KR20070117592A - Thermoplastic vulcanizate comprising interpolymers of ethylene/alpha-olefins - Google Patents

Abstract

Thermoplastic vulcanizates comprise at least an ethylene/alpha-olefin interpolymer and at least one thermoplastic polymer, such as polyolefin. The ethylene/alpha-olefin interpolymer is a block copolymer having at least a hard block and at least a soft block. The soft block comprises a higher amount of comonomers than the hard block. The block interpolymer has a number of unique characteristics disclosed here. The block interpolymer is either used as a compatibilizer between a vulcanizable elastomer and a thermoplastic polymer or as a vulcanizable elastomer when it is in the EPDM form. The thermoplastic vulcanizates can be profiled extruded to make profiles and gaskets.

Description

Thermoplastic Vulcanizate Comprising Interpolymers of Ethylene / α-Olefins

The present invention relates to thermoplastic vulcanizates with improved mechanical properties.

Elastomers are defined as materials that exhibit large reversible deformation under relatively low stress. Elastomers are typically characterized as having structural irregularities, non-polar structures, or flexible units in the polymer chain. Some examples of commercially available elastomers include natural rubber, ethylene / propylene (EPM) copolymers, ethylene / propylene / diene (EPDM) copolymers, styrene / butadiene copolymers, chlorinated polyethylene, and silicone rubbers.

Thermoplastic elastomers are elastomers having thermoplastic properties. That is, the thermoplastic elastomer is optionally molded or otherwise formed and reworked at temperatures above its melting or softening point. One example of a thermoplastic elastomer is a styrene-butadiene-styrene (SBS) block copolymer. SBS block copolymers exhibit a biphasic shape composed of glassy polystyrene domains connected by rubbery butadiene segments.

In contrast, thermoset elastomers are elastomers having thermosetting properties. That is, thermoset elastomers are generally irreversibly solidified or "cured" upon heating because of the irreversible crosslinking reaction. Thermogel is considered to be thermoset if the gel content as measured by xylene extraction is at least about 20% by weight based on total elastomer. Two examples of thermoset elastomers are crosslinked ethylene-propylene monomer rubber (EPM) and crosslinked ethylene-propylene-diene monomer rubber (EPDM). EPM materials are prepared by copolymerization of ethylene and propylene. EPM materials are typically cured and crosslinked with peroxides, thereby causing thermosetting properties. EPDM materials are linear interpolymers of ethylene, propylene, and non-conjugated dienes (eg, 1,4-hexadiene, dicyclopentadiene, or ethylidene norbornene). EPDM materials are typically vulcanized with sulfur to induce thermoset properties, but they can also be cured by peroxides. EPM and EPDM materials have utility in high temperature applications, and are advantageous in that EPM and EPDM elastomers have relatively low raw material strength (at low ethylene content), relatively low oil resistance, and relatively low surface modification resistance.

The thermoplastic vulcanizate (TPV) comprises a thermoplastic matrix, preferably crystalline, uniformly dispersed throughout the thermoset elastomer. Examples of thermoplastic vulcanizates are ethylene-propylene monomer rubbers and ethylene-propylene-diene monomer rubber thermosets dispersed in a crystalline polypropylene matrix. One example of a commercial TPV is Satoprene® thermoplastic rubber (manufactured by Advanced Elastomer Systems), which is a mixture of crosslinked EPDM particles in a crystalline polypropylene matrix. These materials are used in many applications using conventional vulcanized rubbers such as hoses, gaskets, and the like.

Commercially available TPVs are typically based on vulcanized rubber and diene (or more generally poly) using a phenolic resin or sulfur curing system by dynamic vulcanization, ie crosslinking, while mixing (typically strongly) in a thermoplastic matrix. N) The copolymer rubber is vulcanized, ie crosslinked.

Although many types of thermoplastic vulcanizates are known, there is still a need for improved thermoplastics with elastomeric properties. In particular, there is a need for a process for preparing thermoplastic vulcanizates having improved tensile properties, elongation, compression set and / or oil resistance. The improved properties would be beneficial for new applications such as blow molded articles, foams and wire cables as well as current applications of thermoplastic vulcanizates requiring high melt strength.

Summary of the Invention

The above needs are met by various aspects of the present invention.

In one aspect, the present invention

(i) vulcanizable elastomers;

(ii) thermoplastic polyolefins;

(iii) crosslinking agents; And

(iv) a thermoplastic vulcanizate comprising or obtainable from a reaction mixture comprising an ethylene / α-olefin interpolymer. In another aspect, the invention

(i) thermoplastic polyolefins;

(ii) crosslinking agents; And

(iii) a thermoplastic vulcanizate comprising or obtainable from a reaction mixture comprising a vulcanizable elastomer which is an ethylene / propylene / diene interpolymer. In some embodiments, the ethylene / α-olefin interpolymer or ethylene / α-olefin / diene interpolymer

(a) has an M _w / M _n of about 1.7 to about 3.5, one or more melting points T _m (° C.), and a density d (g / cm 3), wherein the values of T _m and d are represented by the following relation:

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

Or

(b) having a M _w / M _n of about 1.7 to about 3.5, the difference amount ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak; Wherein the values of ΔT and ΔH are as follows:

For ΔH above 0 and below 130 J / g, ΔT> -0.1299 (ΔH) + 62.81,

ΔT ≥ 48 ° C for ΔH above 130 J / g

The CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C, or

(c) has a 300% strain and an elastic recovery rate R _e (%) in one cycle, and a density d (g / cm 2) measured with a compression-molded film of an ethylene / α-olefin interpolymer, wherein R _e and d The value of is given by the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinked phases:

R _e > 1481-1629 (d)

Characterized by satisfying

(d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, the fraction being at least 5% higher than the mole comonomer content of the comparative random ethylene interpolymer fraction eluting at the same temperature range Have a molar content (wherein the comparative random ethylene interpolymer has the same comonomer (s) as the ethylene / α-olefin interpolymer and has a melt index, density and co-occupation within 10% of the ethylene / α-olefin interpolymer) Monomer molar content (based on total polymer);

(e) has a storage modulus G '(25 ° C) at 25 ° C and a storage modulus G' (100 ° C) at 100 ° C, wherein the ratio of G '(25 ° C) to G' (100 ° C) is about 1 From 1 to about 10: 1, or

(f) at least one molecule eluted at 40 ° C. to 130 ° C. using TREF, with a block index of fractions of at least 0.5 and about 1 or less and a molecular weight distribution M _w / M _n of greater than about 1.3 Have fractions,

(g) a thermoplastic vulcanizate having an average block index greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3.

In some embodiments, the interpolymer has the following relationship:

R _e > 1491-1629 (d);

R _e > 1501-1629 (d); or

R _e> satisfies 1511-1629 (d).

In another embodiment, the melt index of the interpolymer is from about 0.1 to about 2000 g / 10 minutes, from about 1 to about 1500 g / 10 minutes, from about 2 to about as measured according to ASTM D-1238, conditions 190 ° C./2.16 kg. About 1000 g / 10 minutes, about 5 to about 500 g / 10 minutes. In some embodiments, the interpolymer is present from about 55% to about 90% or from about 5% to about 45% of the total composition weight in the thermoplastic vulcanizate.

“Α-olefin” in the “ethylene / α-olefin interpolymer” or “ethylene / α-olefin / diene interpolymer” herein refers to C ₃ and higher α-olefins. In some embodiments, the α-olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, or a combination thereof, and the diene is norbornene, 1,5-hexadiene, or a combination thereof.

Preferably, the polyolefin used in the thermoplastic vulcanizate is a homopolymer such as polyethylene or polypropylene. Preferably, the vulcanizable elastomer is an ethylene / higher α-olefin copolymer or terpolymer, such as an ethylene-higher α-olefin-polyene (EPDM) polymer.

Thermoplastic vulcanizates may optionally contain one or more additives such as slippers, antiblocking agents, plasticizers, antioxidants, UV stabilizers, colorants or pigments, fillers, lubricants, invincible agents, flow aids, coupling agents, crosslinkers, nucleating agents, surfactants, Solvents, flame retardants, antistatic agents, or combinations thereof. Various products can be made from the thermoplastic vulcanizate compositions disclosed herein. Furthermore, methods of making and manufacturing thermoplastic vulcanizate compositions are provided.

Further aspects of the invention and features and characteristics of various embodiments of the invention will become apparent from the following detailed 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

5 is a plot of the octene content of the TREF fractionated ethylene / 1-octene copolymer fraction versus the ATREF elution temperature of the polymer fraction of Example 5 (curve 1) and the polymer fraction of Comparative Example F (curve 2). Squares represent Example F ^* and triangles represent Example 5.

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.

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 is comprised in at least about 60 mol%, at least about 70 mol%, or at least about 80 mol%, with the substantial remainder of the total polymer being at least one α-olefin having 3 or more carbon atoms. It includes the above other comonomers. 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.

Ethylene / α-olefin interpolymers comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form and are characterized by a plurality of blocks or segments having two or more polymerized monomer units that differ in chemical or physical properties. do. 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.

In other words, block copolymers typically do not have a structure as follows:

AAA --- AA-BBB --- BB

In another embodiment, the block copolymers typically do not have a third type of block comprising different comonomers. In another embodiment, each of block A and block B has monomers or comonomers distributed substantially randomly within the block. In other words, both block A and block B do not include two or more sub-segments (or sub-blocks) of different composition, such as a tip segment having a composition that is substantially different from the rest of the block.

Multiblock polymers typically include varying amounts of "hard" and "soft" segments. A "hard" segment refers to a block of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, preferably greater than about 98 weight percent, based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5% by weight, preferably less than about 2% by weight, based on the polymer weight. In some embodiments, the hard segments consist entirely or substantially all of ethylene. In contrast, a "soft" segment has a comonomer content (content of monomers other than ethylene) of greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or about 15 weight based on the polymer weight. It refers to a block of polymerized units that are greater than%. In some embodiments, the comonomer content in the soft segment is greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, about 50 Greater than or equal to about 60 weight percent.

Soft segments are often from about 1% to about 99% by weight of the total weight of the block interpolymer in the block copolymer, preferably from about 5% to about 95%, from about 10% to about 90% by weight of the block interpolymer. Wt%, about 15 wt% to about 85 wt%, about 20 wt% to about 80 wt%, about 25 wt% to about 75 wt%, about 30 wt% to about 70 wt%, about 35 wt% to about 65 Weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent. Hard segments may be present in a similar range to the contrary. Soft segment weight percent and hard segment weight percent can be calculated based on data obtained from DSC or NMR. These methods and calculations are described in Colin L. P .. Applied on March 15, 2006 under the names Colin LP Shan, Lonnie Hazlitt and assigned to Dow Global Technologies Inc. the name "ethylene / α-olefin block Pending US patent application serial number (insert if known), agent case number 385063-999558, the disclosure of which is incorporated herein by reference in its entirety.

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" preferably refers to polymers comprising two or more chemically distinct regions or segments connected in a linear manner, ie polymerized ethylene functional groups rather than pendant or grafted It refers to a polymer comprising end to end linked chemically differentiated units. 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 Differ in amount, uniformity, 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.

The term “thermoplastic vulcanizate” (TPV) refers to engineered thermoplastic elastomers in which the cured elastomeric phase is dispersed in a thermoplastic matrix. This typically includes one or more thermoplastics and one or more cured (ie crosslinked) elastomeric materials. Preferably, the thermoplastic forms a continuous phase and the cured elastomer forms a distinct phase, ie the domains of the cured elastomer are dispersed in the thermoplastic matrix. Preferably, the domain of the cured elastomer is about 0.1 μm to about 100 μm, about 1 μm to about 50 μm, about 1 μm to about 25 μm, about 1 μm to about 10 μm, or about 1 μm to about 5 μm It is completely uniformly distributed over the average domain size of the range. In some embodiments, the matrix phase of TPV is present in less than about 50 volume percent of TPV and the dispersed phase is present in at least about 50 volume percent of TPV. In other words, the crosslinked elastomeric phase is the main phase in TPV, while the thermoplastic polymer is floating. TPVs with this phase composition have good compression set. However, TPV can also be prepared in which the columnar is a thermoplastic polymer and the flotation is a crosslinked elastomer. Generally, cured elastomers have moieties that are insoluble in cyclohexane at 23 ° C. Preferably, the amount of insoluble portion is about 75% or greater than about 85%. In some cases, the amount of insoluble portion is greater than about 90%, greater than about 93%, greater than about 95%, or greater than about 97% of the total elastomer weight.

The branching index is a quantification of the degree of branching of long chains in selected thermoplastic polymers. Preferably, the branching index is less than about 0.9, 0.8, 0.7, 0.6 or 0.5. In some embodiments, the branching index is in the range of about 0.01 to about 0.4. In other embodiments, the branching index is less than about 0.01, less than about 0.001, less than about 0.0001, less than about 0.00001, or less than about 0.000001. This is defined by the following relationship:

Wherein g 'is the branching index, IV _Br is the intrinsic viscosity of the branched thermoplastic polymer (eg polypropylene), and IV _Lin is the corresponding linear thermoplastic having the same weight average molecular weight as the branched thermoplastic polymer. It is the inherent viscosity of the polymer, and for copolymers and terpolymers, the monomer units have substantially the same relative molecular weight ratios.

Intrinsic viscosity, also known as extreme viscosity number, is generally a measure of the capacity of a polymer molecule to improve the viscosity of a solution. This depends on both the size and shape of the dissolved polymer molecule. Comparing non-linear polymers with linear polymers having substantially the same weight average molecular weight is an indication of the composition of the non-linear polymer molecules. Indeed, this ratio of intrinsic viscosity is a measure of the degree of branching of the non-linear polymer. Methods for determining the intrinsic viscosity of propylene polymer materials are described by Elliott et al., J. App. Poly. Sci., 14, pp 2947-2963 (1970). In this application, the inherent viscosity in each case is measured using a polymer dissolved in decahydronaphthalene at 135 ° C. Another method of measuring the intrinsic viscosity of a polymer is ASTM D5225-98— Standard Test Method or Measuring Solution Viscosity of Polymers with a Differential Viscometer , which is hereby incorporated by reference in its entirety.

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 is also specifically disclosed as defined by the two R values defined above.

Embodiments of the present invention provide two types of thermoplastic vulcanizates (TPV) compositions and methods of making various TPVs. These TPVs have low compressive permanent strain, low tensile permanent strain, high tensile strength, elongation, tear strength, wear resistance, good dynamic properties and / or oil resistance. First, the thermoplastic vulcanizate composition comprises (1) a thermoplastic polymer, preferably a branched polyolefin having a branching index of less than 1.0; (2) vulcanizable elastomers; And (3) a mixture or reaction product of a crosslinking agent capable of vulcanizing the elastomer. Preferably, the crosslinker does not substantially degrade or crosslink the thermoplastic polymer. One class of new ethylene / α-olefin interpolymers in the form of EPDM is used alone or in combination with typical elastomers as vulcanizable elastomers. Alternatively, the thermoplastic vulcanizate composition may comprise (1) a thermoplastic polymer, preferably a branched polyolefin having a branching index of less than 1.0; (2) vulcanizable elastomers; (3) compatibilizers; And (4) a mixture or reaction product of a crosslinking agent capable of vulcanizing the elastomer, wherein any chemical form of ethylene / α-olefin interpolymer is used as a further component as a compatibilizer between the thermoplastic polymer and the vulcanizable elastomer . When compatibilizers are used, the ethylene / α-olefin interpolymers are present in TPV of less than 50%, but more than 0% of the total composition weight. Preferably, the ethylene / α-olefin interpolymers are greater than 0 weight percent and less than 40 weight percent, greater than 0 weight percent and less than 30 weight percent, greater than 0 weight percent and less than 20 weight percent, greater than 0 weight percent and less than 10 weight percent, 0 weight More than 8% by weight, more than 0% by weight and less than 6% by weight, more than 0% by weight and less than 5% by weight. In some embodiments, the compatibilizer is about 1% to about 10%, about 2% to about 9%, about 3% to about 8%, about 4% to about 7%, or about It is present in an amount from 5% by weight to about 8% by weight.

Ethylene / α-olefin Interpolymers

Ethylene / α-olefin interpolymers (also referred to as “interpolymers of the invention” or “polymers of the invention”) used in embodiments of the invention are polymerized forms of ethylene and one or more copolymerizable α-olefin comonomers. And multiblock or segment (block interpolymers), preferably multiblock copolymers, of two or more polymerized monomer units having different chemical or physical properties. The ethylene / α-olefin interpolymers are characterized by one or more of the following aspects.

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 ) (° C.) and density (d) (g / cm ³ ), and the numerical values of these variables correspond to the following relationship.

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 (° C.), and heat of fusion ΔH (J / g), defined as the temperature of the peak, wherein ΔT and ΔH satisfy the following relationship for ΔH of 130 J / g or less.

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”), the fractions having a comonomer molar content, Higher than the comonomer molar content of the comparative random ethylene interpolymer fraction eluting in the same temperature range, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer is the same comonomer (S) and characterized in that the melt index, density and comonomer molar content (based on the total polymer) are 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 10 weights for the block interpolymer. It is within%.

In another aspect, the ethylene / α-olefin interpolymer has a 300% strain and elastic recovery rate (Re) (%), and density (d) measured in a compression molded film of ethylene / α-olefin interpolymer. ) (g / cm ³ ), wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinked phases.

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 other embodiments, the ethylene / α-olefin interpolymer has a storage modulus ratio G ′ (25 ° C.) / G ′ (100 ° C.) of about 1: 1 to 50: 1, about 1: 1 to 20: 1, or about 1: 1 to 10: 1. Preferably, the storage modulus ratio G ′ (25 ° C.) / G ′ (100 ° C.) is about 1: 1 to about 9: 1, about 1: 1 to about 8: 1, about 1: 1 to about 7: 1 , About 1: 1 to about 6: 1, about 1: 1 to about 5: 1, or about 1: 1 to about 4: 1.

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.

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, the polymers are first fractionated into fractions having an elution temperature range of 10 ° C. or lower, respectively, using TREF. 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.

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 degrees Celsius.

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. In addition, the comonomer content for the fractions of the various block ethylene / 1-octene block interpolymers of the present invention are shown. 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. The peaks eluting at 40 ° C. to 130 ° C., preferably 60 ° C. to 95 ° C., for the two polymers were fractionated into three parts, each part eluting at a temperature range below 10 ° C. Actual data for Example 5 are shown as triangles. One skilled in the art can construct an appropriate calibration curve for interpolymers containing different comonomers, and the lines used as comparisons for TREF temperature values are comparative interpolymers with the same monomers, preferably metallocenes or other It can be appreciated that it is obtained using a random copolymer prepared using a homogeneous catalyst composition. The interpolymers of the present invention are characterized by a comonomer molar content that is greater than, preferably at least 5% and more preferably at least 10% greater than the value measured from the calibration curve at the same TREF 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. The silver comonomer molar content is higher than the comonomer molar content of the comparative random ethylene interpolymer fraction eluting in the same temperature range, preferably at least 5% higher, more preferably 10%, 15%, 20% or 25 At least% high, wherein the comparative random ethylene interpolymer comprises the same comonomer (s), preferably copper And in that the comonomer (s), and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of the cases of the blocked interpolymer characterized. Preferably, in the case of a copolymer in which 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 blocked It is within 10 weight%.

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. At least an amount of interpolymers of ethylene and at least one α-olefin, where T is the value of the peak ATREF elution temperature of the TREF fraction to be compared, measured in ° C.

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, the polymers are first fractionated into fractions having an elution temperature range of 10 ° C. or lower, respectively, using TREF. 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 comonomer content predicted by infrared spectroscopy at development using full width at half maximum (FWHM) area calculations, and average comonomer moles Average porosity of comparative random ethylene interpolymer peaks at the same elution temperature, with content developed using full width at half maximum (FWHM) area calculation Higher than the body molar content, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer has the same comonomer (s) as the blocked interpolymer and has a melt index, density and The comonomer molar content (based on the total polymer) is characterized by being within 10% by weight of the block interpolymer. 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 in the case of block interpolymers. It is 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, with techniques based on nuclear magnetic resonance (NMR) spectroscopy preferred. Using this technique, the blocked interpolymers have a higher comonomer molar content than the corresponding comparative interpolymers.

Preferably, especially for interpolymers having an overall polymer density of from about 0.855 to about 0.935 g / cm ³ , more particularly for polymers having more than about 1 mol% comonomer, the blocked interpolymer is 40 ° C. Is a copolymer of ethylene and one or more α-olefins, wherein the comonomer content of the TREF fraction eluting at 130 ° C. is at least an amount of (-0.2013) T + 20.07, more preferably at least an amount of (-0.2013) T + 21.07. Where T is the value of the peak ATREF elution temperature of the compared TREF fraction, measured in ° C.

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 about 6 mol% or more 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 higher. 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 polymers of the present invention preferably comprise ethylene and at least one copolymerizable comonomer in polymerized form and have a plurality of blocks or segments having at least two polymerized monomer units having 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, and ATREF All fractions having an elution temperature of at least about 76 ° C. are characterized by having a melting enthalpy (heat of fusion) corresponding to the following formula measured by DSC.

Heat of fusion (J / g) ≤ (3.1718) (ATREF elution temperature (° C)) -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 (° C)) + 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 α-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 copolymer", Polymeric Material 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 copolymer using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170.] Included for reference).

In other embodiments, the ethylene / α-olefin interpolymers of the invention 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 weight average of the block index (“BI”) for each polymer fraction obtained in the preparative TREF at 20 ° C. to 110 ° C. in 5 ° C. increments.

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.

For each polymer fraction, BI is defined by one of the following two equations, both of which give the same BI value.

Where T _X is the preparative ATREF elution temperature (preferably expressed in Kelvin) for the i-th fraction and P _X is the ethylene mole fraction for the i-th fraction, which can be measured by NMR or IR as above. 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). If the actual value for the "hard segment" is not valid, the T _A and P _A values as first approximations are set to the values for the high density polyethylene homopolymer. For the calculations performed herein, T _A is 372 Kelvin and P _A is 1.

T _AB is the ATREF elution temperature for random copolymers of the same composition with an ethylene mole fraction of P _AB . T _AB can be calculated from the following equation.

Ln P _AB = α / T _AB + β

Wherein α and β are two constants that can be determined by calculation using a large number of known random ethylene copolymers. It should be noted that α and β may vary from instrument to instrument. In addition, there is a need to generate calibration curves by the polymer composition of interest and also in similar suitable molecular weight ranges for the fractions. 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, the random ethylene copolymer meets the following relationship.

Ln P = -237.83 / T _ATREF + 0.639

T _XO is the ATREF temperature for a random copolymer of the same composition with an ethylene mole fraction of P _X. T _XO can be calculated from LnP _X = α / T _XO + β. Conversely, P _XO is the ethylene mole fraction for random copolymers of the same composition whose ATREF temperature is T _X (which can be calculated from Ln P _XO = 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 0.3, or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.3 and up to about 1.0. Preferably, 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 having a block index greater than about 0.1 up to about 1.0, which can be obtained by preparative TREF. Including a fraction, 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.

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 from 0 to 100 ° C. (shown in FIG. 6), which is a property of the block copolymers, which means that olefin copolymers, in particular ethylene and at least one C _The copolymer of _3-8 aliphatic α-olefins has not been known so far. (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 ). 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.

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 / 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 one or more addition polymerizable monomers other than ethylene and optionally 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) chain transfer agent

Contacting with a catalyst composition comprising a mixture or reaction product formed in combination.

Representative catalysts and chain transfer agents are as follows.

Catalyst (A1) : [N- (2,6-di (1-methylethyl) prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024 (filed May 2, 2003) and WO 04/24740. ) Phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A2) : [N- (2,6-di (1-methylethyl) prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024 (filed May 2, 2003) and WO 04/24740. ) Phenyl) amido) (2-methylphenyl) (1,2-phenylene- (6-pyridin-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) substantially prepared according to the teachings of US-A-2004 / 0010103 2-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) silane substantially prepared according to the teachings of USP 6,268,444 Titanium dimethyl.

Catalyst ( C2 ) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a-η- substantially prepared according to the teachings of US-A-2003 / 004286 Inden-1-yl) silanetitanium dimethyl.

Catalyst ( C3 ) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a-η- substantially prepared according to the teachings of US-A-2003 / 004286 s-indasen-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 embodiments of the present invention are preferably interpolymers of ethylene and one or more C ₃ -C ₂₀ α-olefins. 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.

The amount of polymer blend in the ethylene / α-olefin interpolymers disclosed herein can be from about 5 to about 95 weight percent, from about 10 to about 90 weight percent, from about 20 to about 80 weight percent, from about 30 to about 30 weight percent, based on the total weight of the polymer blend. About 70%, about 10% to about 50%, about 50% to about 90%, about 60% to about 90%, or about 70% to about 90% by weight.

Thermoplastic Polyolefin

As discussed above, TPV comprises at least a thermoplastic polymer as a matrix phase. Suitable thermoplastic polymers include, but are not limited to, branched polyethylene (eg, high density polyethylene), branched polypropylene, branched polycarbonate, branched polystyrene, branched polyethylene terephthalate, and branched nylon. Although other thermoplastic polymers can be used, thermoplastic polyolefins, especially branched polyolefins, are preferred.

Preferably, the polyolefin should have a melt strength (“MS”) of at least about 6 cN. In some embodiments, the MS of the polyolefin is at least about 7 cN, at least about 8 cN, at least about 9 cN, at least about 10 cN, at least about 13 cN, at least about 15 cN, at least about 17 cN, or at least about 20 cN. . Generally, the MS of the polyolefin is less than about 200 cN, preferably less than about 150 cN, less than about 100 cN, or less than about 50 cN. Typically, the compression set at 70 ° C. of such polyolefins is greater than about 50%. In some embodiments, the compression set at 70 ° C. is greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90%.

Suitable polyolefins are polymers derived from one or more olefins. Olefins (ie, alkenes) are hydrocarbons containing one or more carbon-carbon double bonds. Some non-limiting examples of olefins are linear or branched, cyclic or acyclic alkenes having 2 to about 20 carbon atoms. In some embodiments, alkenes have 2 to about 10 carbon atoms. In other embodiments, the alkenes contain two or more carbon-carbon double bonds, for example butadiene and 1,5-hexadiene. In further embodiments, at least one of the hydrogen atoms of the alkene is substituted with alkyl or aryl. In a particular embodiment, the alkenes are ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, norbornene, 1-decene, butadiene, 1,5-hexa Dienes, styrene or combinations thereof.

Any of the polyolefins that meet the various criteria disclosed herein can be used to prepare the polymer blends disclosed herein. Non-limiting examples of polyolefins include polyethylene (eg, ultra low density, low density, linear low density, medium density, high density and ultra high density polyethylene); Polypropylene (eg, low density and high density polypropylene); Polybutylene (eg polybutene-1); Polypentene-1; Polyhexene-1; Polyoctene-1; Polydecene-1; Poly-3-methylbutene-1; Poly-4-methylpentene-1; Polyisoprene; Polybutadiene; Poly-1,5-hexadiene; Interpolymers derived from olefins; Interpolymers derived from olefins and other polymers (eg, polyvinyl chloride, polystyrene, polyurethane, etc.); And mixtures thereof. In some embodiments, the polyolefin is a homopolymer, such as polyethylene, polypropylene, polybutylene, polypentene-1, poly-3-methylbutene-1, poly-4-methylpentene-1, polyisoprene, polybutadiene, poly -1,5-hexadiene, polyhexene-1, polyoctene-1 and polydecene-1. In other embodiments, the polyolefin is polypropylene or high density polyethylene (HDPE).

The amount of polyolefin in the polymer blend is about 5 to about 95 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 30 to about 70 weight percent, and about 10 to about based on the total weight of the polymer blend. 50 weight percent, about 50 to about 80 weight percent, about 60 to about 90 weight percent, or about 10 to about 30 weight percent.

Preferred classes of polyolefins are high MS ethylene polymers. Any ethylene polymer with MS of 6 cN or more can be used. Ethylene polymers are any polymers comprising more than 50 mole percent -CH ₂ -CH ₂ -repeating units derived from ethylene monomers or comonomers. Suitable ethylene polymers for use in embodiments of the present invention include any ethylene-containing polymer, ie both homopolymers and copolymers. Examples of ethylene polymers include ethylene homopolymers and ethylene interpolymers, such as low density polyethylene (LDPE), heterogeneously branched ethylene / α-olefin interpolymers (ie, linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE)), substantially Linear ethylene polymers (SLEP), and homogeneously branched ethylene polymers, but are not limited to these.

In some embodiments, the ethylene polymer is a homogeneously branched (“homogeneous”) ethylene polymer, such as the homogeneously branched linear ethylene / a-olefin interpolymers described in Elston, US Pat. No. 3,645,992, or Lai. Homogeneously branched substantially linear ethylene polymers described in US Pat. Nos. 5,272,236, 5,278,272, 5,665,800, and 5,783,638, et al., Which are incorporated herein by reference.

In other embodiments, polypropylene polymers are used as thermoplastic polymers. Polypropylene can be branched or non-branched. One class of branched polypropylenes is coupled impact propylene polymers. As used herein, "coupling" refers to reacting a polymer with a suitable coupling agent to effect the rheology of the polymer. A "coupled polymer" is a rheologically modified polymer following the coupling reaction. The coupled polymer is characterized by an increase in melt strength of at least about 25% and a decrease in melt flow rate relative to the polymer before coupling. The coupled polymer is thermoplastic and has a low gel level, i.e., a gel content of less than about 50 weight percent, preferably less than about 30 weight percent, less than about 20 weight percent, less than about 10 weight percent, or less than about 5 weight percent. In that respect, they are different from highly crosslinked polymers. In contrast, as a result of a high degree of crosslinking (also known as “vulcanization”), the gel level is high, ie the gel content is greater than about 50%, preferably greater than about 70%, greater than about 80%, about 90% A thermosetting polymer is obtained which is more than% or more than about 95% by weight.

One class of suitable coupled propylene polymers is what is known as "coupled impact polypropylene polymers." Such polymers and methods for their preparation are disclosed in US Pat. No. 6,359,073, US Patent Application No. 09 / 017,230, filed June 23, 2000, and PCT Application No. WO 00/78858 A2, filed June 23, 2000. ), Which are incorporated by reference in their entirety. Methods of making coupled impact propylene copolymers include coupling the impact propylene copolymer with a coupling agent. The coupling reaction is performed by reactive extrusion, or by any other method that can mix the coupling agent with the impact propylene copolymer and add sufficient energy to cause the coupling reaction between the coupling agent and the impact propylene copolymer. Preferably, the process is carried out in a single vessel, such as a melt mixer or polymer extruder, such as US patent application Ser. No. 09 / 133,576 (filed Aug. 13, 1998; filed Aug. 27, 1997; Claim 057,713, the entirety of which is incorporated herein by reference in its entirety.

The term “impact propylene copolymer” as used herein is an ideal propylene copolymer in which polypropylene is a continuous phase and an elastomeric phase is dispersed therein. Those skilled in the art recognize that this elastomeric phase may also contain crystalline regions, which regions are considered part of the elastomeric phase for the purposes of embodiments of the present invention. Impact propylene copolymers are obtained from in-reactor processes rather than physical blending. Usually, the impact propylene copolymer is formed in a two stage or multistage process, which process optionally comprises a single reactor in which at least two stages are carried out, or comprises multiple reactors. Impact propylene copolymers are commercially available and are well known in the art and are described, for example, in E.P. Moore, Jr in Polypropylene Handbook, Hanser Publishers, 1996, page 220-221 and US Pat. Nos. 3,893,989 and 4,113,802, all of which are incorporated herein by reference in their entirety. Further suitable impact propylene copolymers are described in US Pat. No. 4,434,264; No. 4,459,385; No. 4,489,195; 4,493,923; 4,508,872; No. 4,535,125; 4,588,775; 4,588,775; 4,843,129; 4,843,129; 4,966,944; 5,011,891; 5,034,449; 5,034,449; 5,066,723; 5,066,723; 5,177,147; 5,177,147; 5,314,746; 5,314,746; 5,336,721; 5,336,721; 5,367,022; 5,367,022; 6,207,754; 6,207,754; 6,268,064, the entirety of which is incorporated herein by reference.

Suitable coupling agents are poly (sulfonyl azide), more preferably bis (sulfonyl azide). The term "poly (sulfonyl azide)" as used herein refers to two or more reactive groups with -CH groups, preferably primary or secondary -CH groups and / or unsaturated groups (eg -C = C-). Any compound having a sulfonyl azide group (-SO ₂ N ₃ ). Preferably, it can react with primary or secondary -CH groups of polyolefins or elastomers. Poly (sulfonyl azide) is used as coupling agent or crosslinking agent in an embodiment of the present invention. Preferably, the poly (sulfonyl azide) is X--R--X wherein each X is SO ₂ N ₃ and R is unsubstituted or inertly substituted hydrocarbyl, hydrocarby Represents a bill ether or silicon-containing group, preferably sufficient carbon, oxygen or silicon, preferably carbon atoms, more preferably sufficient to separate the sulfonyl azide group to allow for a smooth reaction between the polyolefin and sulfonyl azide Between functional groups one or more, more preferably two or more, most preferably three or more carbon, oxygen or silicon, preferably carbon atoms). The term "inertly substituted" refers to being substituted with atoms or groups that do not adversely affect the desired reaction or desired properties of the resulting crosslinked polymer. Such groups include fluorine, aliphatic or aromatic ethers, siloxanes, as well as sulfonyl azide groups when two or more polyolefin chains are connected. In a suitable structure, R is an aryl, alkyl, aryl alkaryl, arylalkyl silane, or heterocyclic group, and other groups that inactivate and separate the sulfonyl azide groups described. More preferably, R between sulfonyl groups includes at least one aryl group, most preferably at least two aryl groups (eg, R is 4,4'-diphenylether or 4,4'-biphenyl). have. When R is one aryl group, as in the case of naphthalene bis (sulfonyl azide), the group preferably has one or more rings. Poly (sulfonyl) azides include 1,5-pentane bis (sulfonyl azide), 1,8-octane bis (sulfonyl azide), 1,10-decane bis (sulfonyl azide), 1,10 -Octadecane bis (sulfonyl azide), 1-octyl-2,4,6-benzene tris (sulfonyl azide), 4,4'-diphenyl ether bis (sulfonyl azide), 1,6- Bis (4′-sulfonazidophenyl) hexane, 2,7-naphthalene bis (sulfonyl azide), and chlorinated aliphatic containing an average of 1 to 8 chlorine atoms and about 2 to 5 sulfonyl azide groups per molecule Compounds such as mixed sulfonyl azide of hydrocarbons, and mixtures thereof. Preferred poly (sulfonyl azide) s include oxy-bis (4-sulfonylazidobenzene), 2,7-naphthalene bis (sulfonyl azido), 4,4'-bis (sulfonyl azido) biphenyl, 4 , 4'-diphenyl ether bis (sulfonyl azide) and bis (4-sulfonyl aziphenyl) methane, and mixtures thereof.

Examples of poly (sulfonyl azide) s useful for thermoplastic vulcanizates are described in WO 99/10424. Poly (sulfonyl) azides include 1,5-pentane bis (sulfonyl azide), 1,8-octane bis (sulfonyl azide), 1,10-decane bis (sulfonyl azide), 1,10 -Octadecane bis (sulfonyl azide), 1-octyl-2,4,6-benzene tris (sulfonyl azide), 4,4'-diphenyl ether bis (sulfonyl azide), 1,6- Bis (4′-sulfonazidophenyl) hexane, 2,7-naphthalene bis (sulfonyl azide), and chlorinated aliphatic containing an average of 1 to 8 chlorine atoms and about 2 to 5 sulfonyl azide groups per molecule Compounds such as mixed sulfonyl azide of hydrocarbons, and mixtures thereof. Preferred poly (sulfonyl azide) s include oxy-bis (4-sulfonylazidobenzene), 2,7-naphthalene bis (sulfonyl azido), 4,4'-bis (sulfonyl azido) biphenyl, 4 , 4'-diphenyl ether bis (sulfonyl azide) and bis (4-sulfonyl aziphenyl) methane, and mixtures thereof.

Sulfonyl azide is commercially available and can be prepared conventionally by reaction of sodium azide with the corresponding sulfonyl chloride, but sulfonyl using various reagents (nitric acid, dinitrogen tetraoxide, sodium nitride tetrafluoroborate) Oxidation of hydrazine has been used.

Bis (sulfonyl azide) is used as coupling agent and is preferably at least about 100 ppm azide, more preferably about 150 ppm, based on the total weight of the impact propylene copolymer for coupling the impact propylene copolymer. More than one azide, most preferably at least about 200 ppm of azide. In some instances, where it is desired, for example, that the soft-brittle transition temperature is significantly reduced as compared to the base comparative non-coupled impact propylene copolymer, the total of the impact propylene copolymer for coupling of the impact propylene copolymer At least about 300 ppm bis (sulfonyl azide) by weight, preferably at least about 450 ppm bis (sulfonyl azide) are used. In selecting the impact propylene copolymer to be coupled, the polymer has a sufficiently high melt flow rate, and after coupling with the desired amount of coupling agent, the melt flow rate high enough for the coupled impact propylene copolymer to be easily processed. It is important to choose a polymer so that

In some embodiments, the coupled impact propylene copolymer is characterized by the following formula:

X = [(A-C) / (B-D)] <0.75;

Y ≧ 1.25; And

A ≤ B-10

Wherein A is from a notched Izod value (measured according to ASTM D-256) measured using a notch perpendicular to the polymer injection flow direction for the product made from the coupled impact propylene copolymer resin. Calculated soft-brittle transition temperature, B is the Notch Izod value measured using a notch perpendicular to the polymer injection flow direction for products made from the corresponding non-coupled impact propylene copolymer resin (ASTM D- Notched Izod value (ASTM) measured using a notch parallel to the polymer injection flow direction for a product made from coupled impact propylene copolymer resin, calculated from the soft-brittle transition temperature calculated in accordance with 256). Soft-brittle transition temperature, calculated from D-256), and D is prepared from the corresponding non-coupled impact propylene copolymer resin. The soft-brittle transition temperature calculated from the Notch Izod value (measured according to ASTM D-256) measured using a notch parallel to the polymer injection flow direction for the product.

Y is the ratio of the melt strength of the coupled impact propylene copolymer resin to the melt strength of the corresponding non-coupled impact propylene copolymer resin. In some embodiments, Y is at least about 1.5, at least about 2, at least about 5, or at least about 10. In other embodiments, X is less than about 0.5, less than about 0.33, or less than about 0.25.

The coupled impact propylene copolymer has improved impact properties compared to the non-coupled impact propylene copolymer, and the melt strength of the resulting coupled impact propylene copolymer resin has a corresponding non-coupled impact propylene air. At least about 1.25 times, preferably at least about 1.5 times, greater than the coalescence. The corresponding non-coupled impact propylene copolymer is the same polymer used to prepare the coupled impact propylene copolymer, except that it is not coupled. Preferably, the melt strength of the coupled impact propylene copolymer resin is at least about 8, at least about 15 cN, at least about 30 cN, at least about 50 cN, or at least about 60 cN. In some embodiments, the melt flow rate of the coupled impact propylene polymer may be from about 0.01 to about 100 g / 10 minutes as measured according to ASTM 1238 at 230 ° C. and 2.16 kg. Preferably, the melt flow rate is about 0.05 to about 50 g / 10 minutes, about 0.1 to about 10 g / 10 minutes, or about 0.5 to about 5 g / 10 minutes.

An example of the impact properties of the coupled impact propylene copolymer improved over the corresponding non-coupled impact propylene copolymer is, for example, high impact at low temperatures exerted by products made from the coupled impact propylene copolymer. There is an improvement in strength and reduced soft-brittle transition temperature in articles made from coupled impact propylene copolymers.

“Impact properties” refer to the properties of the product, such as impact strength measured by any person skilled in the art, eg, Izod impact energy measured according to ASTM D 256, MTS peak impact measured according to ASTM D 3763-93. Energy (dart impact), and MTS total impact energy measured according to ASTM D-3763. Ductile-brittle transition temperature (DBTT) also represents the impact properties of articles made from polymers. Ductile-brittle transition temperature is defined as the temperature at which an object transitions from the predominance of the wavefront's ductile mode to the predominance of the wavefront's embrittlement mode. Ductile-brittle transition temperatures can be calculated using methods known in the art.

Any amount of coupled impact propylene polymer may be used to make TPV, so long as the coupled impact propylene polymer is sufficient to be a thermoplastic matrix. Typically, the coupled impact propylene polymer is at least 10% by volume, preferably about 15 to about 65%, about 20 to about 50%, 25 to about 45%, or about 30 to about 10% by volume of the total TPV composition. Present in an amount of 45% by volume. Preferably, the coupled impact propylene polymer is floating, ie is present at less than 50% by volume of the TPV composition.

Examples of representative branched propylene polymers include Profax® 814 and Propax® 611 from Basell Polyolefins, The Netherlands, or The Dow, Midland, Michigan. Comparative Polypropylene from Chemical Company.

In addition to the branched propylene polymers described herein, suitable branched propylene polymers include US Pat. No. 4,311,628; 4,521,566; 4,916,198; 5,047,446; 5,047,446; 5,047,485; 5,414,027 and 5,849,409, and PCT Patent Application WO 01/53078; WO 97/20888; WO 97/20889; WO 99/10423; There are those described in WO 99/10424 and WO 99/16797. All of these patents and patent applications are incorporated herein by reference in connection with the disclosure of the branched propylene polymer.

Vulcanizable  Elastomer

Any vulcanizable elastomer can be used to form TPV as long as it can be crosslinked (ie, vulcanized) by a crosslinking agent. Vulcanizable elastomers are generally classified as thermosetting because they are thermoplastic in the uncured state, but are irreversibly thermoset in an unprocessable state. Preferably, the vulcanized elastomer is dispersed in the matrix of the thermoplastic polymer as a domain. The average domain size may be about 0.1 μm to about 100 μm, about 1 μm to about 50 μm, about 1 μm to about 25 μm, about 1 μm to about 10 μm, or about 1 μm to about 5 μm. Preferred elastomers are ethylene-higher α-olefin copolymers and terpolymers.

One class of preferred elastomers is, but is not limited to, ethylene-higher α-olefin-polyene (EPDM) polymers. Any EPDM rubber that can be fully cured (crosslinked) by a phenolic curing agent or other crosslinking agent is satisfactory. In some embodiments, ethylene / α-olefin interpolymers in EPDM form are used as vulcanizable elastomers. Suitable monoolefin terpolymer rubbers include essentially non-crystalline rubber-based terpolymers of two or more alpha monoolefins, and are preferably copolymerized using one or more polyenes, usually non-conjugated dienes. Suitable EPDM rubbers include products formed from the polymerization of two monoolefins, generally ethylene and propylene, and monomers comprising lower quality non-conjugated dienes. The amount of non-conjugated diene is usually about 2 to about 10 weight percent of the rubber. Any EPDM rubber that is sufficiently cured by having sufficient reactivity with the phenol crab curing agent is suitable. The reactivity of EPDM rubbers depends on the amount of unsaturation and the type of unsaturation present in the polymer. For example, EPDM rubbers derived from ethylidene norbornene are more reactive to phenolic curing agents than EPDM rubbers derived from dicyclopentadiene, and EPDM rubbers derived from 1,4-hexadiene are dicyclopenta. It is more reactive against phenolic curing agents than EPDM rubbers derived from dienes. However, differences in reactivity can be overcome by polymerizing smaller amounts of active dienes into rubber molecules. For example, 2.5% by weight of ethylidene norbornene or dicyclopentadiene is sufficient to impart sufficient reactivity to EPDM, while it can be fully cured by phenolic curing agents including conventional curing activators, At least 3.0% by weight is required to obtain sufficient reactivity in EPDM rubber derived from 1,4-hexadiene. EPDM rubbers of a grade suitable for embodiments of the present invention are commercially available and are described in Rubber World Blue Book 1975 Edition, Material and Compounding Ingredients for Rubber, pages 406-410.

Generally, EPDM elastomers have an ethylene content of about 10 to about 90 weight percent, a higher α-olefin content of about 10 to about 80 weight percent, and a polyene content of about 0.5 to about based on the total weight of the polymer. 20 wt%. Higher α-olefins contain about 3 to about 14 carbon atoms. Examples are propylene, isobutylene, 1-butene, 1-pentene, 1-octene, 2-ethyl-1-hexene, 1-dodecene and the like. Polyenes include conjugated dienes such as isoprene, butadiene, chloroprene and the like; Non-conjugated dienes; Triene, or higher polyenes. Examples of trienes include 1,4,9-decatene, 5,8-dimethyl-1,4,9-decatene, 4,9-dimethyl-1,4,9-decatene and the like. Non-conjugated dienes are more preferred. Non-conjugated dienes contain 5 to about 25 carbon atoms. Examples include non-conjugated diolefins such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene Etc; Cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene and the like; Vinyl cyclic enes such as 1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexene and the like; Alkylbicyclo nonadienes such as 3-methyl-bicyclo (4,2,1) nona-3,7-diene, 3-ethylbicyclononadiene and the like; Indenes such as methyl tetrahydroindene and the like; Alkenyl norbornene, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-nor Bornen, 5- (1,5-hexadienyl) -2-norbornene, 5- (3,7-octadienyl) -2-norbornene and the like; And tricyclo dienes such as 3-methyl-tricyclo- (5,2,1,0.sup.2,6) -358-decadiene and the like.

In some embodiments, the EPDM polymer contains about 20 to about 80 weight percent ethylene, about 19 to about 70 weight percent higher α-olefin, and about 1 to about 10 weight percent non-conjugated diene. More preferred higher α-olefins are propylene and 1-butene. More preferred polyenes are ethylidene norbornene, 1,4-hexadiene, and dicyclopentadiene.

In other embodiments, the EPDM polymer has an ethylene content of about 50 to about 70 weight percent, a propylene content of about 20 to about 49 weight percent, and a non-conjugated diene content based on the total weight of the polymer. About 10% by weight.

Examples of representative EPDM polymers used are Nordel IP 4770R, Nordel 3722 IP (available from DuPont Dow Elastomers, Wilmington, DE) and Keltan 5636A (Louisiana) Addis-based DSM Elastomers Americas.

EPDM polymers, also known as elastomeric copolymers of ethylene, higher α-olefins and polyenes, have a molecular weight of about 20,000 to about 2,000,000 or more. Its physical form varies from waxy material to rubber or hard plastic-like polymers. Their dilution viscosity (DSV) is about 0.5 to about 10 when measured at 30 ° C. for a solution of 0.1 g of polymer in 100 cc of toluene.

Ethylene-α-olefin copolymers are also suitable for use in thermoplastic vulcanizates as long as the curing system does not require the presence of non-conjugated dienes.

Further suitable elastomers are described in US Pat. No. 4,130,535; 4,111,897; No. 4,311,628; 4,594,390; No. 4,645,793; No. 4,808,643; 4,894,408; 4,894,408; No. 5,393,796; 5,936,038; 5,985,970 and 6,277,916, the entirety of which is incorporated herein by reference.

Crosslinking agent

In embodiments of the present invention, any crosslinking agent capable of curing the elastomer without substantially degrading and / or curing the thermoplastic polymer used in the TPV can be used. Preferred crosslinking agents are phenolic resins. Other curing agents include peroxides, azides, aldehyde-amine reaction products, vinyl silane graft residues, hydrosilylation, substituted ureas, substituted guanidines; Substituted xanthates; Substituted dithiocarbamates; Sulfur-containing compounds such as thiazoles, imidazoles, sulfenamides, thiuramidodisulfides, paraquinonedioximes, dibenzoparaquinonedioximes, sulfur; And combinations thereof, but is not limited thereto. Encyclopedia of Chemical Technology, Vol. 17, 2nd edition, Interscience Publishers, 1968; Organic Peroxides, Daniel Seern, Vol. 1, Wiley-Interscience, 1970), which is incorporated herein by reference in its entirety. Unless stated otherwise, the curing systems described below require elastomers containing conjugated or non-conjugated dienes.

Any phenolic curing agent system capable of fully curing the EPDM rubber is suitable. It is desirable, but not necessarily, to cure the elastomer completely. In some embodiments, the elastomer is partially cured or substantially cured. The basic component of such a system is the condensation of a halogen-substituted phenol, a C ₁ -C ₁₀ alkyl substituted phenol or an unsubstituted phenol with an aldehyde, preferably formaldehyde, or a condensation of a bifunctional phenoldialcohol in an alkaline medium. It is a phenol type cured resin manufactured by Preference is given to dimethylol phenols substituted in the para position by C ₅ -C ₁₀ alkyl groups. Also suitable are halogenated alkyl substituted phenol cured resins prepared by halogenation of alkyl substituted phenol cured resins. Particularly recommended are phenolic curing agent systems comprising methylol phenolic resins, halogen donors and metal compounds, the details of which are described in US Pat. No. 3,287,440 to Giller and US Pat. And the documents are hereby incorporated by reference in their entirety. Another suitable class of phenolic curing agents systems is disclosed in US Pat. No. 5,952,42, which is incorporated herein by reference in its entirety. Non-halogenated phenol cured resins are used with halogen donors, preferably with hydrogen halide scavengers. Typically, halogenated, preferably brominated phenolic resins containing from about 2 to about 10 weight percent bromine do not require a halogen donor, but hydrogen halide scavengers such as metal oxides such as iron oxide, titanium oxide, magnesium oxide, It is used in combination with magnesium silicate, silicon dioxide, preferably zinc oxide, the presence of which promotes the crosslinking function of the phenolic resin. However, in the case of rubber which is not easily cured by phenolic resins, joint use of halogen donor and zinc oxide is recommended. The production of halogenated phenolic resins and their use in hardener systems with zinc oxide are disclosed in US Pat. Nos. 2,972,600 and 3,093,613, which are hereby incorporated by reference in their entirety. Examples of suitable halogen donors are tin chloride, ferric chloride, or halogen donor polymers such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene, and polychlorobutadiene (neoprene rubber). As used herein, the term "activator" refers to any material that increases the crosslinking efficacy of phenolic cured resins, including metal oxides and halogen donors (used alone or together). For further details on phenolic curing agent systems, see "Vulcanization and Vulcanizing Agents," W. Hoffman, Palmerton Publishing Company. Suitable phenolic cured resins and brominated phenolic cured resins are commercially available, for example such resins are trademarks SP-1045, CRJ-352, SP-1055 from Schenectady Chemicals, Inc. And SP-1056. Similar phenolic cured resins that are functionally equivalent are available from other sources. As described above, a sufficient amount of curing agent is used to cure the rubber essentially completely.

Of course, it is understood that sufficient phenolic curing agent is desirable to fully cure the rubber. The minimum amount of phenolic curing agent required to cure the rubber depends on the type of rubber, the phenolic curing agent, the type of curing accelerator and the curing conditions such as temperature. Typically, the amount of phenolic curing agent used to fully cure the EPDM rubber is from about 5 parts by weight to about 20 parts by weight based on 100 parts by weight of EPDM rubber. Preferably, the amount of phenolic curing agent is about 7 parts by weight to about 14 parts by weight based on 100 parts by weight of EPDM rubber. In addition, an appropriate amount of curing activator is used to ensure complete curing of the rubber. The amount of satisfactory cure activator varies from about 0.01 parts to about 10 parts by weight based on 100 parts by weight of EPDM rubber, although higher amounts may be used if the desired satisfactory cure is achieved. The term “phenolic curing agent” includes phenolic curing agents (resins) and curing activators. However, from the fact that the amount of the phenolic curing agent is based on the EPDM rubber content of the blend, it should not be assumed that the phenolic curing agent does not react with the thermoplastic polymer resin or that no reaction occurs between the thermoplastic polymer resin and the EPDM rubber. . Very significant reactions may be involved to a limited extent, ie the graft between the thermoplastic polymer resin and the EPDM rubber is not formed in substantial amounts. Essentially all cured EPDM rubber and thermoplastic polymer resins can be separated and isolated from the blend by high temperature solvent extraction, such as boiling xylene extraction, and the infrared analysis of the isolated fractions grafts between the EPDM rubber and thermoplastic polymer resin. It indicates that little copolymer is formed.

In addition to the phenolic curing agent, azide may also be used as the crosslinking agent. Suitable azides include azidoformates such as tetramethylenebis (azidoformate) (see US Pat. No. 3,284,421 to Breslow, issued Nov. 8, 1966); Aromatic polyazides such as 4,4'-diphenylmethane diazide (see US Pat. No. 3,297,674 to Breslow et al., Issued January 10, 1967); And sulfonazides such as p, p'-oxybis (benzene sulfonyl azide). Ethylene-α-olefin copolymers or ethylene-α-olefin-polyene terpolymers are suitable for the vulcanization of elastomers for such curing systems.

A preferred class of azide is the poly (sulfonyl azide) described above. For crosslinking, the poly (sulfonyl azide) is used in an amount for crosslinking, i.e. in an amount effective to crosslink the elastomer as compared to the starting material, i.e., insolubility of the gel in boiling xylene when tested according to ASTM D-2765A-84 It is used in an amount of poly (sulfonyl azide) sufficient for gel formation of at least about 10% by weight as identified by. Preferably at least about 0.5% by weight, more preferably at least about 1.0% by weight and most preferably 2.0% by weight of poly (sulfonyl azide) is used, based on the total weight of the elastomer, these values being azide And the molecular weight or melt index of the elastomer. In order to avoid uncontrolled heating, unnecessary costs, and deterioration of physical properties, the amount of poly (sulfonyl azide) is preferably less than about 10% by weight, more preferably less than about 5% by weight.

Suitable peroxides as crosslinkers include aromatic diacyl peroxides; Aliphatic diacyl peroxides; Dibasic acid peroxides; Ketone peroxide; Alkyl peroxyesters; Alkyl hydroperoxides (eg, diacetylperoxide; dibenzoylperoxide; bis-2,4-dichlorobenzoyl peroxide; di-tert-butyl peroxide; dicumylperoxide; tert-butylperbenzoate; tert-butylcumylperoxide; 2,5-bis (t-butylperoxy) -2,5-dimethylhexane; 2,5-bis (t-butylperoxy) -2,5-dimethylhexine-3; 4 , 4,4 ', 4'-tetra- (t-butylperoxy) -2,2-dicyclohexylpropane; 1,4-bis- (t-butylperoxyisopropyl) -benzene; 1,1- Bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane; lauroyl peroxide; succinic peroxide; cyclohexanone peroxide; t-butyl peracetate; butyl hydroperoxide and the like, Ethylene-α-olefin copolymers or ethylene-α-olefin-polyene terpolymers are suitable for the vulcanization of elastomers for such curing systems.

The vulcanized elastomer can be grafted to the vinyl silane monomer in the presence of low levels of peroxide through a separate reactive extrusion process. Suitable vinyl silanes include, but are not limited to, vinyl trimethoxysilane, vinyl triethoxysilane. The grafted elastomer can be reacted with water in the presence of a catalyst such as dibutyl tin laurate to cure the polymer during the dynamic vulcanization process. Suitable water sources include, but are not limited to, steam, water / ethylene glycol mixtures, aluminum trihydrate, and magnesium hydroxide. Ethylene-α-olefin copolymers or ethylene-α-olefin-polyene terpolymers are suitable for the vulcanization of elastomers for such curing systems.

Silicon hydrides having two or more SiH groups in the molecule can be reacted with carbon-carbon multiple bonds of the unsaturated rubber component in the presence of a hydrosilylation catalyst to form useful crosslinks during the dynamic vulcanization reaction. Suitable silicon hydride compounds include, but are not limited to, methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers, methylhydrogen alkyl methyl polysiloxanes, bis (dimethylsilyl) alkanes and bis (dimethylsilyl) benzenes. The amount of silicon hydride compound useful for processing the composition is from about 0.1 to about 10.0 molar equivalents of SiH per carbon-carbon double bond of the rubber, preferably from about 0.5 to about 5.0 molar equivalents per carbon-carbon double bond of the rubber component of the thermoplastic elastomer May be SiH. Suitable catalysts for hydrosilylation vulcanization are transition metals of group VIII, such as palladium, rhodium, platinum and the like, or complexes of these metals. Platinum chloride as a useful catalyst is described in US Pat. No. 4,803,244 and US Pat. No. 5,597,867. Dynamically vulcanization of EPDM by hydrosilylation crosslinking to produce TPV is described in US Pat. No. 6,251,998 (Medsker et al., June 26, 2001), which is incorporated herein in its entirety. Included as.

Generally, the thermoplastic elastomer in TPV is fully cured. Such fully cured vulcanizates are processable as thermoplastics, but crosslink until the rubber portion is almost completely insoluble in common solvents. If the measurement of the extract is an appropriate measure of the curing state, the blend is vulcanized so that the thermoplastic vulcanizate contains up to about 3% by weight of rubber extractable in cyclohexane at 23 ° C., preferably extractable in cyclohexane at 23 ° C. It is prepared to contain up to about 2% by weight of rubber. In general, the fewer the extracts, the better the properties, and more preferably the vulcanizates are essentially free (less than 0.5% by weight) of extractable rubber in cyclohexane at 23 ° C. The gel content, expressed as percent gel, is determined by measuring the amount of insoluble polymer by impregnating the specimen in cyclohexane at 23 ° C. for 48 hours, weighing the dried residue, and suitably correcting based on the known composition. Measurement can be made according to the procedure of US Pat. No. 3,203,937, including the step of making it. Thus, the calibrated initial and final weights are used by subtracting the weight of components that are soluble in cyclohexane other than the rubber, such as extender oils, plasticizers, and resin components, that are soluble in cyclohexane. Any insoluble pigments, fillers and the like are subtracted from both initial and final weights.

additive

The properties of TPV can be modified by adding components conventional to the formulation of EPDM rubber, thermoplastic polymer resins and blends thereof before or after the vulcanization reaction. Examples of such components include particulate fillers such as carbon black, amorphous pulverized or pyrolytic silica, titanium dioxide, colored pigments, clays, talc, calcium carbonate, wollastonite, mica, montmorillonite, glass beads, hollow glass spheres, glass Fibers, zinc oxide and stearic acid, stabilizers, antidegradants, flame retardants, processing aids, adhesives, thickeners, plasticizers, waxes, discontinuous fibers such as wood cellulose fibers, and extender oils. Particularly recommended is that carbon black, extender oil or both are preferably added prior to dynamic curing. Carbon black tends to improve tensile strength and promote phenolic curing agents. Extending oils can improve resistance to oil expansion, thermal stability, hysteresis, cost, and permanent strain in elastomeric compositions. Aromatic, naphthenic and paraffinic oils are satisfactory. Addition of extender oil may also improve processability. For suitable extension oils, see Rubber World Blue Book, supra, pages 145-190. The amount of extender oil added depends on the desired properties, the upper limit depends on the compatibility of the particular oil and blend components, and is beyond the point at which excessive exudation of the extender oil occurs. Typically, about 5 to about 300 parts by weight of extender oil is added per 100 parts by weight of the blend of olefin rubber and thermoplastic polymer resin. Usually, it is preferred to add about 30 to about 250 parts by weight of extender oil per 100 parts by weight of rubber present in the blend and add about 70 to about 200 parts by weight of extender oil per 100 parts by weight of rubber. The amount of extender oil depends at least in part on the type of rubber. High viscosity rubbers are even more oil extensible.

Colorable compositions are prepared by incorporating non-black fillers instead of carbon black. Colorless, off-white or white pigments (fillers, extenders, or reinforcing pigments) such as amorphous ground or pyrolytic silica, aluminum silicate, magnesium silicate, kaolin clay, montmorillonite, wollastonite, and titanium dioxide are suitable for this purpose Do. Preferably, a coupling agent such as titanate or silane is used together with the non-black filler, in particular kaolin clay. Typically, about 5 to about 100 parts by weight of non-black pigment is added per 100 parts by weight of rubber in the blend. Typical additions of fillers, ie carbon black or non-black fillers, are from about 40 to about 250 parts by weight of carbon black per 100 parts by weight of EPDM rubber, and from about 10 to about 100 parts by weight of filler per 100 parts by weight of EPDM rubber and extender oil. . The amount of filler that can be used depends on the type of filler and the amount of extender oil used.

TPV Manufacturing method

Thermoplastic vulcanizates can be prepared by blending plastics and cured rubbers, typically by dynamic vulcanization. The composition may be prepared by any suitable mixing method of the rubber polymer, including mixing in a rubber and or internal mixer, such as a Banbury mixer. In the compounding process, conventional compounding ingredients are incorporated. These components include one or more types of carbon black, additional extender oils, other fillers such as clays, silicas, thickeners, waxes, boiling resins, such as zinc oxides, antioxidants, antiozonants, processing aids, and cure activators. have. In general, it is preferred to add a curing activator in the formulation of the second stage, which may be carried out in a rubber mill and / or in an internal mixer operating at a temperature not exceeding about 60 ° C. Curing activators include sulfur and various sulfur containing accelerators. The compound is cured by conventional manner by heating at a temperature of about 150 ° C. to about 200 ° C. for about 5 to about 60 minutes to form a novel elastomer vulcanizate having the useful properties described herein. Specific embodiments of the invention are hereinafter described for illustrative purposes only.

Dynamic vulcanization is a process by which the blend of plastics, rubber and rubber hardener is sovietized while the rubber is cured. The term "dynamic" denotes that the mixture receives shear forces during the vulcanization step, as opposed to "static" vulcanization, where the vulcanizable composition is immobilized (in a fixed reaction space) during the vulcanization step. One advantage of dynamic vulcanization is that an elastomeric (thermoplastic elastomer) composition can be obtained when the blend contains an appropriate proportion of plastic and rubber. Examples of dynamic vulcanization are described in US Pat. No. 3,037,954; 3,806,558; 3,806,558; 4,104,210; 4,104,210; 4,116,914; 4,116,914; 4,130,535; 4,130,535; 4,141,863; 4,141,863; 4,141,878; 4,141,878; No. 4,173,556; No. 4,207,404; No. 4,271,049; 4,287,324; No. 4,288,570; 4,299,931; 4,311,628 and 4,338,413, the entirety of which is incorporated herein by reference.

Any mixer capable of generating a shear rate of 2000 sec ⁻¹ or higher is suitable for performing the processing. In general, this requires a high speed internal mixer having a narrow void between the tip of the kneading member and the wall. Shear velocity is the velocity gradient in the space between the tip and the wall. In order to generate a sufficient shear rate, it is generally suitable for the kneading member to rotate about 100 to about 500 revolutions per minute (rpm), depending on the gap between the tip and the wall. Depending on the number and rotation speed of the tips on a given kneading member, the number of times the composition is kneaded by each member is about 1 to about 30 times / second, preferably about 5 to about 30 times / second, more preferably about 10 To about 30 times / second. This typically means that the material is kneaded about 200 to about 1800 times during the vulcanization reaction. For example, in a typical process using a rotor with three tips rotating at about 400 rpm in a mixer having a residence time of about 30 seconds, the material is kneaded about 600 times.

A satisfactory mixer for carrying out the process is a high shear mixing extruder from Warner & Pfleiderer, Germany. The Warner and Flyder (W & P) extruder is a twin screw extruder in which two crossed screws rotate in the same direction. Details of such extruders are described in US Pat. Nos. 3,963,679 and 4,250,292, and German Patents 2,302,546; 2,473,764 and 2,549,372, the entirety of which is incorporated herein by reference. Screw diameters vary from about 53 mm to about 300 mm and barrel lengths vary, but in general, the maximum barrel length is the length needed to maintain the length at a diameter ratio of about 42. The shaft screws of these extruders are generally made up of a series of alternations of delivery zones and kneading zones. The delivery zone allows the material to move into each kneading zone of the extruder. Typically there is an equal number of delivery and kneading zones distributed evenly along the length of the barrel. Kneading members containing one, two, three or four tips are suitable, but a kneading member of about 5 to about 30 mm width with three tips is preferred. At recommended screw speeds of about 100 to about 600 rpm and radial voids of about 0.1 to about 0.4 mm, these mixed extruders provide shear rates of about 2000 sec ⁻¹ to about 7500 ⁻¹ or more. The net mixed power consumed in the process, including homogenization and dynamic vulcanization, is usually about 100 to about 500 W · h / kg produced product, about 300 to about 400 W · h / kg produced product.

The process is described using a W & P twin screw extruder, model ZSK-53 or ZSK-83. Unless stated otherwise, all plastics, rubbers and other compounding components except the curing activator are fed to the inlet of the extruder. At one third of the extruder, the composition is soviet to melt the plastic and form an essentially uniform blend. A cure activator (vulcanization accelerator) is added downstream from the first inlet through another inlet about one third of the length of the barrel. The remaining two thirds of the extruder (between the curing activator inlet and the outlet of the extruder) is considered a dynamic vulcanization zone. A vent operated under reduced pressure is located near the outlet to remove any byproducts. Occasionally, additional extender oil or plasticizer and colorant are added to another inlet located approximately in the middle of the vulcanization zone.

The residence time in the vulcanization zone is the time during which a given amount of material is in the vulcanization zone. Since the extruder is typically operated under tight conditions filled with about 60 to about 80%, the residence time is essentially directly proportional to the feed rate. Thus, the residence time in the vulcanization zone is calculated by multiplying the total volume of the dynamic vulcanization zone by the filling factor and dividing by the volume flow rate. Shear rate is calculated by multiplying the circumference of the product produced by the screw tip by the number of screw revolutions per second and dividing by the tip void. In other words, the shear rate is the tip speed divided by the tip feed.

The composition can be prepared using methods other than the dynamic curing of the rubber / thermoplastic polymer resin blend. For example, in the absence of a thermoplastic polymer resin, the rubber can be fully cured, powered up and powered up dynamically or statically and mixed at a temperature above the melting or softening point of the resin. If the crosslinked rubber particles are small, well dispersed and have the appropriate concentration, the composition can be easily obtained by blending the crosslinked rubber and the thermoplastic polymer resin. It is desirable to obtain a mixture comprising well dispersed small particles of crosslinked rubber. Mixtures containing poorly dispersed or too large rubber particles may be ground by low temperature grinding to reduce the particle size to less than about 50 μm, preferably less than about 20 μm, more preferably less than about 5 μm. After sufficient grinding or crushing, a TPV composition is obtained. Often, poorly dispersed or too large rubber particles are visible to the naked eye and are observed in the molded sheet. This is especially true where pigments and fillers are absent. In this case, crushing and reshaping are performed to provide a sheet in which rubber particles or agglomerates of large particles are not apparent or less apparent to the naked eye and the mechanical properties are much improved.

In some embodiments of the invention, TPV is prepared using one or two or more compounding processes, wherein the thermoplastic polymer is branched with the production of TPV. In one-step blending using a phenolic curing agent, the blending temperature is preferably kept below 220 ° C in order to avoid breaking of the phenolic curing agent. In a two stage formulation, the phenolic curing agent is typically added during the second stage and the temperature of the second stage is maintained below 220 ° C.

Three simple examples of the on-line branching process of thermoplastic polymers with dynamic vulcanization are described below:

Single step: Charge a mixture of polypropylene (homopolymer or copolymer (random polymer or impact copolymer)), EPDM, stabilizer, processing aid, and ZnO, and halogen donor such as tin dichloride. Add or add oil. A phenolic curing agent (eg SP 1055 or SP 1045) is fed through the side arm feed at a point along the extruder barrel so that all other components are intimately mixed. Alternatively, a non-halogenated phenolic curing agent (eg SP 1045) may be added in place of the halogen donor along with other components. The halogen donor is then added downstream of the extruder via the side feed. Optionally, 50 ppm to 450 ppm DPO-BSA concentrated master batch can be added with polypropylene and / or EPDM to add long chain branching. Typical formulations used are shown in Table 1 below. The extruder or mixer is operated such that the temperature profile in the extruder zone does not exceed 22O &lt; 0 &gt; C. For the extruder approach, suitable mixing screws are required to achieve homogeneous mixing. Finally, the melt is cooled and pelletized.

Step 2 in the extruder: On one side, a screw compounding extruder with a high aspect ratio and two feed hoppers is used. Polypropylene (homopolymer or copolymer (random or impact copolymer)), and optionally 0 to 450 ppm of DPO-BSA master batch is added via the first feed. The temperature of the first zone is maintained at 200 to 250 ° C. until reaching the second feed hopper. The temperature of the extruder adjacent to the second feed hopper is lowered to 190 ° C to 220 ° C. In the second feed hopper, EPDM, stabilizers, processing aids, fillers and halogen donors are added. After that, oil is added. Phenol-based curing agent (SP 1055 or SP 1045) is added via the side arm feed. In addition, a non-halogenated phenolic curing agent may be added in place of the halogen donor during the mixing process, and the halogen donor may replace the non-halogenated phenolic curing agent. Typical formulations are listed in Table 1. The final melt discharged from the extruder is cooled and pelletized.

Single step in the mixer: Fill the mixer (eg, Brabender batch mixer) with PP (homopolymer or copolymer (random or impact copolymer)), EPDM, stabilizer and processing aids, and halogen donor . Add oil to the formulation, increase the torque and continue mixing for 2 more minutes. Mix for approximately 2 minutes and add phenolic curing agent. Typical formulations are listed in Table 1. Finally, the melt is cooled and pelletized.

Step 2 in the Mixer: Fill a mixer (e.g., a brabender batch mixer) with PP (homopolymer or copolymer (random or impact copolymer)) and 0-450 ppm DPO-BSA, and Mix into a uniform melt at a temperature of. The mixture is cooled to approximately 190 ° C. and EPDM, stabilizer and processing aid are added. Add oil to the formulation, increase torque and continue mixing for 2 more minutes. Mix for approximately 2 minutes and add phenolic curing agent. Typical formulations are listed in Table 1. Finally, the melt is cooled and pelletized.

The TPV mixtures prepared by the one- and two-step processes described above will have properties similar to those exemplified in the earlier examples.

In some embodiments, the thermoplastic vulcanizate composition comprises (1) branched polypropylene with a branching index of less than 1.0; (2) ethylenically unsaturated EPDM elastomers; (3) the ethylene / α-olefin interpolymers disclosed herein; And mixtures or reaction products of phenolic resins, wherein the branched polypropylene has a weight-average molecular weight of about 100,000 to 1,000,000 and is at least about 50% of the linear polypropylene having the same weight-average molecular weight.

TPV Application of

Thermoplastic vulcanizate compositions are useful in the manufacture of a variety of products such as tires, hoses, belts, gaskets, shaped articles and molded parts. In particular, they are useful for products requiring high melt strength, such as large part blow molded articles, foams, and wire cables. It is also useful for modifying thermoplastic resins, especially thermoplastic polymer resins. The composition may be blended with the thermoplastic resin using conventional mixing equipment to produce rubber modified thermoplastic resins. The properties of the modified thermoplastic resins depend on the amount of blended thermoplastic elastomer composition.

Thermoplastic vulcanizate compositions may also be used to prepare microfoamable TPV foams using supercritical fluids (eg, CO or N ₂ ). Such techniques are described in US Pat. No. 5,158,986; 5,160,674; 5,160,674; 5,334,356; 5,334,356; 5,866,053; 5,866,053; No. 6,169,122; No. 6,2,810,810; And 6,294,115, which are hereby incorporated by reference in their entirety. The methods disclosed herein can be used in embodiments of the invention with or without modification.

Further TPV uses are disclosed in the following US patents: US Pat. No. 6,329,463 entitled "High temperature, oil resistant thermoplastic vulcanizates made from polar plastics and acrylate or ethylene-acrylate elastomers"; No. 6,288,171, entitled "Modification of thermoplastic vulcanizates using random propylene copolymer"; 6,277,916, entitled "Process for preparing thermoplastic vulcanizates"; No. 6,270,896, entitled "Elastic fiber"; 6,235,166, entitled "Sealing means for electrically driven water purification units"; 6,221,451, entitled "Synthetic closure"; 6,207,752, entitled "Thermoplastic vulcanizates of carboxylated nitrile rubber and thermoplastic polyurethanes"; 6,174,962, entitled "Free radically cured thermoplastic vulcanizates of a polyolefin and a acrylate modified paraalkylstyrene / isoolefin copolymer"; 6,169,145, entitled "Vulcanization of carboxyl containing elastomers using reductive hydrosilylation with extension into dynamic vulcanization"; 6,150,464, entitled "Preferred process for silicon hydride addition and preferred degree of polymerization for silicon hydride for thermoplastic vulcanizates"; No. 6,147,160, entitled "Organosilane cured butyl rubber / polypropylene TPV"; 6,100,334, entitled "Thermoplastic vulcanizates from a cyclic olefin rubber, a polyolefin, and a compatiblizer"; 6,084,031, entitled "TPV from hydrosilylation crosslinking of acrylic modified bromo XP-50 butyl rubber"; 6,069,202 entitled "Thermoplastic elastomer triblend from an engineering, functionalized ethylene and or diene polymer, and brominated isobutylene p-methylstyrene copolymer"; No. 6,066,697, entitled "thermoplastic compositions containing elastomers and fluorine containing thermoplastics"; 6,028,137, entitled "Elastomeric compounds incorporating silicon-treated carbon blacks"; 6,020,427, entitled "Thermoplastic vulcanizates of carboxylated nitrile rubber and polyester thermoplastics"; 5,977,271, entitled "Process for preparing thermoset interpolymer and foam"; No. 5,960,977, entitled "Corrugated polymeric filler neck tubing"; No. 5,957,164 entitled "Refrigerant hose"; No. 5,952,425, entitled "Preferred structure of phenolic resin curatives for thermoplastic vulcanizate"; 5,939,464, entitled "High elasticity foam"; No. 5,936,038, entitled "vulcanizable elastomeric composition and thermoplastic vulcanizate employing the same"; 5,869,591, entitled "Thermoset interpoymer and foam"; No. 5,750,625, entitled "Phenolic resin curatives which form nonstaining thermoplastic elastomers"; 5,744,238, entitled "Dimensionally stable sheet handling shaft assembly and method of making same"; 5,621,045, entitled "Thermoplastic vulcanizates from isobuthylene rubber and either EPDM or a conjugated diene rubber," and 4,783,579, titled "Flat multi-conductor power cable with two insulating layers." All such documents are incorporated herein by reference in their entirety.

Profile extrusion is widely used for the production of continuous homogeneous thermoplastic articles with complex cross sections for applications such as automotive exteriors. The profile ensures the shape of the selected extrusion die and is cut and end capped to form such a product as a bodyside molded article. Single profiles can be designed for different models of vehicles, and profile extrusion is still widely available after sale. The wide processing range of thermoplastics allows for the high production of profile extrusions. Continuous operation of the extruder allows for uniform production of the plastic product. The temperature required for the extrusion barrel, adapter and die depends on the specific extrusion process performed and the properties of the plastic used.

The following examples are provided to illustrate embodiments of the invention. All figures are approximate. When numerical ranges are given, it should be understood that embodiments outside the presented ranges may also fall within the scope of the present invention. The details described in each example should not be understood as essential features of the present 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, the preferred processing parameter is to perform parameter flattening 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.

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

The gel permeation chromatography system consisted of either 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-trichloro benzene. 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. The narrow standard mixture was 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. A pressure of 0 at 190 ° C. for 3 minutes followed by 86 MPa at 190 ° C. for 2 minutes followed by cooling water at 86 MPa was cooled 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 through which cooling water flowed 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 Copolymer, 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 Polymer fractionation by

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 rapidly cooled to 125 ° C., then slowly cooled to 0.04 ° C./min to 20 ° C. and held for 1 hour, 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 leaving the concentrate 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 Copolymer, 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-octyl aluminum 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

In general High throughput  Parallel polymerization condition

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 with pre-weighed glass tubes 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 2. In Table 2 and other parts 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 2 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 (T _m ) 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 DSC T _m and T _crystaf 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 (T _m ) 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 DSC T _m and T _crystaf 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 (T _m ) 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 DSC T _m and T _crystaf 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 (T _m ) 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 DSC T _m and T _crystaf 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 (T _m ) 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 DSC T _m and T _crystaf 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 (T _m ) 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 DSC T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 3. Selected polymer properties are listed in Table 4.

^* 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and the T _crystaf 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 T _m and the T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 T _m and the T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and the T _crystaf 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 (T _m ) of 113.2 ° C. The corresponding CRYSTAF curve did not show a peak above 30 ° C. (Thus, T _crystaf was set to 30 ° C. for further calculation.) The delta between the DSC T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and the T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and T _crystaf 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 (T _m ) 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 T _m and the T _crystaf 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 ™ PL1840 available from The Dow Chemical Company) Comparative Example J was hydrogenated styrene / butadiene / styrene triblock copolymer (KRATON® G1652 available from KRATON polymer) and Comparative K was a thermoplastic vulcanizate (TPV, Polyolefin blends in which the crosslinked elastomer is dispersed). The results are shown in Table 5.

In Table 5, 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 5 shows a low (good) storage modulus ratio (G ′ (25 ° C.) / G ′ (100 ° C.)) of 6 or less for the polymers of the 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 5 also demonstrates that 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 6 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 6, 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 6 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 6 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 7 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 hours 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 8.

Additional polymers Example  19A to F, continuous solution polymerization, catalyst A1 / B2 + DEZ

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.

Process details and results are included in Table 8a below. Selected polymer properties are provided in Table 9a below.

¹ standard cm3 / 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

Final product (ppm) calculated as ⁴ mass resin

⁵ Polymer Producing Rate

⁶ % conversion of ethylene in the reactor

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

¹ Further information on calculating the block index of various polymers can be found in Colin L.P. US Patent Application Serial Number (insert if known) filed March 15, 2006, under the name of Shan, Ronnie Hartslit, and assigned to Dow Global Technologies Inc. The disclosure of which is incorporated herein by reference in its entirety.

² Zn / C ₂ * 1000 = (Zn feed flow * Zn concentration / 1000000 / Zn molecular weight) (total ethylene feed flow * (1-fraction ethylene conversion) / ethylene molecular weight) * 1000. "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.

Example 1 of the present invention is a thermoplastic vulcanizate (TPV) compound containing the ethylene / α-olefin interpolymer (EAO1) of the present invention. The components and amounts are listed in Table 10 below. Comparative Example A is a TPV compound that does not contain the ethylene / α-olefin interpolymer of the present invention. Its components and amounts are also listed in Table 10 below.

EAO of the present invention has a composite 1-octene content of 77% by weight, a density of 0.854 g / cc, a DSC peak melting point of 105 ° C, a heat of fusion of 10.6 J / g, an ATREF crystallization temperature of 73 ° C, water An average molecular weight of 188,254 g / mol, a weight average molecular weight of 329,600 g / mol, a melt index of 1.0 dg / min at 190 ° C., 2.16 Kg, and a melt index of 37.0 dg / min at 190 ° C., 10 Kg Ethylene / 1-octene olefin block copolymer.

EPDM is an ethylene / propylene / ethylidene norbornene terpolymer having a Mooney viscosity (ML 1 + 4) of 70, an ethylene content of 70% by weight and an ethylidene norbornene content of 5% by weight at 125 ° C. . Polypropylene is a general purpose homopolymer with a melt flow index of 1.0 dg / min at 230 ° C., 2.16 Kg. The extender oil is a paraffinic refined petroleum based processed oil. Antioxidants are 1: 1 blends of high molecular weight phenolic primary antioxidants and phosphite secondary antioxidants.

Thermoplastic vulcanizates were prepared by filling a 310 cc capacity batch mixer heated to 190 ° C. using EPDM, EAO1 and polypropylene. The rotor speed was set to 30 rpm. After 2 minutes, antioxidant and oxidized polyethylene wax were added. Then oil was slowly added to the mixture. Thereafter, methylol phenol-based cured resin was added to the mixture and mixed in a batch. Then, the rotor speed was raised to 75 rpm and tin chloride was added. The rubber part is cured. Thereafter, the mixture was mixed for an additional 5 months. The rotor was then stopped, the mixture was taken out of the mixer and cooled to crude plaque via compression molding. The finished plaques were made 15 cm × 25 cm × 1.5 mm by compression molding at 190 ° C. and then cooled under compression.

TPV was tested for tensile properties according to ASTM D412. The tensile property of Example 1 of the present invention was significantly higher than that of Comparative Example A.

As described above, embodiments of the present invention provide a variety of TPV compositions that are molded for the manufacture of products suitable for extrusion and useful. The manufactured articles have good compression set, tensile set, increased service temperature, increased tensile strength, elongation, tear resistance, scratch / damage, wear, good dynamic loading properties and / or oil resistance. Additional advantages and characteristics will be apparent to those skilled in the art.

Although the present invention has been described with respect to a limited number of embodiments, the specific features of one embodiment should not be attributed to other embodiments of the invention. No single embodiment is representative of all aspects of the invention. In some embodiments, a composition or method may comprise a number of compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not comprise or substantially have any compounds or steps not listed herein. There are variations and variations of the described embodiments. Finally, any number disclosed herein should be construed to mean approximate, regardless of whether the word "about" or "approximately" has been used to describe the number. The appended claims are within the scope of the present invention. It is intended to include all such variations and modifications as belonging.

Claims (23)

(i) vulcanizable elastomers; (ii) thermoplastic polyolefins; (iii) crosslinking agents; And (iv) comprises or is obtainable from a reaction mixture comprising an ethylene / α-olefin interpolymer, The ethylene / α-olefin interpolymer (a) has an M _w / M _n of about 1.7 to about 3.5, one or more melting points T _m (° C.), and a density d (g / cm 3), wherein the values of T _m and d are represented by the following relation: T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² Or (b) having a M _w / M _n of about 1.7 to about 3.5, the difference amount ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak; Wherein the values of ΔT and ΔH are as follows: For ΔH above 0 and below 130 J / g, ΔT> -0.1299 (ΔH) + 62.81, ΔT ≥ 48 ° C for ΔH above 130 J / g The CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C, or (c) has a 300% strain and an elastic recovery rate R _e (%) in one cycle, and a density d (g / cm 2) measured with a compression-molded film of an ethylene / α-olefin interpolymer, wherein R _e and d The value of is given by the following relationship where the ethylene / α-olefin interpolymers are substantially free of crosslinked phases: R _e > 1481-1629 (d) Characterized by satisfying (d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, the fraction being at least 5% higher than the mole comonomer content of the comparative random ethylene interpolymer fraction eluting at the same temperature range Have a molar content (wherein the comparative random ethylene interpolymer has the same comonomer (s) as the ethylene / α-olefin interpolymer and has a melt index, density and co-occupation within 10% of the ethylene / α-olefin interpolymer) Monomer molar content (based on total polymer); (e) has a storage modulus G '(25 ° C) at 25 ° C and a storage modulus G' (100 ° C) at 100 ° C, wherein the ratio of G '(25 ° C) to G' (100 ° C) is about 1 Thermoplastic vulcanizate, characterized in that from 1: 1 to about 10: 1. (i) vulcanizable elastomers; (ii) thermoplastic polyolefins; (iii) crosslinking agents; And (iv) comprises or is obtainable from a reaction mixture comprising an ethylene / α-olefin interpolymer, The ethylene / α-olefin interpolymer (a) at least one molecule which is eluted at 40 ° C. to 130 ° C. when fractionated using TREF and has a molecular weight distribution M _w / M _n of greater than about 1.3 and a block index of fractions greater than 0.5 Have fractions, (b) a thermoplastic vulcanizate having an average block index greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3. (i) thermoplastic polyolefins; (ii) crosslinking agents; And (iii) comprises or is obtainable from a reaction mixture comprising a vulcanizable elastomer that is an ethylene / α-olefin / diene interpolymer, The ethylene / α-olefin / diene interpolymer (a) at least one molecule which is eluted at 40 ° C. to 130 ° C. when fractionated using TREF and has a molecular weight distribution M _w / M _n of greater than about 1.3 and a block index of fractions greater than 0.5 Have fractions, (b) a thermoplastic vulcanizate having an average block index greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3. (i) thermoplastic polyolefins; (ii) crosslinking agents; And (iii) comprises or is obtainable from a reaction mixture comprising a vulcanizable elastomer that is an ethylene / α-olefin / diene interpolymer, The ethylene / α-olefin / diene interpolymer (a) has an M _w / M _n of about 1.7 to about 3.5, one or more melting points T _m (° C.), and a density d (g / cm 3), wherein the values of T _m and d are represented by the following relation: T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² Or (b) having a M _w / M _n of about 1.7 to about 3.5, the difference amount ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak; Wherein the values of ΔT and ΔH are as follows: For ΔH above 0 and below 130 J / g, ΔT> -0.1299 (ΔH) + 62.81, ΔT ≥ 48 ° C for ΔH above 130 J / g The CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C, or (c) has a 300% strain and an elastic recovery rate R _e (%), and density d (g / cm 2) measured with the compression-molded film of the interpolymer, wherein the values of R _e and d are Where the interpolymer is substantially free of crosslinked phases R _e > 1481-1629 (d) Characterized by satisfying (d) having a molecular fraction eluted at 40 ° C. to 130 ° C. when fractionated using TREF, the fraction having at least 5% higher comonomer mole content of the comonomer mole of the comparative random interpolymer fraction eluting at the same temperature range Content (wherein the comparative random interpolymer has the same comonomer (s) as the interpolymer and has a melt index, density and comonomer molar content (based on total polymer) within 10% of the interpolymer) ); (e) has a storage modulus G '(25 ° C) at 25 ° C and a storage modulus G' (100 ° C) at 100 ° C, wherein the ratio of G '(25 ° C) to G' (100 ° C) is about 1 Thermoplastic vulcanizate, characterized in that from 1: 1 to about 10: 1. The method of claim 1, wherein the interpolymer has an M _w / M _n of about 1.7 to about 3.5, and at least one melting point T _m (° C.), and a density d (g / cm 3). Wherein the values of T _m and d are given by T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² Corresponding to the thermoplastic vulcanizate. The method of claim 1, wherein the interpolymer has an M _w / M _n of about 1.7 to about 3.5, and the heat of fusion ΔH (J / g), and the largest DSC peak and the largest CRYSTAF. Has a difference amount ΔT (° C.) defined as the temperature difference between the peaks, and the numerical values of ΔT and ΔH are given by the following relation: For ΔH above 0 and below 130 J / g, ΔT> -0.1299 (ΔH) + 62.81, ΔT ≥ 48 ° C for ΔH above 130 J / g Wherein the CRYSTAF peak is determined using at least 5% of the cumulative polymer and the CRYSTAF temperature is 30 ° C. when less than 5% of the polymer has an identifiable CRYSTAF peak. The method according to any one of claims 1 to 4, wherein the interpolymer is 300% strain measured with its compression-molded film and elastic recovery rate R _e (%) in one cycle, and density d (g / cm 2). Wherein the numerical values of R _e and d are as follows when the interpolymer is substantially free of a crosslinked phase: R _e > 1481-1629 (d) Thermoplastic vulcanizate, characterized in that to satisfy. 8. The method of claim 7, wherein the values of R _e and d are as follows: R _e > 1491-1629 (d) Thermoplastic vulcanizate to satisfy. 8. The method of claim 7, wherein the values of R _e and d are as follows: R _e > 1501-1629 (d) Thermoplastic vulcanizate to satisfy. 8. The method of claim 7, wherein the values of R _e and d are as follows: R _e > 1511-1629 (d) Thermoplastic vulcanizate to satisfy. 5. The thermoplastic vulcanizate according to claim 1, wherein the interpolymer comprises at least one molecular fraction having a block index of at least 0.5 and a molecular weight distribution M _w / M _n of greater than about 1.3. 6. 5. The method of claim 1, wherein the interpolymer has a storage modulus G ′ (25 ° C.) at 25 ° C. and a storage modulus G ′ (100 ° C.) at 100 ° C. 25 ° C.) to G ′ (100 ° C.) ratio of about 1: 1 to about 10: 1. 3. Thermoplastic vulcanizing according to claim 1 or 2, wherein said α-olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, or a combination thereof. water. The thermoplastic vulcanizate according to claim 3 or 4, wherein the ethylene / α-olefin / diene interpolymer is an ethylene / propylene / diene (EPDM) copolymer. The thermoplastic vulcanizate according to claim 14, wherein the diene is norbornene, 1,5-hexadiene or a combination thereof. The method of claim 1, wherein the interpolymer has a melt index in the range of about 5 to about 500 g / 10 minutes as measured according to ASTM D-1238, Condition 190 ° C./2.16 kg. Thermoplastic vulcanizates. The thermoplastic vulcanizate according to any one of claims 1 to 4, wherein the interpolymer is present in the range of about 5% to about 95% by weight of the total composition. The thermoplastic vulcanizate according to any one of claims 1 to 4, wherein the interpolymer is present in the range of about 5% to about 45% by weight of the total composition. The thermoplastic vulcanizate according to any one of claims 1 to 4, wherein the polyolefin is a homopolymer. The thermoplastic vulcanizate according to any one of claims 1 to 4, wherein the polyolefin is polypropylene. The thermoplastic vulcanizate according to any one of claims 1 to 4, wherein the polyolefin is polyethylene. The thermoplastic vulcanizate according to any one of claims 1 to 4, wherein the vulcanizable elastomer is an ethylene / higher alpha -olefin copolymer or terpolymer. An article made from the thermoplastic vulcanizate of claim 1.

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