefin interpolymer of claim 1 or 2 having a density in the range of from about 0.86 g / cc to about 0.91 g / cc. 3. The method of claim 1, wherein the α-olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5- Ethylene / α-olefin interpolymers that are hexadienes, or combinations thereof. The ethylene / α-olefin interpolymer according to claim 1 or 2, wherein the α-olefin is 1-butene. The ethylene / α-olefin interpolymer according to claim 1 or 2, wherein the α-olefin is 1-octene. The ethylene / α-olefin interpolymer of claim 1 or 2, wherein M _w / M _n is greater than about 1.5. The ethylene / a-olefin interpolymer of claim 1 or 2, wherein M _w / M _n is greater than about 2.0. 3. The ethylene / α-olefin interpolymer of claim 1, wherein M _w / M _n is from about 2.0 to about 8. 4. The ethylene / a-olefin interpolymer of claim 1 or 2, wherein M _w / M _n is from about 1.7 to about 3.5. According to claim 1 or 2, wherein the melting point (T _m) (degrees C) and density ^{(d) (g / cm 3} ) number is equivalent to the following relation of the ethylene that is characterized by one or more of T _m and d / α-olefin interpolymers. T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² The method according to claim 1 or 2, wherein the ethylene / α-olefin interpolymer is 300% strain and 1 cycle measured by compression molded film of the ethylene / α-olefin interpolymer when the crosslinked phase is substantially free of An ethylene / α-olefin interpolymer characterized by Re and d in which the numerical values of the elastic recovery rate (Re) (%) and the density (d) (g / cm ³ ) satisfy the following relationship. Re> 1481-1629 (d) Molecular weight distribution (M _w / M), comprising polymerized ethylene and α-olefin units, having one or more fractions having a block index greater than about 0.3 and up to about 1.0, obtained by temperature rise eluting fractionation ("TREF") ethylene / α-olefin interpolymer, wherein _n ) is greater than about 1.3. At least one fraction having a block index of greater than about 0 and up to about 0.4, obtained by TREF, and having a molecular weight distribution (M _w / M _n ) greater than about 1.3; Ethylene / α-olefin interpolymers. 21. The ethylene / a-olefin interpolymer of claim 19 or 20, wherein the fraction's block index is greater than about 0.4. 21. The ethylene / α-olefin interpolymer of claim 19 or 20, wherein the fraction's block index is greater than about 0.5. 21. The ethylene / a-olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.6. 21. The ethylene / α-olefin interpolymer of claim 19 or 20, wherein the fraction's block index is greater than about 0.7. 21. The ethylene / α-olefin interpolymer of claim 19 or 20 wherein the block index of the fraction is greater than about 0.8. 21. The ethylene / α-olefin interpolymer of claim 19 or 20, wherein the fraction's block index is greater than about 0.9. The ethylene / α-olefin interpolymer according to claim 1, 2, 19 or 20, wherein the ethylene content is greater than 50 mol%. 21. The ethylene / α-olefin interpolymer of claim 1, 2, 19 or 20 comprising at least one hard segment and at least one soft segment. The ethylene / α-olefin interpolymer of claim 1, 2, 19, or 20, wherein the hard segment is present in an amount from about 5% to about 85% by weight of the interpolymer. 21. The ethylene / α-olefin interpolymer of claim 1, 2, 19 or 20, wherein the hard segment comprises at least 98% by weight of ethylene. 21. The ethylene / α-olefin interpolymer of claim 1, 2, 19 or 20 wherein the soft segment comprises less than 90% by weight ethylene. 21. The ethylene / α-olefin interpolymer of claim 1, 2, 19 or 20, wherein the soft segment comprises less than 50 wt% ethylene. 21. The ethylene / a-olefin interpolymer of claim 1, 2, 19 or 20 comprising at least 10 hard and soft segments that are linked in a linear manner to form a linear chain. 34. The ethylene / α-olefin interpolymer of claim 33 wherein the hard and soft segments are randomly distributed along the chain. 21. The ethylene / α-olefin interpolymer of claim 1, 2, 19 or 20, wherein the soft segment does not comprise a tip segment. 21. The ethylene / α-olefin interpolymer of claim 1, 2, 19 or 20, wherein the hard segment does not comprise a tip segment.

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