KR20070121677A - Polymer blends from interpolymers of ethylene / alpha-olefins and flexible molded articles made therefrom - Google Patents

Abstract

The present invention relates to a polymer blend comprising 1) at least one ethylene / α-olefin interpolymer and 2) at least one polyolefin, or at least one styrenic block copolymer, or a combination thereof. Such polyolefins include, but are not limited to, high melt strength high density polyethylene and high melt strength polypropylene. Ethylene / α-olefin interpolymers are random block copolymers comprising one or more hard blocks and one or more soft blocks. The polyolefin may be a homopolymer or interpolymer. The resulting polymer blend can be used to make flexible molded articles.

Description

Polymer Blends from Interpolymers of Ethylene / Alpha-olefins and Flexible Molded Articles Made Therefrom}

The present invention relates to a polymer blend comprising at least one ethylene / α-olefin interpolymer and at least one polyolefin, to a process for making the blend, and to molded articles made from the blend.

The manufacturing of durable products only in the United States accounts for one million tons of plastic annually. Durable products are long-lived manufactured products found in a variety of markets such as the automotive, construction, pharmaceutical, food and beverage, electrical, appliance, office equipment, and consumer markets. Some applications within this market require the use of flexible polymers or polymer blends. Such applications include toys, sacks, soft hand grips, bumper friction strips, floors, car floor mats, wheels, casters, furniture and appliance undercarriage, tags, seals, gaskets such as static and dynamic gaskets, car doors, bumper strips, grills Elements, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchenware, footwear, shoe bladder and footwear Including but not limited to soles.

For use in durable product applications, the polymer or polymer blend has good processability (eg, formability), attractive appearance (eg, transparency or colorability), suitable surface properties (eg, good adhesion to a substrate, Rubbery feel, non-sticky and good paintability), and a combination of good mechanical properties (eg, flexibility, heat resistance, abrasion resistance and / or scratch resistance, toughness, tensile strength and compression set) Do. Some polymers with suitable properties for durable products include flexible polyvinylchloride (f-PVC), poly (styrene-butadiene-styrene) (SBS), poly (styrene-ethylene / butadiene-styrene) (SEBS), thermoplastic vulcanizates (TPV), thermoplastic poly (urethane) (TPU), and polyolefins such as polyolefin homopolymers and polyolefin interpolymers.

Wide water solubility of some polyolefins, such as polypropylene (PP) and low density polyethylene (LDPE), has been found for use in durable product applications for ease of molding, good heat resistance and mechanical properties. In addition, many formulations have been developed based on blends of polyolefins and other polymers that meet the demands required by the manufacture of parts of durable products. For example, blends of polypropylene and polyethylene can be used to make fibers for artificial turf applications.

In addition, some flexible polymers, including some polyolefin homopolymers or polyolefin interpolymers, may be tacky and this property is undesirable in some processing or applications. In general, additives such as fatty acid amides, waxes or other non-tacky polymers can be mixed with these flexible polymers to reduce their tack. However, such additives are known to be effective only to a certain extent, and they themselves have some undesirable properties.

Despite the availability of various polyolefins and blends thereof, there is a continuing need for new polymers or new polymer blends with improved properties and properties.

<Overview of invention>

The foregoing needs are met by various aspects of the present invention. In one aspect, the invention relates to a polymer blend comprising at least one ethylene / α-olefin interpolymer and at least one additional polymer. Additional polymers may be polyolefins, styrenic block copolymers, polyvinylchloride, thermoplastic polyurethanes, and the like. In one embodiment, the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5, has one or more melting points (Tm) (degrees C), and a density (d) (g / cm ³ ), The numerical values of Tm and d correspond to the following relations.

Tm ≥ -2002.9 + 4538.5 (d)-2422.2 (d) ²

In another embodiment, the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5, defined by the heat of fusion (ΔH) (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak. Delta T (degree Celsius), wherein the values of ΔT and ΔH have the following relationship.

ΔT> -0.1299 (ΔH) + 62.81 if ΔH is greater than 0 and less than or equal to 130 J / g

ΔT ≥ 48 ° C when ΔH is greater than 130 J / g

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

In another embodiment, the ethylene / α-olefin interpolymers are characterized by 300% strain and elastic recovery in one cycle (Re) (%) as measured by compression molded films of ethylene / α-olefin interpolymers, (d) When (g / cm ³ ), and the ethylene / α-olefin interpolymers contain substantially no crosslinked phase, the values of Re and d satisfy the following relationship.

Re> 1481-1629 (d)

In another embodiment, the ethylene / α-olefin interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fractions of the comparative random ethylene interpolymer fractions are eluted at the same temperature range. And a comonomer molar content of at least 5% higher than the comonomer molar content, wherein the comparative random ethylene interpolymer has the same comonomer as the ethylene / α-olefin interpolymer, and the ethylene / α-olefin interpolymer Melt index, density, and comonomer molar content (based on total polymer) of less than 10%.

In another embodiment, the ethylene / α-olefin interpolymer is characterized by a storage modulus at 25 ° C. (G ′ (25 ° C.)), and a storage modulus at 100 ° C. (G ′ (100 ° C.)), The ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: 1 to about 10: 1.

In another embodiment, the ethylene / α-olefin interpolymer has a block index of at least 0.5 and about 1 or less and a molecular weight distribution (Mw / Mn) of greater than about 1.3, eluted at 40 ° C. to 130 ° C. when fractionated using TREF. At least one molecular fraction characterized in that. In yet another embodiment, the average block index of the ethylene / α-olefin interpolymers is greater than 0 and up to about 1.0 and the molecular weight distribution (Mw / Mn) is greater than about 1.3.

In another embodiment, the α-olefins in the ethylene / α-olefin interpolymers are styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, or a combination thereof.

In another embodiment, the ethylene / α-olefin interpolymer is present in the range of about 5% to about 95% by weight of the total composition.

In another embodiment, the polyolefin is an olefin homopolymer, olefin copolymer, olefin terpolymer or a combination thereof.

In another embodiment, the additional polymer is a high melt strength polypropylene, high melt strength high density polyethylene, ethylene / propylene copolymer, styrene-butadiene-styrene block copolymer, ethylene / propylene / diene terpolymer, styrene-ethylene-co -(Butene) -styrene block copolymers or combinations thereof, but is not limited thereto.

In another embodiment, the polymer blend is in some cases a slip agent, antiblocking agent, plasticizer, oil, antioxidant, UV stabilizer, colorant or pigment, filler, lubricant, antifogging agent, flow aid, coupling agent, crosslinker, It further comprises one or more additives which may be nucleating agents, surfactants, solvents, flame retardants, antistatic agents or combinations thereof.

In another aspect, the present invention relates to a flexible molded article comprising the polymer blends disclosed herein. In some embodiments, the flexible molded article may be a toy, a sack, a soft hand grip, a bumper friction strip, a floor, an automobile floor mat, wheels, casters, furniture and utensil undercarriage, tags, seals, gaskets such as static and dynamic gaskets, Automotive doors, bumper straps, grill elements, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchenware, shoes, shoe bladders, shoe soles and their Combinations.

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 ^* .

Figure 3 (represented by squares and circles) copolymer of the present invention and the conventional copolymer density on elastic recovery for the produced non-oriented film from (various Dow Affinity (Dow AFFINITY) and ^® polymer, indicated by a triangle) Indicates the effect. Squares represent ethylene / butene copolymers of the present invention, and circles represent ethylene / octene copolymers of the present invention.

4 shows TREF fractionated ethylene / 1-octene copolymer fractions for the TREF elution temperature of the polymer fraction of Example 5 (shown as circles) and the comparative polymers Comparative Examples E ^* and F ^* (shown with the symbol “X”). It is a plot of octene content. 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 TREF elution temperature of the polymer of Example 5 (curve 1) and the polymer fraction of Comparative Example F ^* (curve 2). Squares represent polymer Example F ^* and triangles represent Example 5.

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

FIG. 7 shows a plot of TMA (1 mm) versus flexural modulus for some polymers of the present invention (represented with diamonds) compared to some known polymers. Triangles represent various Dow beosi pie (Dow VERSIFY) ^® polymer, a circle is shown a variety of different Dow Affinity ^® polymer random ethylene / styrene copolymers show the square.

Figure 8 is the component A (i.e., KRATON (KRATON) ^® G1652, SEBS) and Component B tensile recovery ratio of the two-component blend containing (i. E., Dow Affinity ^® EG8100 or Polymer 19a, 19b or 19i of the present invention) Indicates. Circles represent the blend (i.e., Comparative Examples Y1 to Y5 each having a 0%, Dow Affinity ^® EG8100 25%, 50%, 75% and 100%) containing KRATON ^® G1652 and Dow Affinity ^® EG8100 . Diamond represents the KRATON ^® G1652 and the blend containing the polymer of the invention 19a (19a in the embodiment having a polymer that is, 25%, 50%, 75% and 100% Examples 34 to 37). Triangle represents the KRATON ^® G1652 and the 19b containing a polymer blend of the invention (embodiment that is, having 25%, 50%, 75% and 100% of Polymer 19b of Example 38 to 41). Square represents the KRATON ^® G1652 and the blend containing the polymer 19i of the invention (prepared with the polymer of 19i that is, each 25%, 50%, 75% and 100%, for example 42 to 45).

9 is component A (i.e., KRATON ^® G1652, SEBS) and Component B (i.e., Dow Affinity ^® EG8100 or Polymer 19a, 19b or 19i of the present invention) the two-component heat-resistant properties of the blend (i.e., TMA containing Temperature). Circles represent the blend (i.e., Comparative Examples Y1 to Y5 each having a 0%, Dow Affinity ^® EG8100 25%, 50%, 75% and 100%) containing KRATON ^® G1652 and Dow Affinity ^® EG8100 . Diamond represents the KRATON ^® G1652 and the blend containing the polymer of the invention 19a (19a in the embodiment having a polymer that is, 25%, 50%, 75% and 100% Examples 34 to 37). Triangle represents the KRATON ^® G1652 and the 19b containing a polymer blend of the invention (embodiment that is, having 25%, 50%, 75% and 100% of Polymer 19b of Example 38 to 41). Square represents the KRATON ^® G1652 and the blend containing the polymer 19i of the invention (prepared with the polymer of 19i that is, each 25%, 50%, 75% and 100%, for example 42 to 45).

General definition

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

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

The term “ethylene / α-olefin interpolymer” generally refers to a polymer comprising ethylene and an α-olefin having at least 3 carbon atoms. Preferably, ethylene comprises most of the mole fraction of the total polymer, ie ethylene comprises at least about 50 mol% of the total polymer. More preferably, ethylene comprises at least about 60 mol%, at least about 70 mol%, or at least about 80 mol%, with the substantial remainder of the entire polymer being preferably an α-olefin having 3 or more carbon atoms. It consists of more than one species of 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 ethylene / α-olefin interpolymers as prepared are substantially pure and often constitute 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 multiple blocks or segments of 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 substantially linear manner as opposed to a substantially branched or substantially star form. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. That is, the block copolymer usually does not have a structure as follows.

AAA-AA-BBB-BB

In another embodiment, the block copolymers usually do not have a third type of block comprising different comonomer (s). In another embodiment, block A and block B each have monomers or comonomers substantially distributed randomly within the block. That is, block A and block B both do not include two or more sub-segments (or sub-blocks) having separate compositions, such as tip segments having compositions that are substantially different from the remaining blocks.

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. That is, the comonomer content (monomer content other than ethylene) in the hard segment is less than about 5 weight percent, preferably less than about 2 weight percent based on the weight of the polymer. In some embodiments, the hard segments are all or substantially all composed of ethylene. In contrast, “soft” segments have a comonomer content (monomer content 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 percent based on the weight of the polymer. Blocks of excess polymerized units are shown. 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.

The soft segment is often from about 1% to about 99% by weight of the total weight of the block interpolymer in the block interpolymer, preferably from about 5% to about 95%, about 10% by weight to the total weight of the block interpolymer From about 90 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% About 65%, about 40% to about 60%, or about 45% to about 55% by weight. In contrast, hard segments may exist within a similar range. Soft segment weight percentages and hard segment weight percentages can be calculated based on data obtained from DSC or NMR. These methods and calculations are filed on March 15, 2006, under the name of "ethylene / α-olefin block interpolymers", in the name of Colin LP Shan, Lonnie Hazlitt, et al. And the entirety of the specification, assigned to Dow Global Technologies Inc., incorporated herein by reference and simultaneously filed (Inserted if known), agent case number 385063-999558.

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

The term "multiblock copolymer" or "segmented copolymer" is preferably a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") connected in a linear manner, ie pendant or grafted manner. Rather, it refers to a polymer comprising chemically differentiated units that are linked end to end with respect to the polymerized ethylene functional group. In a preferred embodiment, the block comprises the amount or type of comonomer incorporated therein, the density, the amount of crystallization, the microcrystalline size attributable to the polymer of this composition, the type or degree of tacticity (isotactic or syn Different amounts, homogeneity, or any other chemical or physical property of branching, including diotactic), regio-regular or site-irregularity, long chain branching or hyper-branching. Multiblock copolymers are characterized by the distribution of specific polydispersity indices (PDI or Mw / Mn), block length distribution and / or block number distribution due to specific copolymer preparation methods. More specifically, when produced in a continuous process, the polymer preferably has a PDI of 1.7 to 2.9, preferably 1.8 to 2.5, more preferably 1.8 to 2.2 and most preferably 1.8 to 2.1. When produced in a batch or semi-batch process, the polymer has a PDI of 1.0 to 2.9, preferably 1.3 to 2.5, more preferably 1.4 to 2.0 and most preferably 1.4 to 1.8.

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

Embodiments of the present invention provide a polymer blend comprising at least one ethylene / α-olefin block interpolymer (described below) and at least one polymer different from the ethylene / α-olefin block interpolymer. Additional polymers include, but are not limited to, thermoplastic polymers, elastomers, and rubbers such as polyolefins, styrenic block copolymers, and the like. The term “different” when referring to two polymers means that the two polymers differ in composition (comonomer type, comonomer content, etc.), structure, properties, or combinations thereof. For example, although they have the same amount of comonomers, the block ethylene / octene copolymers differ from the random ethylene / octene copolymers. Block ethylene / octene copolymers differ from ethylene / butane copolymers whether they are random copolymers or block copolymers or have the same comonomer content. Two polyolefins are also considered different if they have different molecular weights, even if they have the same structure and composition. Also, although all other parameters may be the same, the random homogeneous ethylene / octene copolymer is different from the random heterogeneous ethylene / octene copolymer.

Polymer blends have unique physical and mechanical properties suitable for the manufacture of shaped articles for various applications. The blend has a relatively low modulus while maintaining a relatively high heat resistance. This balance of properties makes the blend suitable for making flexible molded articles. The upper use or service temperature of the molded article should be at least 40 ° C, at least 50 ° C, at least 60 ° C, at least 80 ° C, or at least 90 ° C. The flexural modulus of the blend should be less than 20,000 psi, less than 10,000 psi, less than 5000 psi, less than 1000 psi, less than 500 psi.

Ethylene / α-olefin Interpolymers

Ethylene / α-olefin interpolymers (also referred to as “interpolymers” or “polymers of the present invention”) used in embodiments of the present invention are multi-components of two or more polymerized monomer units that differ in chemical or physical properties. Polymerized forms (block interpolymers) characterized by blocks or segments, preferably in multiblock copolymers, comprise ethylene and at least one copolymerizable α-olefin comonomer. The ethylene / α-olefin interpolymers are characterized by one or more of the aspects described below.

In one aspect, the ethylene / α-olefin interpolymers used in embodiments of the present invention have an Mw / Mn of about 1.7 to about 3.5, and at least one melting point (Tm) (degrees C) and density (d) (g / cm ³ ), the numerical values of these variables correspond to the relation

Tm> -2002.9 + 4538.5 (d)-2422.2 (d) ² ,

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

More preferably Tm> 858.91-1825.3 (d) + 1112.8 (d) ² .

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

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

ΔT> -0.1299 (ΔH) + 62.81,

Preferably ΔT ≧ −0.1299 (ΔH) +64.38,

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

In addition, when (DELTA) H exceeds 130 J / g, (DELTA) T is 48 degreeC or more. CRYSTAF peaks are measured using at least 5% of the cumulative polymer (ie, peaks must represent at least 5% of the cumulative polymer), and if less than 5% of the polymers have an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C. And ΔH are numerical values of heat of fusion (J / g). More preferably, the highest CRYSTAF peak contains at least 10% of the cumulative polymer. 2 shows the data plotted for the polymers of the invention as well as the comparative examples. 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, The comparative random ethylene interpolymers eluting at the same temperature range are higher than the molar comonomer content of the fraction, preferably at least 5% higher, more preferably at least 10% higher. It contains the same comonomer (s) as the blocked interpolymer and the melt index, density and comonomer molar content (based on total polymer) are within 10% of the melt index, density and comonomer molar content of the block interpolymer. Preferably, the Mw / Mn of the comparative interpolymers is also within 10% of the Mw / Mn of the block interpolymers and / or the total comonomer content of the comparative interpolymers is within 10% by weight of the block interpolymers. .

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

Re> 1481-1629 (d);

Preferably Re ≧ 1491-1629 (d);

More preferably Re ≧ 1501-1629 (d);

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

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

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

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

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

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

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

In some embodiments, the multiblock copolymer has a PDI fitting 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, preferably the TREF is first used to fractionate the polymers into fractions each having an elution temperature range of 10 ° C. or less. That is, each eluted fraction has a collection temperature window of 10 ° C. or less. By 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 ethylene and one or more copolymerizable comonomers in polymerized form and differing in 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 satin 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 melts The index, density and comonomer molar content (based on total polymer) are within 10% for block interpolymers. Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of the Mw / Mn of the blocked interpolymer and / or the total comonomer content of the comparative interpolymer is within 10% by weight of the block interpolymer. to be. 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, in the interpolymers of ethylene and 1-octene, the block interpolymers have a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. of at least (-0.2013) T + 20.07, more preferably (- Greater than or equal to 0.2013) T + 21.07 (where T is the value of the peak elution temperature of the compared TREF fraction, measured in ° C.).

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

FIG. 5 graphically illustrates the TREF curve and comonomer content for the polymer fractions of Example 5 and Comparative Example F, discussed below. The peaks eluting at 40 ° C. to 130 ° C., preferably 60 ° C. to 95 ° C., for both polymers were separated into three parts and each part was eluted over a temperature range of less than 10 ° C. The actual data of Example 5 is shown in triangles. One skilled in the art can construct appropriate calibration curves for interpolymers containing different comonomers and obtain TREFs from random copolymers prepared using comparative interpolymers of the same monomer, preferably metallocenes or other homogeneous catalyst compositions. It can be appreciated that a line matching the value can be used for comparison. 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 aspects and properties described herein, the polymers of the 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 is the same as the blocked interpolymer. To include, and preferably the dimer (s) is within 10% of the same comonomer (s), and a melt index, density, and molar comonomer content (based on the whole polymer) in the case of the blocked interpolymer. Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of the Mw / Mn of the blocked interpolymer, and / or 10% by weight for the interpolymer with the total comonomer content of the comparative interpolymer Within.

Preferably, the interpolymers, in particular, have a total polymer density of from about 0.855 to about 0.935 g / cm ³ , more particularly of polymers of at least one α-olefin with ethylene having more than about 1 mol% comonomer Interpolymers, wherein the blocked interpolymers have a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. of at least (−0.1356) T + 13.89, more preferably at least (−0.1356) T + 14.93, Most preferably greater than or equal to (-0.2013) T + 21.07, where T is the value of the highest ATREF elution temperature measured in degrees Celsius of the TREF fraction being compared.

Preferably, for interpolymers of ethylene and one or more alpha-olefins, in particular for the interpolymers having an overall polymer density of about 0.855 to about 0.935 g / cm ³ , more particularly greater than about 1 mol% In the case of the polymer having a comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. in the amount of (-0.2013) T + 20.07 or more, more preferably (-0.2013) T + 21.07 More than, most preferably (-0.2013) T + 21.07, where T is the value of the highest elution temperature measured in degrees Celsius of the TREF fraction being compared.

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

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

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

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

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

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

Measured by an infrared detector ATREF  peak Comonomer  Furtherance

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

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

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

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

The application of infrared spectroscopy to determine the comonomer content of polymers in this ATREF-infrared method is in principle similar to that of the GPC / FTIR system as described in the following references: Markovich, Ronald P .; Hazlitt, Lonnie G .; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers", Polymeric Materials Science and Engineering (1991), 65, 98-100 .; And Deslauriers, P. J .; Rohlfing, D. C .; Shieh, E. T .; "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170.] Introduced for reference).

In another embodiment, 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 (Mw / Mn) of greater than about 1.3. The average block index (ABI) is the weight average of the block index (“BI”) of 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.

Wherein 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 measured value for "hard segment" is invalid, T _A and P _A as first approximation The value is set to the value for the high density polyethylene homopolymer. In the calculations performed herein, T _A is 372 ° K and P _A is 1.

T _AB is the ATREF temperature for a random copolymer 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 correction using a number of known random ethylene comonomers. It should be noted that α and β may vary from instrument to instrument. In addition, the polymer compositions of interest also need to obtain their own calibration curves within the molecular weight range similar to 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 satisfies the following relationship.

Ln P = -237.83 / T _ATREF + 0.639

T _XO is the ATREF temperature for random copolymers of the same composition with an ethylene mole fraction of P _X. T _XO can be calculated from Ln P _X = α / T _XO + β. Conversely, P _XO is the ethylene mole fraction for random copolymers of the same composition with an ATREF temperature of T _X , and T _X 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 a block index greater than about 0.1 and up to about 1.0, which can be obtained by preparative TREF, At least one polymer fraction having a molecular weight distribution (Mw / Mn) 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 yet 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 and also a single Tm.

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

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

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

The polymer has a molecular weight (Mw) 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 ) The density of the polymer of the present invention may be 0.80 to 0.99 g / cm ³ , preferably 0.85 g / cm ³ to 0.97 g / cm ³ for ethylene containing polymers. In certain embodiments, the density of the ethylene / α-olefin polymer is in the range of 0.860 to 0.925 g / cm ³ or 0.867 to 0.910 g / cm ³ .

Methods of making polymers are disclosed in the following patent applications: US Provisional Application No. 60 / 553,906, filed March 17, 2004; 60 / 662,937, filed March 17, 2005; 60 / 662,939, filed March 17, 2005; 60/5662938, filed March 17, 2005; PCT Application No. PCT / US2005 / 008916, filed March 17, 2005; PCT Application No. PCT / US2005 / 008915, filed March 17, 2005; And PCT / US2005 / 008917, filed March 17, 2005, all of which are incorporated herein by reference in their entirety. For example, one such method involves the process of adding ethylene and optionally one or more addition polymerizable monomers other than ethylene under addition polymerization conditions,

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

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

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

It comprises contacting with a catalyst composition comprising a.

Representative catalysts and chain transfer agents are as follows.

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

Catalyst (A2) : [N- (2,6-di (1-methyl), prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024, and WO 04/24740, filed May 2, 2003. Ethyl) 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 substantially prepared according to the teachings of US Pat. No. 6,268,444 Silantitanium dimethyl.

Catalyst ( C2 ) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a-η- 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), ethylaluminum bis (t-butyl Dimethylsiloxide), 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 ).

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 in the highest peak temperature range measured using DSC. It is believed that this particular feature of the interpolymers of this invention 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 transparency, tear strength and high temperature recovery properties increase while the haze decreases. By selecting a combination of a catalyst and a transfer agent having the desired chain transfer capacity (high transfer rate at low chain termination), other forms of polymer termination are effectively suppressed. Thus, the polymerization of ethylene / α-olefin comonomer mixtures according to embodiments of the present invention results in very little β-hydride removal, even when present, and the resulting crystalline blocks have little or no long chain branching and are very or substantially Completely linear.

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

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

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

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

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 This includes. 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 (Mw) 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, and Mooney ) Is a 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 optionally further 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 will typically be present in the copolymerized functionalized interpolymer in an amount of less than about 40 wt%, preferably less than about 30 wt%, more preferably less than about 25 wt%.

The amount of ethylene / α-olefin interpolymers in the polymer blends disclosed herein may 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 70 weight of the total weight of the polymer blend. Weight percent, about 10 to about 50 weight percent, about 50 to about 90 weight percent, about 60 to about 90 weight percent, or about 70 to about 90 weight percent.

Polyolefin

The polymer blends disclosed herein may comprise one or more polyolefins. Preferably, the melt strength (“MS”) of a suitable polyolefin should be 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%.

Polyolefins are polymers derived from two or more olefins (ie alkenes). Olefins (ie alkenes) are hydrocarbons containing at least one carbon-carbon double bond. The olefins are monoenes (ie, olefins with one carbon-carbon double bond), dienes (ie, olefins with two carbon-carbon double bonds), trienes (ie, olefins with three carbon-carbon double bonds) ), Tetraenes (ie, olefins having four carbon-carbon double bonds), and other polyenes. Olefins or alkenes such as monoenes, dienes, trienes, tetraenes and other polyenes may have at least 3 carbon atoms, at least 4 carbon atoms, at least 6 carbon atoms, at least 8 carbon atoms. In some embodiments, the olefin has 3 to about 100 carbon atoms, 4 to about 100 carbon atoms, 6 to about 100 carbon atoms, 8 to about 100 carbon atoms, 3 to about 50 carbons An atom, 3 to about 25 carbon atoms, 4 to about 25 carbon atoms, 6 to about 25 carbon atoms, 8 to about 25 carbon atoms, or 3 to about 10 carbon atoms. In some embodiments, the olefin is a linear or branched, cyclic or acyclic monoene having 2 to about 20 carbon atoms. In other embodiments, the alkenes are dienes such as 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 certain embodiments, 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.

The amount of polyolefin in the polymer blend is about 0.5 to about 99 weight percent, about 1 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 of the total weight of the polymer blend. %, About 5 to about 50 weight percent, about 50 to about 95 weight percent, about 10 to about 50 weight percent, about 10 to about 30 weight percent, or about 50 to about 90 weight percent. In some embodiments, the amount of polyolefin in the polymer blend can be about 1 to about 25 weight percent, about 5 to about 15 weight percent, about 7.5 to about 12.5 weight percent, or about 10 weight percent of the total weight of the polymer blend.

Any polyolefin known to those of ordinary skill in the art can be used to prepare the polymer blends disclosed herein. The polyolefins can be olefin homopolymers, olefin copolymers, olefin terpolymers, olefin quaternary copolymers, and the like, and combinations thereof.

In some embodiments, one of the two or more polyolefins is an olefin homopolymer. The olefin homopolymer can be derived from one olefin. Any olefin homopolymer known to those skilled in the art can be used. Non-limiting examples of olefin homopolymers include polyethylene, polypropylene, polybutylene, polypentene-1, polyhexene-1, polyoctene-1, polydecene-1, poly-3-methylbutene-1, poly-4- Methylpentene-1, polyisoprene, polybutadiene, poly-1,5-hexadiene.

In other embodiments, the olefin homopolymer is polyethylene. Any polyethylene known to those skilled in the art can be used to prepare the polymer blends disclosed herein. Non-limiting examples of polypropylene include ultra low density polyethylene (ULDPE), low density polyethylene (LDPE), linear high density low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high melt strength high density polyethylene (HMS-HDPE). ), And ultra high density polyethylene (UHDPE), and the like, and combinations thereof. In some embodiments, the olefin homopolymer is a HMS-HDPE such as HDPE 2492 ^® (Dow Chemical (Midland, MI available from United States)) Dow Conti titanium (CONTINUUM). In other embodiments, the amount of HMS-HDPE in the polymer blend can be about 1 to about 25 weight percent, about 5 to about 15 weight percent, about 7.5 to about 12.5 weight percent, or about 10 weight percent of the total weight of the polymer blend. have.

In other embodiments, the olefin homopolymer is polypropylene. Any of the polypropylenes known to those skilled in the art can be used to prepare the polymer blends disclosed herein. Non-limiting examples of polypropylene include low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), isotactic polypropylene (iPP), syndio Tactile polypropylene (sPP) and the like, and combinations thereof. In some embodiments, the olefin homopolymer is available (Dow Chemical (Michigan, USA, Midland,), available from) Dow Inspire (INSPIRE) ^® Dl14, (Basel polyolefin's (Basell Polyolefins) (available from Maryland Elkton material) ) PROFAX ^® PF814, HMS-PP such as DAPLOY® WB130 and WB260 (available from Borealis A / S, Ringby, Denmark). In other embodiments, the amount of HMS-PP in the polymer blend can be about 1 to about 25 weight percent, about 5 to about 15 weight percent, about 7.5 to about 12.5 weight percent, or about 10 weight percent of the total weight of the polymer blend. have.

In other embodiments, the polyolefin is an olefin copolymer. The olefin copolymer can be derived from any two different olefins. Any olefin polymer known to those skilled in the art can be used in the polymer blends disclosed herein. Non-limiting examples of olefin copolymers include copolymers derived from ethylene and monoenes having three or more carbon atoms. Non-limiting examples of monoenes having three or more carbon atoms include propene, butenes (eg 1-butene, 2-butene and isobutene) and alkyl substituted butenes; Pentenes (eg 1-pentene and 2-pentene) and alkyl substituted pentenes (eg 4-methyl-1-pentene); Hexene (eg 1-hexene, 2-hexene and 3-hexene) and alkyl substituted hexene; Heptenes (eg 1-heptene, 2-heptene and 3-heptene) and alkyl substituted heptenes; Octenes (eg 1-octene, 2-octene, 3-octene and 4-octene) and alkyl substituted octenes; Nonene (eg 1-nonene, 2-nonene, 3-nonene and 4-nonene) and alkyl substituted nonene; Decene (eg, 1-decene, 2-decene, 3-decene, 4-decene and 5-decene) and alkyl substituted decene; Dodecene and alkyl substituted dodecene; And butadiene. In some embodiments, the olefin copolymer is an ethylene / alpha-olefin (EAO) copolymer or an ethylene / propylene copolymer (EPM).

In other embodiments, the polyolefin is an olefin terpolymer. The olefin terpolymer can be derived from three different olefins. Any olefin terpolymer known to those skilled in the art can be used in the polymer blends disclosed herein. Non-limiting examples of olefin terpolymers include (i) ethylene, (ii) monoenes having three or more carbon atoms, and (iii) terpolymers derived from dienes. In some embodiments, the olefin terpolymers are ethylene / alpha-olefin / diene terpolymers (EAODM) and ethylene / propylene / diene terpolymers (EPDM).

Some of the important properties of suitable polyolefins include tensile strength, tear strength, modulus, top service temperature, scratch and scratch resistance, and the like. The combination of high tensile strength, heat resistance and processability of polypropylene homopolymers, propylene-alpha-olefin copolymers, propylene impact copolymers, high density polyethylene, low density polyethylene, linear low density polyethylene and ethylene-alpha-olefin copolymers make these polymers preferred. Made with blend ingredients. In addition, a styrene-based block copolymer (styrene-ethylene-butene-styrene) may be blended to obtain a unique balance of elastic recovery and heat resistance (see below).

Styrene series  Block copolymer

The polymer blend may also include one or more styrenic block copolymers in addition to or in place of the one or more polyolefins described above. The amount of styrenic block copolymer in the polymer blend is about 0.5 to about 99 weight percent, about 1 to about 95 weight percent, about 10 to about 90 weight percent, about 20 to about 80 weight percent, about 30 of the total weight of the polymer blend. To about 70 weight percent, about 5 to about 50 weight percent, about 50 to about 95 weight percent, about 10 to about 50 weight percent, about 10 to about 30 weight percent, or about 50 to about 90 weight percent. In some embodiments, the amount of styrenic block copolymer in the polymer blend is about 1 to about 25 weight percent, about 5 to about 15 weight percent, about 7.5 to about 12.5 weight percent, or about 10 weight percent of the total weight of the polymer blend. Can be.

Generally speaking, the styrenic block copolymer comprises two or more monoalkenyl arene blocks, preferably two polystyrene blocks separated by blocks of saturated conjugated dienes, preferably saturated polybutadiene blocks. Although branched or radical polymers or functionalized block polymers make useful compounds, styrenic block copolymers having a linear structure are preferred. If the copolymer has a linear structure, the total number average molecular weight of the styrenic block copolymer is preferably 30,000 to about 250,000. The average polystyrene content of such block copolymers may be 10% to 40% by weight.

Suitable unsaturated block copolymers include, but are not limited to, those represented by the formula:

Wherein each A is a polymer block comprising a vinyl aromatic monomer, preferably styrene, and each B is a polymer block comprising a conjugated diene, preferably isoprene or butadiene, and optionally a vinyl aromatic monomer, preferably styrene R is a residue of the polyfunctional coupling agent (if R is present, the block copolymer may be a star or branched block copolymer), n is an integer from 1 to 5, x is 0 or 1, y is a real number from 0 to 4.

Methods of making such block copolymers are known in the art. See, for example, US Pat. No. 5,418,290. Suitable catalysts for preparing useful block copolymers with unsaturated rubber monomer units include lithium based catalysts and in particular lithium-alkyl. U. S. Patent No. 3,595, 942 describes a process suitable for hydrogenation of block copolymers with unsaturated rubber monomer units to block copolymers with saturated rubber monomer units. The structure of the polymer is determined by their polymerization method. For example, linear polymers can be introduced by sequentially introducing the desired rubber monomer into the reaction vessel when using an initiator such as lithium-alkyl or dithiostilbene, or coupling the bifunctional coupling agent with the two segment block copolymers. To create. Branched structures, on the other hand, can be obtained using suitable coupling agents that have functionality for block copolymers having three or more unsaturated rubber monomer units. Coupling can be carried out with dihaloalkenes or with polyfunctional coupling agents such as alkenes and divinyl benzenes and also with certain polar compounds such as esters of monohydric alcohols with silicone halides, siloxanes or carboxylic acids. The presence of any coupling residues in the polymer can be ignored for proper description of the block copolymer.

Suitable block copolymers with unsaturated rubber monomer units include styrene-butadiene (SB), styrene-ethylene / butadiene (SEB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS ), but is not limited to α-methylstyrene-butadiene-α-methylstyrene and α-methylstyrene-isoprene-α-methylstyrene.

The styrenic portion of the block copolymer is preferably a polymer or interpolymer of styrene and analogs and homologues thereof, including α-methylstyrene and ring substituted styrenes, in particular ring methylated styrene. Preferred styrene systems are styrene and α-methylstyrene, with styrene being particularly preferred.

Block copolymers with unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene or they may comprise copolymers of one or both of these two dienes which are minor styrene-based monomers. In some embodiments, the block copolymers (i) a C _{3 -20} olefin substituted with an alkyl or aryl (e.g., 4-methyl-1-pentene and styrene) and (ii) a diene (e.g. butadiene, 1 , 5-hexadiene, 1,7-octadiene and 1,9-decadiene). Non-limiting examples of such olefin copolymers include styrene-butadiene-styrene (SBS) block copolymers.

Preferred block copolymers with saturated rubber monomer units include segments of one or more styrene-based units and segments of one or more ethylene-butene or ethylene-propylene copolymers. Preferred examples of such block copolymers with saturated rubber monomer units are styrene / ethylene-butene copolymers, styrene / ethylene-propylene copolymers, styrene / ethylene-butene / styrene (SEBS) copolymers, styrene / ethylene-propylene / styrene (SEPS) copolymers.

Hydrogenation of block copolymers with unsaturated rubber monomer units preferably nickel or cobalt carboxylate under conditions for hydrogenating up to 25% or less of styrenic aromatic double bonds while substantially completely hydrogenating at least 80% of aliphatic double bonds. Or a catalyst comprising a reaction product of an alkoxide and an aluminum alkyl compound. Preferred block copolymers are those in which less than 5% of the aromatic double bonds are hydrogenated while at least 99% of the aliphatic double bonds are hydrogenated.

The proportion of styrenic blocks is generally from 8 to 65% by weight of the total weight of the block copolymer. Preferably, the block copolymer contains 10 to 35 weight percent styrenic block segments and 90 to 65 weight percent rubber monomer block segments based on the total weight of the block copolymer.

The average molecular weight of the individual blocks can vary within certain limits. In most cases, the number average molecular weight of the styrenic block segments will be in the range of 5,000 to 125,000, preferably 7,000 to 60,000, while the number average molecular weight of the rubber monomer block segments will be in the range of 10,000 to 300,000, preferably 30,000 to 150,000. will be. The total average molecular weight of the block copolymer is typically in the range of 25,000 to 250,000, preferably 35,000 to 200,000.

In addition, various block copolymers suitable for use in embodiments of the present invention may be modified by graft incorporation of small amounts of functional groups, such as maleic anhydride, by any method well known in the art.

Suitable block copolymers are commercially available, such as Kraton ™ supplied by KRATON Polymers LLC, Houston, TX, and Dexco Polymers L.P., Houston, TX, USA. Vectors (VECTOR) ™ supplied by (Dexco Polymers, L.P.) include, but are not limited to.

additive

Optionally, the polymer blends disclosed herein may include one or more additives for the purpose of improving and / or controlling the processability, appearance, physical, chemical, and / or mechanical properties of the polymer blend. In some embodiments, the polymer blend does not contain additives. Any plastic additive known to those skilled in the art can be used in the polymer blends disclosed herein. Non-limiting examples of suitable additives include slip agents, 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, and combinations thereof. The total amount of additives may be from about 0 to about 80%, about 0.001% to about 70%, about 0.01% to about 60%, about 0.1% to about 50%, about 1% to about 40%, of the total weight of the polymer blend, Or from about 10% to about 50%. Some polymer additives are described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001), which is hereby incorporated by reference in its entirety.

In some embodiments, the polymer blends disclosed herein comprise a slip agent. In other embodiments, the polymer blends disclosed herein do not include slip agents. Slip is sliding of the film surface over each other or some other substrate. The slip performance of the film can be measured by ASTM D 1894 [Static and Kinetic Coefficients of Friction of Plastic Film and Sheeting], incorporated herein by reference. In general, slip agents modify the surface properties of the film and can impart slip properties by reducing friction between the film layers and between the film and other surfaces that come into contact.

Any slip agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of slip agents include primary amides having about 12 to about 40 carbon atoms (eg, erucamide, oleamide, stearamide, and behenamide); Secondary amides having from about 18 to about 80 carbon atoms (eg, stearyl erucamide, behenyl erucamide, methyl erucamide and ethyl erucamide); Secondary-bis-amides having about 18 to about 80 carbon atoms (eg, ethylene-bis-stearamid and ethylene-bis-oleamide); And combinations thereof. In certain embodiments, the slip agent for the polymer blends disclosed herein is an amide represented by Formula 1 below.

Wherein each of R ¹ and R ² is independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl, and R ³ is each from about 11 to about 39 carbon atoms, about 13 to about 37 Alkyl or alkenyl having about 15 to about 35 carbon atoms, about 17 to about 33 carbon atoms, or about 19 to about 33 carbon atoms. In some embodiments, R ³ is alkyl or alkenyl, each having at least 19 to about 39 carbon atoms. In other embodiments, R ³ is pentadecyl, heptadecyl, nonadecyl, henecosanyl, tricosanyl, pentacosanyl, heptacosanyl, nonacosanyl, gentriacontanil, tritricontanil, nonatri Acontanil or combinations thereof. In a further embodiment, R ³ is pentadecenyl, heptadecenyl, nonadesenyl, henecosaneyl, tricosanenyl, pentacosaneyl, heptacosanenyl, nonacosanenyl, gentriacontanenyl, tri Triacontanenyl, nonatriacontanenyl, or a combination thereof.

In a further embodiment, the slip agent for the polymer blends disclosed herein is the amide represented by Formula 2 below.

CH _3- (CH ₂ ) _m- (CH = CH) _p- (CH ₂ ) _n -C (= 0) -NR ¹ R ²

Wherein m and n are each independently an integer from about 1 to about 37, p is an integer from 0 to 3, and R ¹ and R ² are each independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl Or aryl, and the sum of m, n, and p is 8 or more. In some embodiments, R ¹ and R ² in Formulas 1 and 2 are each an alkyl group containing 1 to about 40 carbon atoms or an alkenyl group containing 2 to about 40 carbon atoms. In further embodiments, R ¹ and R ² in Formulas 1 and ² are each H. In certain embodiments, the sum of m, n, and p is at least 18.

Amides of Formula 1 or 2 may be selected from Formula R ³ -CO ₂ H or CH _3- (CH ₂ ) _m- (CH = CH) _p- (CH ₂ ) _n -CO ₂ H, wherein R ³ is at least 19 Alkyl or alkenyl having from about 39 carbon atoms, m and n are each independently an integer from about 1 to about 37, and p is 0 or 1, and a carboxylic acid having the formula H-NR ¹ R ² Wherein R ¹ and R ² are each independently H, alkyl, cycloalkyl, alkenyl or aryl. The amine of formula H-NR ¹ R ² is ammonia (ie R ¹ and R ² are each H), primary amine (ie R ¹ is alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl, R ² is H) or secondary amines (ie, R ¹ and R ² are each independently alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl). Some non-limiting examples of primary amines are methylamine, ethylamine, octadecylamine, behenylamine, tetracosanylamine, hexacosanylamine, octacosanylamine, triacontylamine, dotriacontylamine, tetratri Acontylamine, tetracontylamine, cyclohexylamine and combinations thereof. Some non-limiting examples of secondary amines are dimethylamine, diethylamine, dihexadecylamine, dioctadecylamine, diecosylamine, didocosylamine, diecetylamine, distearylamine, diarachidylamine, dibehenyl Amines, dihydrogenated tallow amines, and combinations thereof. Primary and secondary amines may be prepared by methods known to those of ordinary skill in the art, or may include Aldrich Chemicals (Milwaukee, WI); ICC Chemical Corporation (New York, NY); Chemos GmbH (Regenstauf, Germany); ABCR GmbH & Co. KG (Karlsruhe, Germany); And Acros Organics (Gile, Belgium).

Primary or secondary amines may be prepared by reductive amination reactions. Reductive amination is a process in which ammonia or primary amines are condensed with aldehydes or ketones to form the corresponding imines, which are then reduced to amines. Subsequent reduction of the imines to amines is hydrogen and hydrides such as suitable hydrogenation catalysts such as Raney nickel and platinum oxide, aluminum-mercury amalgam, or lithium aluminum hydride, sodium cyanoborohydride, and sodium borohydride. This can be achieved by reacting with imine. Reductive amination is described in US Pat. No. 3,187,047, and Haskelberg, “Aminative Reduction of Ketones,” J. Am. Chem. Soc., 70 (1948) 2811-2; Mastagli et al., "Study of the Aminolysis of Some Ketones and Aldehydes," Bull. soc. chim. France (1950) 1045-8; [B. J. Hazzard, Practical Handbook of Organic Chemistry, Addison-Wesley Publishing Co., Inc., pp. 458-9 and 686 (1973); And Alexander et al., “A Low Pressure Reductive Alkylation Method for the Conversion of Ketones to Primary Amines,” J. Am. Chem. Soc, 70, 1315-6 (1948). The above US patents and articles are incorporated herein by reference.

Non-limiting examples of carboxylic acids include straight chain saturated fatty acids such as tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanic acid, heneic acid, docoic acid, Trichoic acid, tetracoic acid, pentacoic acid, hexacoic acid, heptaconic acid, octacoic acid, nonacoic acid, triacontanic acid, hentriconic acid, dotriacontanic acid, tetratriconic acid, hexatriaconic acid , Octatriconic acid and tetracontanic acid; Branched chain saturated fatty acids such as 16-methylheptadecanoic acid, 3-methyl-2-octylnonanoic acid, 2,3-dimethyloctadecanoic acid, 2-methyltetracarboxylic acid, 11-methyltetracarboxylic acid, 2- Pentadecyl-heptadecanoic acid; Unsaturated fatty acids such as trans-3-octadecenoic acid, trans-11-eicosenoic acid, 2-methyl-2-eicosenoic acid, 2-methyl-2-hexacosenoic acid, β-eleostearic acid, α-paris Naric acid, 9-nonadecenic acid, and 22-tricosenoic acid, oleic acid and erucic acid. Carboxylic acids can be prepared by methods known to those of ordinary skill in the art or by Aldrich Chemicals (Milwaukee, WI); IC Chemical Corporation (New York, NY); Chemos geembeha (Regenstaff, Germany); Avechere Geembehaunt Cochage (Carlesruhe, Germany); And commercial sources such as Acros Organics (Gile, Belgium). Some known methods of preparing carboxylic acids include oxidizing the corresponding primary alcohol with an oxidant such as metal chromate, metal dichromate and potassium permanganate. Oxidation of alcohols to carboxylic acids is described in Carey et al., "Advance Organic Chemistry, Part B: Reactions and Synthesis," Plenum Press, New York, 2nd Edition, pages 481-491 (1983 )].

The amidation reaction can be carried out in a solvent that is not reactive to carboxylic acids. Non-limiting examples of suitable solvents include ethers (ie diethyl ether and tetrahydrofuran), ketones (eg acetone and methyl ethyl ketone), acetonitrile, dimethyl sulfoxide, dimethyl formamide and the like. The amidation reaction can be promoted by a base catalyst. Non-limiting examples of base catalysts include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium acetate, ammonium acetate, metal alkoxides such as sodium methoxide, sodium ethoxide, triethylamine, di Amines such as isopropylethylamine and the like. In some embodiments, the catalyst is an amine or metal alkoxide.

In some embodiments, the slip agent is a primary amide (eg, stearamide and behenamide) with saturated aliphatic groups having 18 to about 40 carbon atoms. In other embodiments, the slip agent is a primary amide (eg, erucamide and oleamide) with at least one carbon-carbon double bond and unsaturated aliphatic groups containing 18 to about 40 carbon atoms. In further embodiments, the slip agent is a primary amide having 20 or more carbon atoms. In further embodiments, the slip agent is erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearamid, ethylene-bis-oleamide, stearyl erucamide, behenyl erucamide or combinations thereof to be. In certain embodiments, the slip agent is erucamide. In a further embodiment, the slip agent is from ATMER ™ SA, Akzo Nobel Polymer Chemicals, Chicago, Illinois, USA from Uniqema (Everberg, Belgium). are all sleep (ARMOSLIP) ^®, wit nose (Witco) is a croissant from Kem amide (KEMAMIDE) ^®, and Black is (Croda) (New Jersey, USA Edison material) from the (United States, Connecticut, Greenwich material) mid (CRODAMIDE ) is commercially available having a trade name such as ^®. In use, the amount of slip agent in the polymer blend is greater than about 0 to about 3 weight percent, about 0.0001 to about 2 weight percent, about 0.001 to about 1 weight percent, about 0.001 to about 0.5 weight percent, or about 0.05, of the total weight of the polymer blend. To about 0.25 weight percent. Some slip agents are described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 8, pages 601-608 (2001). .

Optionally, the polymer blends disclosed herein may include antiblocking agents. In some embodiments, the polymer blends disclosed herein do not include antiblocking agents. Antiblocking agents can be used to prevent undesired adhesion between the contact layers of articles made from polymer blends, especially during storage, manufacture or use, under normal pressure and heat. Any antiblocking agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of anti-blocking agent is a mineral (e.g., clays, chalk, and calcium carbonate), synthetic silica gel (e.g., Grace Davison (Grace Davison) (chamber block (SYLOBLOC) from Maryland Columbia material) ^® ), Natural silica (e.g. SUPER FLOSS ^® from Celite Corporation, Santa Barbara, Calif.), Talc (e.g., Luzenac, Colorado, USA OPTIBLOC ^® from Centennial, USA; Zeolite (e.g., SIPERNAT ^® from Degussa, Parsippany, NJ), aluminosilicate (example For example, SILTON ^® from Mizusawa Industrial Chemicals (Tokyo, Japan), limestone (e.g., Car from Omya (Atlanta, GA, USA) CARBOREX ^® , spherical polymer particles (e.g., EPOSTAR ^® , poly (methyl methacrylate) particles and GE silicones from Nippon Shokubai (Tokyo, Japan) GE Silicones) (US Conn wilton toss pearl (TOSPEARL) from the material) ^®, silicone particles), waxes, amides (e.g. erucamide to, oleamide, stearamide, behenamidopropyl amide, ethylene-bis-stearamide, Ethylene-bis-oleamide, stearyl erucamide and other slip agents), molecular sieves, and combinations thereof. Organic antiblocking agents may migrate to the surface to limit surface adhesion, while mineral particles may create physical spacing between articles to lower blocking. In use, the amount of antiblocking agent in the polymer blend can be greater than about 0 to about 3 weight percent, about 0.0001 to about 2 weight percent, about 0.001 to about 1 weight percent, or about 0.001 to about 0.5 weight percent of the total weight of the polymer blend. have. Some antiblocking agents are described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 7, pages 585-600 (2001). .

Optionally, the polymer blends disclosed herein can include a plasticizer. Generally, plasticizers are chemicals that can increase the flexibility of the polymer and lower the glass transition temperature. Any plasticizer known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of plasticizers include abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrate, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates Ates, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, lysine oleates, sebacates, sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates, difuran diesters, fluorine-containing plasticizers, hydrates Oxybenzoic acid esters, isocyanate adducts, polycyclic aromatic compounds, natural product derivatives, nitriles, siloxane based plasticizers, tar based products, thioethers and combinations thereof. In use, the amount of plasticizer in the polymer blend can be greater than 0 to about 15 weight percent, about 0.5 to about 10 weight percent, or about 1 to about 5 weight percent of the total weight of the polymer blend. Some plasticizers are described in George Wypych, "Handbook of Plasticizers," ChemTec Publishing, Toronto-Scarborough, Ontario (2004).

In some embodiments, the polymer blends disclosed herein optionally include antioxidants that can prevent oxidation of the polymer component and organic additives in the polymer blend. Any antioxidant known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable antioxidants include alkyl diphenylamines, phenyl-α-naphthylamines, alkyl or aralkyl substituted phenyl-α-naphthylamines, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamines. Aromatic or hindered amines such as the like; Phenols such as 2,6-di-t-butyl-4-methylphenol; 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) benzene; IRGANOX from tetrakis [(methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (e.g. Ciba Geigy, New York, USA) ) 1010); acryloyl modified phenol; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g. Irganox ™ 1076 available from Ciba Geigy); Pit and phosphonite; hydroxylamine; benzofuranone derivatives; and combinations thereof In use, the amount of antioxidant in the polymer blend is greater than 0 to about 5 weight percent, from about 0.0001 to about 0.00 weight of the total weight of the polymer blend. 2.5 weight percent, about 0.001 to about 1 weight percent, or about 0.001 to about 0.5 weight percent Some antioxidants are described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner, incorporated herein by reference. Publications, Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001). .

In other embodiments, the polymer blends disclosed herein optionally include UV stabilizers that can prevent or reduce degradation of the polymer by UV radiation. Any UV stabilizer known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable UV stabilizers include benzophenone, benzotriazole, aryl esters, oxanilides, acrylic esters, formamidine, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, Metallic salts, zinc compounds and combinations thereof. In use, the amount of UV stabilizer in the polymer blend can be greater than 0 to about 5 weight percent, about 0.01 to about 3 weight percent, about 0.1 to about 2 weight percent, or about 0.1 to about 1 weight percent of the total weight of the polymer blend. have. Some UV stabilizers are described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, pages 141-426 (2001). have.

In further embodiments, the polymer blends disclosed herein optionally include colorants or pigments that can alter the appearance of the polymer blend on the human eye. Any colorant or pigment known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable colorants or pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic dyes such as anthraquinones, anthrones, azo and Monoazo compounds, arylamides, benzimidazolone, BONA lake, diketopyrrolo-pyrrole, dioxazine, disazo compounds, diarylide compounds, flavantrons, indanthrones, isoindolinones, iso Indolin, metal compounds, monoazo salts, naphthol, b-naphthol, naphthol AS, naphthol lake, perylene, perinone, phthalocyanine, pyrantrone, quinacridone, and quinophthalone and combinations thereof. In use, the amount of colorant or pigment in the polymer blend can be greater than 0 to about 10 weight percent, about 0.1 to about 5 weight percent, or about 0.25 to about 2 weight percent of the total weight of the polymer blend. Some colorants are described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 15, pages 813-882 (2001).

Optionally, the polymer blends disclosed herein can include fillers that can be used to specifically adjust volume, weight, cost, and / or technical performance. Any filler known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable fillers include hydrated alumina such as talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, alumina trihydrate , Glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, wood powder, glass fiber, carbon fiber, marble powder, cement powder, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, sulfuric acid Barium, titanium dioxide, titanate and combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fibers, alumina, titanium dioxide, or mixtures thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fibers or mixtures thereof. In use, the amount of filler in the polymer blend is greater than 0 to about 80 weight percent, about 0.1 to about 60 weight percent, about 0.5 to about 40 weight percent, about 1 to about 30 weight percent, or about 10 to about the total weight of the polymer blend. About 40% by weight. Some fillers are described in US Pat. No. 6,103,803 and Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, pages 901-948 (2001), incorporated herein by reference. )].

Optionally, the polymer blends disclosed herein can include a lubricant. In general, lubricants may be used to modify the rheology of the melt polymer blends in particular, to improve the surface finish of the molded article, and / or to facilitate the dispersion of fillers or pigments. Any lubricant known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable lubricants include fatty acid alcohols and their dicarboxylic acid esters, fatty acid esters of short chain alcohols, fatty acids, fatty acid amides, metal soaps, oligomeric fatty acid esters, fatty acid esters of long chain alcohols, montan wax, polyethylene Waxes, polypropylene waxes, natural and synthetic paraffin waxes, fluoropolymers, and combinations thereof. In use, the amount of lubricant in the polymer blend can be greater than 0 to about 5 weight percent, about 0.1 to about 4 weight percent, or about 0.1 to about 3 weight percent of the total weight of the polymer blend. Some suitable lubricants are all disclosed in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001), incorporated herein by reference. have.

Optionally, the polymer blends disclosed herein may include an antistatic agent. In general, antistatic agents can increase the conductivity of the polymer blend to prevent charge charge accumulation. Any antistatic agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable antistatic agents include conductive fillers (eg carbon black, metal particles and other conductive particles), fatty acid esters (eg glycerol monostearate), ethoxylated alkylamines, diethanolamides, ethoxylated Alcohols, alkylsulfonates, alkylphosphates, quaternary ammonium salts, alkylbetaines and combinations thereof. In use, the amount of antistatic agent in the polymer blend can be greater than 0 to about 5 weight percent, about 0.01 to about 3 weight percent, or about 0.1 to about 2 weight percent of the total weight of the polymer. Some suitable antistatic agents are disclosed in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 10, pages 627-646 (2001), incorporated herein by reference. It is.

Optionally, the polymer blend can be partially or fully crosslinked. If crosslinking is desired, the polymer blends disclosed herein can be used to achieve crosslinking of the polymer blend, thereby including crosslinkers that can increase their modulus and stiffness among others. Any crosslinking agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable crosslinkers include organic peroxides (eg, alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, and cyclic peroxides) and silanes ( For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, and 3-methacryloyloxypropyltri Methoxysilane). In use, the amount of crosslinker in the polymer blend can be greater than 0 to about 20 weight percent, about 0.1 to about 15 weight percent, or about 1 to about 10 weight percent of the total weight of the polymer blend. Some suitable crosslinkers are disclosed in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, pages 725-812 (2001), incorporated herein by reference. have.

Crosslinking of the polymer blend may also be initiated with or without a crosslinking catalyst by any spinning means known in the art, including, but not limited to, electron beam irradiation, beta irradiation, gamma irradiation, corona irradiation, and UV radiation. Can be. US Patent Application No. 10 / 086,057 (published as US2002 / 0132923 A1) and US Patent No. 6,803,014 disclose methods of electron beam irradiation that can be used in embodiments of the present invention.

Irradiation can be achieved by the use of high energy, ionized electrons, ultraviolet light, X-rays, gamma rays, beta particles and the like and combinations thereof. Preferably, the former is used at a dose of 70 megarad or less. The radiation source can be any electron beam generator that operates within the range of about 150 kilovolts to about 6 mechabolds, which is a power output capable of supplying the desired dosage. The voltage can be adjusted to an appropriate level, which can be, for example, 100,000, 300,000, 1,000,000 or 2,000,000 or 3,000,000 or 6,000,000 or higher or lower. Many other devices for investigating polymeric materials are known in the art. Irradiation is usually carried out at dosages of about 3 megarad to about 35 megarad, preferably about 8 to about 20 megarad. In addition, higher or lower temperatures, such as 0 ° C. to about 60 ° C., may also be used, but irradiation can typically be carried out at room temperature. Preferably, the irradiation is carried out after formation or manufacture of the article. Also in a preferred embodiment, the ethylene interpolymers incorporated with the pro-rad additives are irradiated with electron beam radiation at about 8 to about 20 megarads.

Crosslinking can be facilitated with a crosslinking catalyst and any catalyst that will provide this function can be used. Suitable catalysts generally include organometallic compounds including organic bases, carboxylic acids, and organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin. Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, tin (I) acetate, tin (I) octoate, lead naphthenate, zinc caprylate, cobalt Naphthenate and the like. Tin carboxylates, in particular dibutyltin dilaurate and dioctyltin maleate, are particularly effective in the present invention. The catalyst (or mixture of catalysts) is typically present in a catalytic amount of about 0.015 to about 0.035 phr.

Representative pro-rad additives include azo compounds, organic peroxides and polyfunctional vinyl or allyl compounds such as triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetramethacrylate, glutaraldehyde, ethylene Glycol dimethacrylate, diallyl maleate, dipropalyl maleate, dipropalyl monoallyl cyanurate, dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, Cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, lauryl peroxide, tert-butyl peracetate, azo Bisisobutyl nitrite and the like and combinations thereof, but is not limited thereto. Preferred pro-rad additives for use in the present invention are compounds having a multifunctional (ie two or more) residues such as C═C, C═N or C═O.

One or more pro-rad additives may be introduced into the ethylene interpolymer by any method known in the art. However, preferably the pro-rad additive is introduced via a masterbatch concentrate comprising a base resin that is the same or different from the ethylene interpolymer. Preferably, the pro-rad additive concentration for the masterbatch is relatively higher, for example about 25% by weight (based on the total weight of the concentrate).

One or more pro-rad additives are introduced into the ethylene polymer in any effective amount. Preferably, the amount of at least one pro-rad additive introduction amount is based on about 0.001 to about 5 weight percent (based on the total weight of the ethylene interpolymer), more preferably about 0.005 to about 2.5 weight percent, most preferably about 0.015 to About 1% by weight.

In addition to electron beam irradiation, crosslinking can also be effected by UV irradiation. US Pat. No. 6,709,742 discloses a crosslinking method by UV radiation that can be used in embodiments of the present invention. The method involves mixing the polymer with the photoinitiator with or without the photocrosslinker before, during, or after the fiber is formed, and then crosslinking the polymer to the desired level by exposing the fiber with photoinitiator to sufficient UV radiation. Include. Photoinitiators used in the practice of the invention are aromatic ketones, for example monoacetals of benzophenone or 1,2-diketone. The primary photoreaction of monoacetal is the homogeneous decomposition of α-bonds to obtain acyl and daalkoxyalkyl radicals. This type of α-degradation is described in W. Horspool and D. Armesto, Organic Photochemistry: A Comprehensive Treatment , Ellis Horwood Limited, Chichester, England, 1992; [J. Kopecky, Organic Photochemistry : A Visual Approach , VCH Publishers, Inc., New York, NY 1992; NJ. Turro, et al., Ace. Chem . Res . , 1972, 5, 92; And in JT Banks, et al., J. Am . Chem . Soc . , 1993, 115, 2473, is known as the Norrish type I reaction more fully described. The synthesis of monoacetal, Ar-CO-C (OR) ₂ -Ar ', of aromatic 1,2-diketones is described in US Pat. No. 4,190,602 and German Publication No. 2,337,813. Preferred compounds from this class are 2,2-dimethoxy-2-phenylacetophenone, C ₆ H ₅ -CO-C (OCH ₃ ) ₂ -C, available from Ciba-Geigy as Irgacure 651 ₆ H ₅ . Examples of other aromatic ketones useful as photoinitiators in the practice of the present invention are Irgacure 184, 369, 819, 907 and 2959, all available from Ciba-Geigy.

In one embodiment of the invention, the photoinitiator is used in combination with a photocrosslinker. In the generation of free radicals, any photoinitiator that forms covalent bonds with the backbone to bond two or more polyolefin backbones together can be used in the present invention. Preferably these photocrosslinkers are multifunctional. That is, they comprise two or more sites that will form covalent bonds with sites on the backbone of the copolymer when activated. Representative photocrosslinkers are polyfunctional vinyl or allyl compounds, for example triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetramethacrylate, ethylene glycol dimethacrylate, diallyl maleate, dipro Palmyl maleate, dipropalyl monoallyl cyanurate, and the like. Preferred photocrosslinkers for use in the present invention are compounds having polyfunctional (ie two or more) residues. Particularly preferred photocrosslinkers are triallycyanurate (TAC) and triallylisocyanurate (TAIC).

Certain compounds act as both photoinitiators and photocrosslinkers in the practice of the present invention. These compounds are characterized by the ability to generate two or more reactive species (e.g., free radicals, carbenes, nitrates, etc.) upon exposure to UV-light and subsequently covalently bond them to the two polymer chains. do. Any compound capable of performing these two functions can be used in the practice of the present invention, and representative compounds include the sulfonyl azides described in US Pat. Nos. 6,211,302 and 6,284,842.

In another embodiment of the invention, secondary crosslinking of the copolymer, ie crosslinking other than photocrosslinking, is carried out. In this embodiment, the photoinitiator is used in combination with a non-photocrosslinker such as silane or the copolymer is subjected to a secondary crosslinking procedure such as exposure to E-beam radiation. Representative examples of silane crosslinkers are described in US Pat. No. 5,824,718, and crosslinking through exposure to E-beam radiation is described in US Pat. Nos. 5,525,257 and 5,324,576. The use of photocrosslinkers in this embodiment is optional.

One or more photoadditives, ie photoinitiators and optionally photocrosslinkers, may be introduced into the copolymer by any method known in the art. Preferably, however, the optical additive is introduced through a masterbatch concentrate comprising a base resin that is the same or different from the copolymer. Preferably, the photoadditive concentration for the masterbatch is relatively higher, for example about 25% by weight (based on the total weight of the concentrate).

One or more photoadditives are introduced into the copolymer in any effective amount. Preferably, the amount of at least one photoadditive introduced is about 0.001 to about 5, more preferably about 0.005 to about 2.5, most preferably about 0.015 to about 1 weight percent (based on the total weight of the copolymer).

Photoinitiators and optional photocrosslinkers may be added during different stages of the fiber or film making process. If the light additive can withstand the extrusion temperature well, the polyolefin resin can be mixed with the additives, for example via masterbatch addition, before feeding to the extruder. Alternatively, the additive may be introduced into the extruder just before the slot die, but in this case effective mixing of the components before extrusion is important. In another approach, the polyolefin fibers can be stretched without photoadditives, and the photoinitiators and / or photocrosslinkers can be kiss-roll, sprayed, immersed in solutions with additives, or other for post-treatment. It is applicable to the fiber extruded by the industrial method. The resulting fiber with the photoadditive is then cured via electromagnetic radiation in a continuous or batch process. Light additives can be blended with polyolefins using conventional blending equipment, including single and twin screw extruders.

The power and irradiation time of electromagnetic radiation are chosen to allow efficient crosslinking without lack of polymer degradation and / or dimensions. Preferred processes are described in EP 0 490 854 Bl. Light additives with sufficient thermal stability are premixed with the polyolefin resin, extruded into fibers, and irradiated in a continuous process using one energy source or several devices connected in series. Using a continuous process as compared to a batch process has several advantages for curing the fibers or sheets of knitted fabric collected on a spool.

Irradiation can be achieved by the use of UV-spinning. Preferably, UV-radiation is used at an intensity of up to 100 J / cm ² . The irradiation source can be any UV-light generator that operates within the range of about 50 watts to about 25000 watts, which is the power output capable of supplying the desired dosage. The wattage may be adjusted to an appropriate level, which may be, for example, 1000 watts or 4800 watts or 6000 watts or higher or lower. Many other devices for UV irradiation of polymeric materials are known in the art. Irradiation is usually carried out at dosages of about 3 J / cm ² to about 500 J / cm ² , preferably about 5 J / cm ² to about 100 J / cm ² . In addition, although higher or lower temperatures, such as 0 ° C. to about 60 ° C., can also be used, irradiation can usually be carried out at room temperature. The photocrosslinking process is faster at higher temperatures. Preferably, the irradiation is carried out after shaping or fabrication of the article. In a preferred embodiment, the copolymer incorporated with the photoadditive is irradiated with UV-radiation at about 10 J / cm ² to about 50 J / cm ² .

polymer Blend  Produce

The components of the polymer blend, ie ethylene / α-olefin interpolymers, polyolefins (ie, first polyolefins and second polyolefins) and optional additives, are known to those skilled in the art, preferably ethylene / α-olefin interpolymers. Mixing or blending can be accomplished using methods that can provide a substantially uniform distribution of polyolefins and / or additives within. Non-limiting examples of suitable blending methods include melt blending, solvent blending, injection, and the like.

In some embodiments, the components of the polymer blend are melt blended by the method described in US Pat. No. 4,152,189 by Guerin et al. First, if any, remove all solvents from the components by heating to a suitable elevated temperature of about 100 ° C. to about 200 ° C. or about 150 ° C. to about 175 ° C. at a pressure between about 5 torr (667 Pa) and about 10 torr (1333 Pa) do. The components are then weighed into the container at the desired ratio and the contents of the container are heated in a molten state with stirring to form a polymer blend.

In other embodiments, the components of the polymer blend are processed using solvent blending. First, the components of the desired polymer blend are dissolved in a suitable solvent and then the mixture is mixed or blended. The solvent is then removed to provide a polymer blend.

In further embodiments, a physical blending device that provides dispersion mixing, dispensing mixing, or a combination of dispersion and dispensing mixing may be useful for producing uniform blends. Both batch and continuous processes of physical blending can be used. Non-limiting examples of batch methods are available from BRABENDER® mixing equipment (e.g., CWBrabender Instruments, Inc., South Haken, NJ). BRABENDER PREP CENTER®) or using the BANBURY® internal mixing and roll rolling equipment (available from Farrel Company, Connecticut). Non-limiting examples of continuous processes include single axis extrusion, biaxial extrusion, disc extrusion, reciprocating single axis extrusion, and pin barrel single axis extrusion. In some embodiments, additives may be added to the extruder through a feed hopper or feed throat during extrusion of the ethylene / α-olefin interpolymer, polyolefin or polymer blend. Mixing or blending of the polymers by extrusion is described in C. Rauwendaal, "Polymer Extrusion," Hanser Publishers, New York, NY, pages 322-334 (1986).

 When one or more additives are required in the polymer blend, the desired amount of additives may be added in one dose or multiple doses to the ethylene / α-olefin interpolymer, polyolefin or polymer blend. In addition, addition can be performed in arbitrary order. In some embodiments, the additive is first added, mixed or blended with the ethylene / α-olefin interpolymer and the additive-containing interpolymer is blended with the polyolefin. In other embodiments, the additive is first added and mixed or blended with the polyolefin and then mixed or blended with the ethylene / α-olefin interpolymer. In a further embodiment, the ethylene / α-olefin interpolymer is first blended with the polyolefin and then the additive is blended with the polymer blend. The polymer blend can also be performed in fabrication equipment such as dry blends (no preliminary formulation is required).

Alternatively, master batches containing high concentrations of additives can be used. In general, master batches can be prepared by blending ethylene / α-olefin interpolymers, polyolefins or polymer blends with high concentrations of additives. The additive concentration of the master batch may be about 1 to about 50 weight percent, about 1 to about 40 weight percent, about 1 to about 30 weight percent, or about 1 to about 20 weight percent of the total weight of the polymer blend. The master batch can then be added to the polymer blend in an amount determined to provide the desired additive concentration in the final product. In some embodiments, the master batch is a slip agent, antiblocking agent, plasticizer, antioxidant, UV stabilizer, colorant or pigment, filler, lubricant, invincible, flow aid, coupling agent, crosslinker, nucleating agent, surfactant, solvent, flame retardant , Antistatic agents, or a combination thereof. In other embodiments, the master batch contains a slip agent, antiblocking agent or a combination thereof. In other embodiments, the master batch contains a slip agent.

polymer Blend  apply

The polymer blends disclosed herein can be used to make durable articles for the automotive, construction, pharmaceutical, food and beverage, electrical, appliance, office equipment, and consumer markets. In some embodiments, the polymer blend is a toy, sack, soft hand grip, bumper friction strip, flooring, car floor mat, wheels, casters, furniture and appliance undercarriage, gaskets such as tags, seals, static and dynamic gaskets, automotive doors. Flexible durability selected from bumper straps, grill elements, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchenware, shoes, shoe bladders, shoe soles Used to manufacture parts or articles. In other embodiments, polymer blends can be used to make durable parts or articles that require high tensile strength and low compression set. In further embodiments, the polymer blend can be used to make durable parts or articles that require high top service temperatures and low modulus.

Polymer blends can be used to make a variety of useful articles by known polymer processes such as extrusion (eg, sheet extrusion and profile extrusion), molding (eg, injection molding, molding, rotational molding, and blow molding). have. In general, extrusion is a method of continuously pushing a polymer along a screw through a high temperature and high pressure region where the polymer is melted and compressed and finally pushed through a die. The extruder may be a single screw extruder, a multiple screw extruder, a disc extruder or a ram extruder. The die may be a film die, blown film die, sheet die, pipe die, tubing die or profile extrusion die. Extrusion of the polymers are all described in C. Rauwendaal, "Polymer Extrusion," Hanser Publishers, New York, NY (1986) and M.J. Stevens, "Extruder Principals and Operation," Ellsevier Applied Science Publishers, New York, NY (1985).

Injection molding is also widely used to manufacture a variety of plastic parts for a variety of applications. In general, injection molding is a method of melting a polymer and injecting it at a high pressure into a mold opposite of the desired shape to form parts of the desired shape and size. The mold can be made from metals such as steel and aluminum. Injection molding of polymers is described in Beaumont et al., “Successful Injection Molding: Process, Design, and Simulation,” Hanser Gardner Publications, Cincinnati, Ohio (2002), which is hereby incorporated by reference in its entirety.

Molding is generally a method of melting a polymer and introducing it into a mold that is the opposite of the desired shape to form parts of the desired shape and size. Molding can be a pressureless or pressure assisted process. Molding of polymers is described in Hans-Georg Elias "An Introduction to Plastics," Wiley-VCH, Weinhei, Germany, pp. 161-165 (2003).

Rotational molding is a commonly used method for producing hollow plastic products. Additional post-molding operations can be used to produce composite components as effectively as other molding and extrusion techniques. Rotational molding differs from other processing methods in that the heating, melting, molding, and cooling steps all occur after the polymer is placed in the mold, and there is no external pressure applied during formation. Rotational molding of polymers is described in Glenn Beall, "Rotational Molding: Design, Materials & Processing," Hanser Gardner Publications, Cincinnati, Ohio (1998).

Blow molding can be used to make hollow plastic containers. The method involves placing a softened polymer in the center of the mold, expanding the polymer towards the mold wall with a blow pin, and solidifying the product by cooling. There are three common types of blow molding: extrusion blow molding, injection blow molding, and stretch blow molding. Injection blow molding can be used to process polymers that cannot be extruded. Stretch blow molding can be used for crystalline and crystalline polymers, such as polypropylene, that are difficult to blow. Blow molding of polymers is described in Norman C. Lee, "Understanding Blow Molding," Hanser Gardner Publications, Cincinnati, Ohio (2000), which is hereby incorporated by reference in its entirety.

The following examples are shown to illustrate embodiments of the invention. All figures are approximate. When provided with a numerical range, it should be understood that embodiments outside the stated range may also be included within the scope of the present invention. The specific details described in each example should not be considered as essential features of the invention.

Test method

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

For samples 1-4 and A-C GPC  Way

Using an automated liquid-handling robot equipped with a heated needle set at 160 ° C., sufficient 1,2,4-trichlorobenzene stabilized by 300 ppm Ionol was added to each dried polymer sample by 30 A final concentration of mg / mL was obtained. A small glass stir bar was placed in each tube and the sample was heated to 160 ° C. for 2 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. Three Plgels placed in series as a mobile phase with 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. Pumped through a 10 micrometer (μm) Mix-B 300 mm × 7.5 mm column and heated to 160 ° C. The Polymer Labs ELS 1000 Detector was set to an evaporator set at 250 ° C., a nebulizer set at 165 ° C., and nitrogen set at 1.8 SLM at a pressure of 60 to 80 psi (400 to 600 kPa) N ₂ . Used with flow rate. 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 ™ software. Peaks were manually integrated and molecular weight information was recorded uncorrected against the polystyrene standard calibration curve.

Standard CRYSTAF  Way

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

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

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

The results of the differential scanning calorimetry were measured using a TAI model Q1000 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 Polymer Laboratories Model PL-210 or Polymer Laboratories Model PL-220 instruments. The column and carousel compartments were operated at 140 ° C. Three Polymer Laboratories 10-micron Mixed-B columns were used. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 g 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 was carried out using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures separated by at least 10 between individual molecular weights. Was performed. Standards were purchased from Polymer Laboratories, Shropshire, UK. Polystyrene standards were prepared in 0.025 g of 50 milliliters of solvent for molecular weights of 1,000,000 or more, and 0.05 g in 50 milliliters of solvent for molecular weights of 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 weights were 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 by flowing cooling water at 1.3 MPa for 1 minute. Compression molded films were used for optical measurements, tensile behavior, recovery and stress relaxation rates.

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

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

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

Mechanical properties-tensile, Hysteresis ( Hysteresis ) And Tear

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

100% and 300% hysteresis was measured from cyclic loading for 100% and 300% strain using ASTM D 1708 microtensile test specimens 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 on samples with 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 at 21 ° C. to 508 mm / min until the sample 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 then air quenched at 180 ° C. and 10 MPa molding pressure for 5 minutes. 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 compression molded discs that were 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, TR; Knobeloch, DC; Peat, IR; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym . Sci . , 20, 441-455 (1982), for analysis of elevated temperature 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 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 triad method (Randall, JC; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989)), which is incorporated herein by reference in its entirety. Comonomer incorporation was measured.

TREF Polymer fractionation by

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

Approximately 2000 ml portions of the eluate from the preparative TREF column were collected in 16 zones of heated fraction collector. The polymer was concentrated in each fraction using a rotary evaporator until about 50-100 ml of polymer solution remained. After 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 carried out 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.

Melt strength

Melt strength (MS) was measured using a capillary rheometer equipped with a 20: 1 die with a diameter of 2.1 mm and 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 Isopar from ExxonMobil Chemical Company. (Isopar) refers to a commercially available mixture of C _{6 -9} aliphatic hydrocarbons, available as E ^®. If a compound name does not match its structural representation herein, the structural representation is governed. The synthesis of all metal complexes and the 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

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 in 600 mL toluene To the solution of Zr (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: Long chain trialkylamines (Armeen ™ M2HT, Akzo-Nobel, Inc.) substantially 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 prepared according to Example 16, bis (tris (pentafluorophenyl) - aluminate only) -2-undecyl-mixing of the microporous Jolly DE C _{14 -18-alkyl} dimethyl ammonium salts.

Transfer agent : The transfer agent used was diethylzinc (DEZ, SA1), di (i-butyl) zinc (SA2), di (n-hexyl) zinc (SA3), triethylaluminum (TEA, SA4), trioctylaluminum ( SA5), triethylgallium (SA6), i-butylaluminum bis (dimethyl (t-butyl) siloxane) (SA7), i-butylaluminum bis (di (trimethylsilyl) amide) (SA8), n-octylaluminum di (Pyridine-2-methoxide) (SA9), bis (n-octadecyl) i-butylaluminum (SA10), i-butylaluminum bis (di (n-pentyl) amide) (SA11), n-octylaluminum bis (2,6-di-t-butylphenoxide) (SA12), n-octylaluminum di (ethyl (1-naphthyl) amide) (SA13), ethylaluminum bis (t-butyldimethylsiloxide) (SA14) , Ethylaluminum di (bis (trimethylsilyl) amide) (SA15), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide) (SA16), n-octylaluminum bis (2, 3,6,7-dibenzo-1-azacycloheptanamide) (SA17), n-octylaluminum bis (dimethyl (t-butyl) Include hydroxide (SA18), ethyl zinc (2,6-diphenyl-phenoxide) (SA19), and zinc acetate (t- butoxide) (SA20).

Example  1 to 4, Comparative example  A to C

General high throughput parallel polymerization conditions

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

Examples 1 to 4 show the products of a very narrow MWD, in particular monomodal copolymers, and also a broad molecular weight distribution of bimodal in the absence of DEZ (mixture of separately prepared polymers) when DEZ is present 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.

It is found that the polymers prepared according to the invention have a relatively narrow polydispersity (Mw / Mn) and higher block-copolymer content (trimers, tetramers or more) compared to polymers prepared in the absence of transfer agents. Can be.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Physical property testing

Polymer samples are evaluated for physical properties such as TMA temperature test, pellet block strength, hot recovery rate, hot compressive strain, and high temperature resistance exhibited by the storage modulus ratio (G '(25 ° C) / G' (100 ° C)). It was. 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 copolymer (The Dow Affinity® EG8100 available from Chemical Company, Comparative Example I ^* was a substantially linear ethylene / 1-octene copolymer (Affinity® PL1840 available from The Dow Chemical Company), and Comparative Example J ^* was hydrogenated Styrene / butadiene / styrene triblock copolymer (KRATON ™ G1652 available from KRATON Polymers) and Comparative Example K ^* is a thermoplastic vulcanizate (TPV, polyolefin with crosslinked elastomer dispersed) Blend). The results are shown in Table 4.

In Table 4, Comparative Example F ^* (which is a physical blend of two polymers resulting from co-polymerization with Catalysts A1 and B1) has a 1 mm penetration temperature of about 70 ° C., while Examples 5-9 are 100 It had a 1 mm penetration temperature of at least &lt; RTI ID = 0.0 &gt; 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 ^* (commercially available 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 was also a high temperature (80 ° C.) 300% deformation. Recovery failed during recovery (sample failure). Thus, the polymers exemplified had a unique combination of properties that could not be obtained even with some commercially available high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio (G '(25 ° C.) / G' (100 ° C.)) of 6 or less for the inventive polymers, while the physical blend (Comparative Example F ^* ) Shows that the storage modulus ratio is 9, and similar density random ethylene / octene copolymers (Comparative Example G ^* ) have a storage modulus ratio 89 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 in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrates that the polymers of the present invention have improved pellet blocking strength. In particular, Example 5 has a pellet blocking strength of 0 MPa, which means free flowing 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 recoverability). Good high temperature compression set (low values) is particularly necessary for applications such as gaskets, window profiles, o-rings, and the like.

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

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

Table 5 also shows that the inventive polymers are better (represented by higher shrinkage stress values) at 150% strain 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 at 500% of 150% strain (Example 11) to about 1100 kPa. (Example 17). Polymers with higher 150% shrinkage stress values will be very useful for elastic applications such as elastic fibers and fabrics, especially nonwovens. Other uses include diapers, hygiene and medical garment waistband articles such as tabs and elastic bands.

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

Optical testing

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

Extraction of Multiblock Copolymers

Extraction studies were performed on the polymers of Examples 5, 7 and Comparative Example E ^* . 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 7.

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

Continuous solution polymerization was carried out in a computer controlled sufficiently 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 with a mass flow controller. The temperature of the feed stream was controlled using a glycol cold heat exchanger prior to introduction into the reactor. The catalyst component solution was metered using a pump and a weight flow meter. The reactor was fully run at approximately 550 psig pressure. When leaving the reactor, water and additives were injected into the polymer solution. Water hydrolyzed the catalyst and terminated the polymerization reaction. The reactor solution was then heated in the production of two stage devolatilization. The solvent and unreacted monomers were removed during the devolatilization process. The polymer melt was injected into a die for cutting underwater pellets.

The description and results of the method are included in Table 8. Selected polymer properties are provided in Table 9.

Comparative example  L to P

Comparative Example L was f-PVC (that is, from Wofoo Plastics, Hong Kong, China), ie flexible poly (vinyl chloride). Comparative Example M was SBS copolymer, Vector ™ 7400 (obtained from Dexco Polymers, Houston, TX). Comparative Example N was a partially crosslinked TPV, VYRAM ™ TPV 9271-65 (obtained from Advanced Elastomer Systems, Akron, Ohio). Comparative Example O was a SEBS copolymer, KRATON ^® G2705 (obtained from Kraton Polymers's (Houston, Texas)). Comparative Example P was a SBS copolymer, KRATON ^® G3202 (obtained from Kraton Polymers's (Houston, Texas)).

Example  20 to 26

Example 20 was 100% Example 19f. Example 21 was similar to Example 20 except that 30% of Example 19f was replaced with High Density Polyethylene (HDPE), DMDA-8007 (from The Dow Chemical Company, Midland, Mich.). Example 22 was similar to Example 20 except that 20% of Example 19f was replaced with DMDA-8007. Example 23 was similar to Example 20 except that 10% of Example 19f was replaced with DMDA-8007. Example 24 was similar to Example 20 except that 30% of Example 19f was replaced with the homopolymer polypropylene, H700-12 (from The Dow Chemical Company, Midland, Mich.). Example 25 was similar to Example 20 except that 20% of Example 19f was replaced with H700-12. Example 26 was similar to Example 20 except that 10% of Example 19f was replaced with H700-12.

Comparative example  Q to X

Comparative Example Q was similar to Example 21 except that Example 19f was replaced with Polyolefin Elastomer, Engage ^® ENR 7380 (from DuPont Dow Elastomers, Wilmington, Delaware, USA). Comparative Example R was similar to Example 24 except that Example 19f was replaced with Engage ^® ENR 7380. Comparative Examples S, and is carried out except for Example 19f the (DuPont Dow Elastomer's (Delaware, USA of Wilmington material) from a) was replaced with a polyolefin elastomer, Playstation3 ^® ENR 8407 that the sample is 30 mil (0.762 mm) Thickness Similar to Example 20. Comparative Example T was similar to the Example 20 except that was replaced in Example 19f (DuPont Dow Elastomer's (Wilmington, Delaware, USA material) from a) a polyolefin elastomer, Playstation3 ^® ENR 8967. Comparative U was similar to Example 24 except that Example 19f was replaced with propylene-ethylene copolymer, Versipy ^® DE3300 (from The Dow Chemical Company, Midland, Delaware, USA). Comparative Example V was similar to Example 24 except that Example 19f was replaced with propylene-ethylene copolymer, Versipy ^® DE3400 (from The Dow Chemical Company, Midland, Delaware, USA). Comparative Example W was similar to Example 22 except that Example 19f was replaced with Versipy ^® DE3300. Comparative Example X was similar to Example 322 except that Example 19f was replaced with Versipy ^® DE3400.

Example  27 to 33

Example 27 was carried out in 56% Example 19f, 16% of H700-12, and 28% of the leno one (RENOIL) ^® 625 (butylene cut five days elbeo oil from Sony (Renkert Oil Elversony) (Pennsylvania, material)) Was a mixture of. Example 28 was similar to Example 27 except that the mixture was 33% Example 19f, 17% H700-12, and 50% Renoyl ^® 625. Example 29 was similar to Example 27 except that the mixture was 56% Example 19f, 16% DMDA-8007, and 28% Renoyl ^® 625. Example 30 was similar to Example 27 except the mixture was 33% Example 19f, 17% DMDA-8007, and 50% Renoyl ^® 625. Example 31 was similar to Example 27 except that the mixture was 17% of Example 19f, 16% of H700-12, 16% of Kraton ^® G2705 and 50% of Renault ^® 625. Example 32 except 1% Ampacet ^® 10090 (erucamide concentrate from Ampacet Corporation, Terrytown, NY) was added as a slip / antiblocking agent. Similar to Example 20. Example 33 was similar to Example 32 except that 5% Amphaset ^® 10090 was added as a slip / antiblocking agent.

Mechanical and physical property measurement

Thermomechanical (TMA), Hardness, Compressive Strain Properties, Flexural Modulus, Gull Wing Tear Strength, Vicat Softening Point, Blocking Properties, Scratch Flaw Resistance, Final Elongation of Comparative Examples L-X and Examples 20-33 Properties, 100% modulus, 300% modulus, final tensile strength, and yield strength were measured and the results are shown in Tables 10 and 11 below.

Penetration temperature techniques by thermal mechanical analysis (TMA) were performed on compression molded discs of 30 mm diameter x 3.3 mm thickness which were air quenched after molding at 180 ° C. and a molding pressure of 10 MPa. The machine used was a Perkin-Elmer TMA 7. In the TMA test, a 1.5 mm radius tip probe (P / N N519-0416) was applied to the surface of the sample disc with a force of 1N. The temperature was increased from 25 ° C. to 5 ° C./min. Probe penetration distance was measured as a function of temperature. The experiment was terminated when the probe penetrated 0.1 mm and 1 mm, respectively, in the sample. The 0.1 mm and 1 mm penetration temperatures of each example are listed in Table 10 below.

Shore D hardness of each sample was measured according to ASTM D 2240, incorporated herein by reference.

The compression set at 23 ° C. and 70 ° C. of each sample was measured according to ASTM D 4703, incorporated herein by reference.

Flexural modulus of each sample was measured according to the method described in ASTM D 790, which is incorporated herein by reference.

Gullwing tear strength of each sample was measured according to the method described in ASTM D 1004, which is incorporated herein by reference.

Vicat softening point of each sample was measured according to the method described in ASTM D 1525, incorporated herein by reference.

Blocking of each sample was measured by stacking each of the six 4 "X 4 'X 0.125" injection molded plaques, leaving the plaques at ambient conditions (73 F) for 24 hours, and then laminating the plaques. Blocking ratings are 1 to 5, 5 is good (all plaques are easily unlaminated) and 1 is unacceptable (six plaques are so sticky with each other that none of the plaques can be separated by hand) )to be

Scratch scratch resistance of each sample was measured by hand carving X from corner to corner using round plastic stylus on 4 × 4 × 0.125 inch plaques. Scratch scratch resistance ratings are 1 to 5, 5 is excellent (if no trace of X is visible) and 1 is unacceptable (if X is visible and cannot be rubbed off).

100% modulus, 300% modulus, final tensile strength, final elongation, and yield strength of each sample were measured according to ASTM D 412, incorporated herein by reference.

Comparative Examples L, M, N, O, and P are industrial flexible molded article resins which are not olefinic substrates. Examples 20-26 are various embodiments of the present invention that show an improved balance of low modulus and high top service temperature (as base resin or as a blend of PP and / or HDPE and base resin). Comparative Examples Q-X are industrial flexible molded article resins which are olefin substrates. Examples 20-26 show an improved balance of low modulus and high top service temperature compared to Comparative Examples Q-X.

SEBS Interpolymers of the Invention Blend

Blends of ethylene / α-olefin block copolymers and hydrogenated styrenic block copolymers (OBC / SEBS) were prepared using a Haake Rheomix 300 flow meter. The temperature of the sample vessel was set to 190 ° C. and the rotor speed was 40 rpm. After all ingredients were added, mixing was continued for about 5 minutes or until stable torque was established. Samples for further testing and evaluation were compression molded for 3 minutes with a Garver automatic press at 190 ° C. under a force of 44.45 kN. The molten material was then quenched at room temperature in an equilibrated press using an electronic cooling bath.

Comparative example Y1  To Y5

Comparative Examples Y1 is 100%, available from the Shell Chemical Company (Shell Chemical Company) (Houston, Texas), Kraton ^® G1652, a styrene-ethylene / butylene-styrene block copolymer was. Comparative Example Y1 was the same as Comparative Example J *. Comparative Example Y2 was of 75% of KRATON ^® G1652 and affinity ^® EG8100 25% of the blend. Comparative Example Y3 was a KRATON ^® G1652 and 50% and 50% blend of Affinity EG8100 ^®. Comparative Example Y4 was of 25% of KRATON ^® G1652 and affinity ^® EG8100 75% of the blend. Comparative Example Y5 was Affinity ^® EG8100 100%. Comparative Example Y1 was the same as Comparative Example H ^* ,

Example  34 to 45

Example 34 was 75% of KRATON ^® G1652 and 25% of Example 19a or polymers of the blend. Example 35 was of 50% KRATON ^® G1652 and 50% of Example 19a of the blend. Example 36 was 25% of KRATON ^® G1652 and 75% of Example 19a of the blend. Example 37 was identical to Example 19a. Example 38 was 75% of KRATON ^® G1652 and 25% of Example 19b of the blend. Example 39 was of 50% KRATON ^® G1652 and 50% of Example 19b of the blend. Example 40 was 25% of KRATON ^® G1652 and 75% of Example 19b of the blend. Example 41 was the same as Example 19b. Example 42 was 75% of KRATON ^® G1652 and 25% of Polymer 19i blend. Polymer 19i was an interpolymer prepared substantially similar to Examples 1-19 and Examples 19a-19h. Those skilled in the art will know how to adjust the treatment conditions, for example shuttle agent ratio, hydrogen flow, monomer concentration, etc., to produce the target polymer using the treatment conditions already described in the instant application. Example 43 was of 50% KRATON ^® G1652 and 50% of the polymer blend 19i. Example 44 was 25% of KRATON ^® G1652 and 75% of the polymer blend 19i. Example 45 was 100% of polymer 19i.

Mechanical and physical property measurement

Thermomechanical (TMA) properties, elastic recovery at 300% strain, elongation at break, tensile strength and Elmendorf tear strength of Comparative Examples Y1 to Y5 and Examples 34 to 45 were measured by methods described herein and known to those skilled in the art. The results are shown in Table 12 below.

The elastic recovery properties of exemplary blends (ie, Examples 34-45) and Comparative Examples Y1-Y5 in various amounts of SEBS (ie, Kraton ^® G1652) in the blend are shown in FIG. 8. Exemplary blends in various amounts of SEBS in the blend and the TMA temperatures of Comparative Examples 1-5 are shown in FIG. 9. As can be seen in Table 12 and FIGS. 8 and 9, exemplary blends (ie, Examples 34-45) exhibit improved heat resistance and elastic recovery properties compared to the corresponding Comparative Examples Y1-Y5.

HMS - HDPE / Interpolymers of the invention or HMS - PP Interpolymers of the Invention Blend

Comparative example Z1  To Z4

Comparative Example Zl was a polymer 19j of 100%. Polymer 19j was the ethylene / octene copolymer of the invention having a Zn level of 517 ppm, a density of 0.877 g / cc, and a melt index (I ₂ ) of 5. Comparative Example Z2 was 100% of polymer 19k. Polymer 19k was the ethylene / octene copolymer of the invention having a Zn level of 693 ppm, a density of 0.877 g / cc, and a melt index (I ₂ ) of 5. Comparative Example Z3 was 19 l of 100% of a polymer. Polymer 19l was an ethylene / octene copolymer of the invention having a density of 0.877 g / cc and a melt index (I ₂ ) of 30. Comparative Example Z4 was 19% of a polymer of 100%. Polymer 19m was an ethylene / octene copolymer of the invention having a Zn level of 255 ppm, a density of 0.866 g / cc, and a melt index (I ₂ ) of 5. Polymers 19j, 19k, 19l and 19m were prepared substantially similarly to Examples 1-19 and Examples 19a-19h. Those skilled in the art will know how to adjust the treatment conditions, for example shuttle agent ratio, hydrogen flow, monomer concentration, etc., to produce the target polymer using the treatment conditions already described in the instant application.

Example  46 to 57

Example 46 was 90% of the polymer 19m and 10% of a pro Fox ^® PF814 (Basel polyolefin's (HMS-PP from Elkton, Maryland material)) blend. Example 47 was of the 85% polymer and 15% of the 19m Pro Fox ^® PF814 blend. Example 48 was of the 95% polymer and 5% of the 19m Pro Fox ^® PF814 blend. Example 49 was of the 95% polymer 19j and 5% of a pro Fox ^® PF814 blend. Example 50 was a polymer of 90% 19j and 10% of the pro Fox ^® PF814 blend. Example 51 was a polymer of 85% 19j and 15% of a pro Fox ^® PF814 blend. Example 52 was of the 85% polymer and 15% of the 19k Pro Fox ^® PF814 blend. Example 53 was of the 90% polymer and 10% of the 19k Pro Fox ^® PF814 blend. Example 54 was a polymer of 95% 19k and 5% of a pro Fox ^® PF814 blend. Example 55 was of the 95% polymer and 5% of 19l Pro Fox ^® PF814 blend. Example 56 was of the 90% polymer and 10% of 19l Pro Fox ^® PF814 blend. Example 57 was a polymer of 85% 19l 15% of the pro Fox ^® PF814 blend.

80 ton Alblog (available from ARBURG GmbH + Co KG, Rosburg, Germany) after dry blending (if blended) Comparative Examples Z1 to Z4 and Examples 46 to 57 Arburg) were injection molded into 4 inch by 6 inch by 0.125 inch test plaques using a 370C injection molding machine. The mold had a polished smooth surface and used a cold runner through the fan gate. Molding conditions were kept constant at a total cycle time of 23 seconds (to test the resin's ability to solidify quickly).

Comparative Examples Z1 to Z4 and Examples 46 to 57 were injection molded into plaques or parts as described above, followed by a "parts stuck in mold" test, a "parts initially stuck together" test, Shore A hardness, "parts Quality "test and" aged part tack "test.

The "part pasted from mold" test included observing whether the molded part adhered to the mold surface and not ejecting from the mold. A "yes" grade is disadvantageous, meaning that the molded part does not stick to the mold and requires manual extraction. "No" is advantageous and means that the molded part does not stick to the mold and falls into the conveyor system without manual extraction. In the "parts initially glued together" test, two molded parts of each sample were placed on top of each other immediately after injection molding, and after applying acupressure, the molded parts were removed from each other. The amount of force required to remove the two parts from each other was measured. Each pair was rated from 3 (best, no stickiness, no force required to remove two samples) to 1 (lowest, excessive stickiness, much hand required to remove both samples). The molded parts were then collected and laid down for 24 hours. After 24 hours, Shore A hardness of each molded part was measured according to ASTM D2240, incorporated herein by reference. The average of two Shore A hardness records for each sample was recorded. In addition, each molded part was rated for "part quality" and "aged part tack". "Part quality" was rated from 5 (absolutely perfect parts without top, gaps, warpage, shrinkage) to 1 (lowest, excessive gaps, chopped parts, excessive shrinkage). "Aged component tack" was tested by placing two molded parts on top of each other, applying pressure and removing the parts from each other. The amount of force required to remove the two parts from each other was measured. Each pair was rated from 5 (best, no stickiness, no force required to remove both samples) to 1 (lowest, excessive stickiness, much hand required to remove both samples). The test results of Comparative Examples Z1 to Z4 and Examples 46 to 57 are shown in Table 13 below.

Test data in Table 13 is an ethylene / α- olefin interpolymer of the present invention (e. G., Polymer 19j, 19k, 19l, and 19m) HMS-PP and blends of these with the adhesive, and the hardness of each of the pro Fox ^® PF814 Indicates that it can be improved.

Some of the polymer blends disclosed herein can provide a better combination of moldability, attractive appearance, non-tackiness, and mechanical properties than any single component of the polymer blend. For example, Examples 21-26, which are polymer blends of polymer 19f and one or more other polymers, have better flexural modulus, tear than Comparative Examples M-P, which are not polymer 19f alone (ie, Example 20) or polymer blends. The balance of strength and 0.1 mm penetration temperature by TMA is shown. Similarly, polymers 19a, 19b, or a polymer blend containing 19i (i.e., Examples 34 to 36, 38 to 40 and 42 to 44) are Kraton ^® G1652, affinity ^® EG8100 or the corresponding Polymer 19a, 19b for a single Or 1 mm penetration temperature and elastic recovery rate by TMA better than 19i. Similarly, polymer blends comprising polymers 19j, 19k, 19l or 19m (ie, Examples 46-57) have better adhesion (i.e., lower adhesion) than the corresponding polymers 19j, 19k, 19l or 19m alone. And hardness (ie higher hardness).

As indicated above, embodiments of the present invention provide a variety of polymer blends having specific physical and mechanical properties suitable for the manufacture of shaped articles for various applications. The blend has a relatively low modulus while maintaining a relatively high heat resistance. This balance of properties makes the blend suitable for the manufacture of flexible molded articles. In addition, some blends show little or no adhesion at the surface.

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

Claims (22)

(i) at least one ethylene / α-olefin interpolymer, and (ii) one or more polyolefins, or one or more styrenic block copolymers, or combinations thereof, The ethylene / α-olefin interpolymer (a) Mw / Mn is from about 1.7 to about 3.5 and has at least one melting point (Tm) (degrees Celsius), and density (d) (g / cm ³ ), wherein the values of Tm and d correspond to the relationship do or, T _m ≥ -2002.9 + 4538.5 (d)-2422.2 (d) ² (b) the amount of delta (ΔT) in degrees Celsius, with Mw / Mn of about 1.7 to about 3.5, defined as the heat of fusion (ΔH) (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak; Characterized in that the value of ΔT and ΔH has the following relationship, ΔT> -0.1299 (ΔH) + 62.81 if ΔH is greater than 0 and less than or equal to 130 J / g ΔT ≥ 48 ° C when ΔH is greater than 130 J / g  (Where the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the cumulative polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C.), (c) 300% strain measured by compression molded film of ethylene / α-olefin interpolymer and elastic recovery rate (Re) (%) in one cycle, and density (d) (g / cm ³ ) When the ethylene / α-olefin interpolymer has substantially no crosslinked phase, the values of Re and d satisfy the following relationship, Re> 1481-1629 (d) (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 Molar content (wherein the comparative random ethylene interpolymer has the same comonomer as the ethylene / α-olefin interpolymer, and has a melt index, density, within 10% of the ethylene / α-olefin interpolymer, And comonomer molar content (based on total polymer)), (e) storage modulus at 25 ° C. (G ′ (25 ° C.)), and storage modulus at 100 ° C. (G ′ (100 ° C.)), wherein G ′ (25 ° C.) versus G ′ (100). C) ratio is about 1: 1 to about 10: 1 Polymer blends. The method of claim 1 wherein the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5, and has at least one melting point (Tm) (degrees C), and a density (d) (g / cm ³ ), Wherein said numerical values of Tm and d correspond to the following relationships. Tm ≥ 858.91-1825.3 (d) + 1112.8 (d) ² The method of claim 1 wherein the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5, and heat of fusion (ΔH) (J / g), and the highest DSC peak and the highest CRYSTAF peak, where the CRYSTAF peak is Delta amount (ΔT) (degrees Celsius), which is determined using at least 5% of the cumulative polymer and less than 5% of the cumulative polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C. Wherein the numerical values of ΔT and ΔH have the following relationship. ΔT> -0.1299 (ΔH) + 62.81 if ΔH is greater than 0 and less than or equal to 130 J / g ΔT ≥ 48 ° C when ΔH is greater than 130 J / g The ethylene / α-olefin interpolymers are characterized by a 300% strain and an elastic recovery rate (Re) (%) in one cycle as measured by a compression molded film of ethylene / α-olefin interpolymers, (d) A polymer blend having (g / cm ³ ) and 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) The polymer blend of claim 4 wherein the values of Re and d satisfy the following relationship.  Re> 1491-1629 (d) The polymer blend of claim 4 wherein the values of Re and d satisfy the following relationship. Re> 1501-1629 (d) The polymer blend of claim 4 wherein the values of Re and d satisfy the following relationship. Re> 1511-1629 (d) (i) at least one ethylene / α-olefin interpolymer, and (ii) one or more polyolefins, or one or more styrenic block copolymers, or combinations thereof, The ethylene / α-olefin interpolymer (a) at least one molecular fraction characterized by a TREF eluting at 40 ° C. to 130 ° C., having a block index of at least 0.5 and about 1 or less and a molecular weight distribution (Mw / Mn) of greater than about 1.3. Have, (b) a polymer blend having an average block index greater than 0 and less than or equal to about 1.0 and a molecular weight distribution (Mw / Mn) greater than about 1.3. The comparative random ethylene of claim 1 or 8, wherein the ethylene / α-olefin interpolymer has molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fractions are eluted at the same temperature range. Having a comonomer molar content of at least 5% higher than the comonomer molar content of the interpolymer fraction, wherein the comparative random ethylene interpolymer has the same comonomer as the ethylene / α-olefin interpolymer, Polymer blend, having a melt index, density, and comonomer molar content (based on total polymer) within 10% of the interpolymer. The ethylene / α-olefin interpolymers of claim 1 or 8 are characterized by a storage modulus at 25 ° C. (G ′ (25 ° C.)) and a storage modulus at 100 ° C. (G ′ (100 ° C.)). Wherein the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is about 1: 1 to about 10: 1. The process according to claim 1 or 8, wherein the α-olefins in the ethylene / α-olefin interpolymers are styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, Polymer blends that are 1-decene, 1,5-hexadiene, or combinations thereof. The polymer blend of claim 1 or 8, wherein the ethylene / α-olefin interpolymer is present in the range of about 5% to about 95% by weight of the total composition. The polymer blend of claim 1 or 8, wherein the polyolefin is an olefin homopolymer, an olefin copolymer, an olefin terpolymer or a combination thereof. The polyolefin of claim 13 wherein the polyolefin is a high melt strength polypropylene, a high melt strength high density polyethylene, ethylene / propylene copolymer, styrene-butadiene-styrene block copolymer, ethylene / propylene / diene terpolymer, styrene-ethylene-co- A polymer blend that is a (butene) -styrene block copolymer or a combination thereof. The polymer blend of claim 1 or 8 further comprising at least one additive. The additive of claim 15 wherein the additive is a slip agent, antiblocking agent, plasticizer, oil, antioxidant, UV stabilizer, colorant or pigment, filler, lubricant, antifogging agent, flow aid, coupling agent, crosslinker, nucleating agent, Polymer blends that are surfactants, solvents, flame retardants, antistatic agents or combinations thereof. A flexible molded article comprising the polymer blend of claim 1. 18. The vehicle door of claim 17, further comprising: toys, sacks, soft hand grips, bumper friction strips, floors, car floor mats, wheels, casters, furniture and appliance undercarriage, tags, seals, gaskets such as static and dynamic gaskets, car doors, Consisting of bumper strips, grill elements, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchenware, shoes, shoe bladders, shoe soles and combinations thereof Flexible molded article selected from the group. The polymer blend of claim 1 or 8 wherein the polyolefin is a polypropylene having a melt strength of at least 6 cN. The polymer blend of claim 1 or 8 wherein the polyolefin is a polypropylene having a melt strength of at least 10 cN. The polymer blend of claim 1 or 8 wherein the styrenic block copolymer is a styrene-butadiene-styrene block copolymer. The polymer blend of claim 1 or 8 wherein the styrenic block copolymer is a styrene-ethylene / butylene-styrene block copolymer.

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