KR20070117593A - Cap liners, closures and gaskets from multi-block polymers - Google Patents

Abstract

A polymer composition comprises at least an ethylene/alpha-oleiln interpolymer and at least one other polymer. The other polymer can be selected from a second ethylene/alpha-olefm interpolymer, an elastomer, a polyolefin, a polar polymer, and an ethylene/carboxylic acid interpolymer or ionomer thereof. The ethylene/alpha-olefm interpolymer is a block copolymer having at least a hard block and at least a soft block. The soft block comprises a higher amount of comonomers than the hard block. The block interpolymer has a number of unique characteristics disclosed here. Also provided are gaskets, bottle cap liners, and closures that comprise or obtained from a compositon comprising at least one ethylene/alpha-olefm interpolymer and at least one polyolefin. The gaskets are capable of compression sealing various containers, without contaminating the contents. Liquid containers particularly benefit from the use of the novel gasket materials disclosed herein.

Description

Cap liners, closures and gaskets from multiblock polymers {CAP LINERS, CLOSURES AND GASKETS FROM MULTI-BLOCK POLYMERS}

The present invention relates to a polymer blend composition comprising at least one ethylene / α-olefin polymer and a second polymer different from the ethylene / α-olefin polymer. In particular, the present invention relates to gaskets, cork closures and bottle cap liners comprising or obtainable from blend compositions.

Gaskets are made from various structural materials including polymers such as ethylene / vinyl acetate (EVA) and polyvinyl chloride (PVC). For example, US Pat. No. 4,984,703 discloses a plastic closure having a sealing liner comprising a blend of ethylene / vinyl acetate and a thermoplastic elastomer composition.

Depending on the environment of use, the gasket may have various properties. For example, in corrosive use conditions, the gasket is impermeable to the material but must have sufficient elasticity to form a seal. Gaskets used in the food and beverage sectors have similar requirements but should not contaminate foodstuffs. For example, if a gasket is used as a bottle cap closure liner and the closure is applied and removed (and / or resealed), the gasket maintains its integrity and does not tear or tear (stringing in the art) It is desirable that the pieces thereof do not contaminate the food product. In addition, the gasket or closure liner should not deform to such an extent that its seal integrity is lost. Depending on the type of food and / or liquid content, the filling temperature may be lower or higher than room temperature, thus placing greater requirements on the gasket.

There are a variety of gasket materials, but there is a continuing need for olefin polymers and olefin polymer compositions that are useful in the manufacture of gasket materials and do not adversely affect the taste and / or aroma of the product.

<Overview of invention>

The aforementioned requirements are met by various embodiments of the present invention. In some embodiments, the polymer blend composition is

(A) at least one ethylene / α-olefin interpolymer and (B) at least one other polymer different from the ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer is

(a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm 3), or

Wherein the numerical values of T _m and d correspond to the following relation:

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

(b) has a M _w / M _n of about 1.7 to about 3.5 and is characterized by a delta heat ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak Or

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 130 J / g)

ΔT ≥ 48 ° C (if ΔH is greater than 130 J / g),

CRYSTAF peak is measured using at least 5% of the cumulative polymer, and if less than 5% of the polymers have the same CRYSTAF peak, the CRYSTAF temperature is 30 ° C.)

(c) is characterized by a 300% strain and an elastic recovery rate Re (%) in one cycle, measured with a compression-molded film of an ethylene / α-olefin interpolymer, having a density d (g / cm 3), or

Wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinking phases:

Re> 1481-1629 (d))

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

(e) has a storage modulus G '(25 ° C.) at 25 ° C., and a storage modulus G' (100 ° C.) at 100 ° C., with a ratio of G ′ (25 ° C.) to G ′ (100 ° C.) being about 1 : 1 to about 9: 1, or

(f) having at least one molecular fraction eluted at 40 ° C. to 130 ° C. when fractionated using TREF, the fraction having a block index of at least 0.5 and about 1 or less, and a molecular weight distribution M _w / M _n of greater than about 1.3; Characterized by having, or

(g) an average block index greater than 0 and up to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3.

In the polymer composition, the other polymer is selected from second ethylene / α-olefin interpolymers, elastomers, polyolefins, polar polymers and ethylene / carboxylic acid interpolymers or ionomers thereof. When the other polymer is a second ethylene / α-olefin interpolymer, the two ethylene / α-olefin interpolymers in the polymer blend composition differ in comonomer content, molecular weight, structure, and the like. In addition, the two ethylene / α-olefin interpolymers may differ in melt index and / or overall density.

In some embodiments, the first ethylene / α-olefin interpolymer in the polymer blend composition is about 1% to about 99.5%, 5 to about 99.5%, 9 to 99.5%, 20 to about 80% or 10% to about 70% In the range of about 1% to about 99.5%, 5% to about 99.5%, 9% to 99.5%, 20% to about 80% or 10% to about 70 by the total weight of the composition. Present in an amount in the range of%.

The ethylene / α-olefin interpolymers used in the polymer blend compositions have processability similar to highly branched low density polyethylene (LDPE), but have the strength and toughness of linear low density polyethylene (LLDPE). However, ethylene / α-olefin polymers are significantly different from conventional Ziegler polymerized heterogeneous polymers (eg, LLDPE) and also different from conventional free radical / high pressure polymerized highly branched LDPE, and are metallocene or single site Different from the catalyzed polymer. The difference is understood to be due to the blocking properties of the interpolymer skeleton. That is, almost all interpolymer molecules (eg, due to more introduction of α-olefin comonomers) are segments of essentially linear monomers alternating with segments of highly short-chain branched ethylene / α-olefins (eg, , High density polyethylene with little or no short chain branching due to comonomer introduction). The blocking properties of the backbone give the copolymer a surprising performance in high temperature performance, particularly for beneficial properties such as wear resistance, and the copolymers are higher than conventional polyethylene and ethylene / α-olefin random interpolymers at the same or similar densities. It has a melting point. For example, block interpolymers useful in embodiments of the present invention having an overall density of about 0.9 g / cm 3 have a melting point of about 120 ° C., while Ziegler-Natta polymerized ethylene polymers (which typically have about the same density) (Named LLDPE) has a melting point of about 122 ° C., and random ethylene / alpha-olefin interpolymers (which are prepared using metallocene or single site catalysts) having approximately the same density have a melting point of about 90 ° C. Have

In some embodiments, the other polymer is an elastomer selected from thermoplastic vulcanizates, block copolymers, neoprene, functionalized elastomers, polybutadiene rubbers, butyl rubbers or combinations thereof. In some embodiments, the other polymer is a polyolefin selected from LDPE, LLDPE, HDPE, EVA, EAA, EMA, ionomers thereof, metallocene LLDPE, impact grade propylene polymer, random grade propylene polymer, polypropylene, and combinations thereof . In some embodiments, the other polymer is nylon, polyamide, ethylene vinyl acetate, polyvinyl chloride, acrylonitrile / butadiene / styrene (ABS) copolymer, aromatic polycarbonate, ethylene / carboxylic acid copolymer, acrylic and Polar polymers selected from combinations thereof. In other embodiments, other polymers include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-itaconic acid copolymers, ethylene methyl hydrogen maleate copolymers, ethylene-maleic acid copolymers, ethylene acrylic acid copolymers, Ethylene-Methacrylate Copolymer, Ethylene-Methacrylic Acid-Ethacrylate Copolymer, Ethylene-Itaconic Acid-Methacrylate Copolymer, Ethylene-Itaconic Acid-Methacrylate Copolymer, Ethylene-Methyl Hydrogen Maleate- Ethyl acrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid-vinyl alcohol copolymer, ethylene-acrylic acid-carbon monoxide copolymer, ethylene-propylene-acrylic acid copolymer, ethylene- Methacrylic acid-acrylonitrile copolymer, ethylene-fumaric acid-vinyl methyl ether copolymer, ethylene vinyl Chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinyl fluoride-methacrylic acid copolymer, ethylene-chlorotrifluorofluoroethylene-methacrylic acid Olefin / carboxylic acid interpolymers selected from copolymers and combinations thereof.

Polymer compositions include slip agents, antiblocking agents, plasticizers, antioxidants, UV stabilizers, colorants, pigments, fillers, lubricants, invincibles, flow aids, coupling agents, crosslinkers, nucleating agents, surfactants, solvents, flame retardants, antistatic agents, oils It may further include an additive selected from extenders, deodorants, barrier resins. The slip agent can be selected from polymethylsiloxanes, erucamides, oleamides, and combinations thereof. Extenders can be mineral oil, polybutenes, siloxanes, or combinations thereof. The deodorant may be calcium carbonate, activated carbon or a combination thereof. As used herein, the barrier resin can be selected from EVOH, PVDC, and combinations thereof.

Also provided are articles comprising a polymer composition. One exemplary article is a gasket comprising a composition provided herein. The ethylene / α-olefin interpolymers in the composition have exceptional combinations of properties that make them particularly useful for the gasket material comprising the composition. Preferably, the ethylene / α-olefin interpolymer is an ethylene / C ₃ -C ₂₀ alpha-olefin interpolymer. In some embodiments, the other polymer in the gasket comprises ethylene / carboxylic acid interpolymer or ionomer thereof in an amount of about 4% to about 12% by weight of the total composition. The ethylene / carboxylic acid interpolymer may have an acid content of about 3% to about 50% by weight of the interpolymer.

In some embodiments, the gasket comprises a primary amide formulation and a secondary amide formulation and comprise slip agents that together make up about 0.05% to about 5% by weight of the total composition. Primary amide formulations may be present at levels two or more times higher than secondary amide formulations. In some embodiments, the slip agent comprises a silane compound.

In other embodiments, the gasket is foamed using a blowing agent such as a physical blowing agent, a gas blowing agent, and a chemical blowing agent. Chemical blowing agents sodium bicarbonate, dinitrosopentamethylenetetramine, sulfonyl hydrazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, diisopropylhydrazodicarboxylate, 5 -Phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one, and sodium borohydride.

In other embodiments, the blowing agent is a gas blowing agent selected from the group consisting of carbon dioxide and nitrogen. In another embodiment, the blowing agent is pentane, hexane, heptane, benzene, toluene, dichloromethane, trichloromethane, trichloroethylene, tetrachloromethane, 1,2-dichloroethane, trichlorofluoromethane, 1,1, 2-trichlorotrifluoroethane, methanol, ethanol, 2-propanol, ethyl ether, isopropyl ether, acetone, methyl ethyl ketone and methylene chloride; Isobutane and n-butane, 1,2-difluoroethane.

In some embodiments, in the gasket provided herein the ethylene / α-olefin interpolymers constitute about 25 to 35 weight percent of the composition, the other polymer comprises about 55 to about 65 weight percent of the composition, and the slip agent comprises About 1 to about 3 weight percent of

In other embodiments, the gasket comprises a polymer composition provided herein having a static or kinetic coefficient of friction, or both, of less than about 1 or less than or equal to about 0.6.

In some embodiments, the composition has a melt index of at least about 5 g / 10 minutes and a compression set of less than 70% and 70 ° C., and a change in compression set at 23 ° C. to 70 ° C. is less than 55%.

In other embodiments, the gaskets provided herein comprise about 80 to about 97.5 weight percent of at least one ethylene / a-olefin interpolymer of the total weight of the composition; From about 2 to about 15 weight percent of at least one ethylene / carboxylic acid interpolymer or ionomer thereof and at least one slip agent, wherein the weight percentage of the two interpolymers is based on the total weight of the composition Include.

Further aspects of the invention and the features and characteristics of the various embodiments of the invention will be apparent from the following description.

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

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

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

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

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

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

General definition

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

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

The term "ethylene / α-olefin interpolymer" refers to a polymer having ethylene that accounts for most of the mole fraction of the total polymer. Preferably at least about 50 mol%, more preferably at least about 60 mol%, at least about 70 mol%, or at least about 80 mol% of the total polymer, with the remainder of the total polymer being at least one other comonomer Has For ethylene / octene copolymers, preferred compositions include an octene content of about 20 mol% or less. In some embodiments, the ethylene / α-olefin interpolymers do not include those produced in low yield or in small amounts or as a byproduct of a chemical process. The ethylene / α-olefin interpolymers may be blended with one or more polymers, but the resulting ethylene / α-olefin interpolymers are substantially pure and are often included as a major component of the reaction product of the polymerization process.

Ethylene / α-olefin interpolymers are polymerized forms characterized by multiblocks (ie, two or more) or segments of two or more polymerized monomer units (preferably multiblock copolymers) that differ in chemical or physical properties. Ethylene and at least one copolymerizable α-olefin comonomer. In some embodiments, the multiblock copolymer can be represented by the following formula.

(AB) _n

Wherein n is an integer of at least 1, preferably at least 2, for example 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or Above, "A" represents a hard block or segment, and "B" represents a soft block or segment)

Preferably, A and B are crosslinked in a linear manner, not in a branched or starred manner. A "hard" segment represents a block of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, preferably greater than about 98 weight percent, based on the weight of the polymer. In other words, the comonomer content (monomer content other than ethylene) of the hard segment is less than about 5 weight percent, and preferably less than about 2 weight percent, based on the weight of the polymer. In some embodiments, the hard segments comprise all or substantially all ethylene. In contrast, a “soft” segment is a block of polymerized units having a comonomer content of greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, and greater than about 15 weight percent, based on the weight of the polymer. Indicates. In some embodiments, the comonomer content of 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.

In some embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymer typically does not have the following structure.

AAA- AA-BBB- BB

In other embodiments, the block copolymers usually do not have a third type of block comprising different copolymer (s). In another embodiment, each of block A and block B has monomers or comonomers distributed substantially randomly within the block. In other words, neither block A nor block B contain two or more sub-segments (or sub-blocks), eg, tip segments, of separate compositions, and have a different composition than the rest of the block.

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

The term “multiblock copolymer” or “segmented copolymer” is preferably a polymer comprising two or more chemically distinct regions or segments connected in a linear manner, ie polymerized ethylene functional groups rather than pendant or grafted modes. Reference is made to polymers comprising end-to-end linked chemically differentiated units. In a preferred embodiment, the block comprises the amount or type of comonomer incorporated therein, the density, the amount of crystallization, the microcrystalline size attributable to the polymer of this composition, the type or degree of tacticity (isotactic or syn Different amounts, homogeneity, or any other chemical or physical property of branching, including diotactic), regio-regular or site-irregularity, long chain branching or hyper-branching. Multiblock copolymers are characterized by the distribution of specific polydispersity indices (PDI or M _w / M _n ), block length distribution and / or block number distribution due to specific copolymer preparation methods. More specifically, when produced in a continuous process, the polymer 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.

The term “polar polymer or“ polar interpolymer ”refers to a polymer comprising at least one polar monomer, which is described by Smith, CP, Dielectric Behavior and Structure, McGraw-Hill Book Company, Inc., New York ( 1955) is a polymerizable ethylenically unsaturated compound having a polar group having a moment of group in the range of about 1.4 to about 4.4 Debye units .. Exemplary polar groups are -CN, -NO _2- , OH, -Br, -Cl , -NH ₂ , --C (O) OR and -OC (O) R, wherein R is alkyl or aryl Preferably, the polar monomers are acrylonitrile, methacrylonitrile and fumaronitrile And alkyl esters of α, β-ethylenically unsaturated acids, such as alkyl acrylates and methacrylates, methyl acrylate, butyl acrylate and methyl methacrylate, with acrylonitrile and methyl methacrylate being most preferred. .

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 falling within the range is specifically disclosed. In particular, the following numerical values within this 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%) . In addition, any numerical range defined by the two R values defined above is also specifically disclosed.

Embodiments of the present invention provide various polymer blend compositions and gaskets, bottle cap liners, and closures made therefrom. The polymer composition comprises at least one ethylene / α-olefin interpolymer and at least one other polymer different from the ethylene / α-olefin interpolymer. Other polymers can be second ethylene / α-olefin interpolymers, elastomers, polyolefins, polar polymers, and ethylene / carboxylic acid interpolymers or ionomers thereof. When the other polymer is a second ethylene / α-olefin interpolymer, the two ethylene / α-olefin interpolymers in the polymer blend composition are different. Polymer blends have inherent physical and mechanical properties suitable for making shaped articles for various applications. Preferably the ethylene / α-olefin interpolymer is a multiblock copolymer comprising at least one soft block and at least one hard block. In some embodiments, the blend has a relatively low modulus and maintains relatively high heat resistance. This balance of properties produces blends suitable for making flexible molded articles. Molded articles shall have an upper limit of service temperature of at least 40 ° C, at least 50 ° C, at least 60 ° C, at least 80 ° C or at least 90 ° C.

The term “different” when referring to two polymers means that the two polymers differ in composition (such as monomer or comonomer type, monomer or comonomer content, etc.), structure, properties or combinations thereof. Two polymers are also considered different if they have different molecular weights, even if they are of the same structure and composition. Conversely, if two polymers have different structures, they are considered different even if they have the same composition and molecular weight. For example, homogeneous ethylene / octene copolymers made with metallocene catalysts differ from heterogeneous ethylene / octene copolymers made with Ziegler-Natta catalysts, even though they have the same comonomer content and molecular weight. In addition, the two ethylene / α-olefin interpolymers may differ in melt index and / or overall density.

Some gaskets must withstand temperatures above room temperature (about 25 ° C.) for a short time, especially when the field is “hot fill” fields. For example, a pasteurized product should have a gasket with a melting point above 100 ° C. Since the ethylene / α-olefin interpolymers described below have an inherent melting point-density relationship, such interpolymers with a wide range of densities can be used to make gaskets. Unlike homogeneously branched linear or homogeneously branched substantially linear olefin polymers having low melting points as the density decreases, the ethylene / α-olefin interpolymers used in embodiments of the present invention have a melting point that is substantially independent of density. Has

The density of the ethylene / α-olefin interpolymers used in embodiments of the present invention is measured according to ASTM D-792 and is generally from about 0.85 g / cm 3 to about 0.96 g / cm 3, preferably from about 0.87 g / cm 3 to about 0.92 g / cm 3, and in particular about 0.89 g / cm 3 to about 0.915 g / cm 3.

The Food and Drug Administration (FDA) currently limits the hexane extract to polypropylene in contact with food to no more than 5.5%. The method is described in FDA regulation 21 CFR Ch. 1 (Apr. 1, 1994 Edition) §177.1520, pages 252-253. Although the molecular weight distribution affects the hexane extract, large amounts of comonomers produce higher levels of hexane extracts, especially for non-uniform polyethylene copolymers. For example, heterogeneous ethylene / 1-octene linear polyethylenes having a density of about 0.9017 to 0.91 g / cm 3 generally have greater than 5% hexane extract. In contrast, the ethylene / 1-octene copolymers described below, having a density as low as at least about 0.8976 g / cm 3, have a hexane extract of less than 5%, preferably less than about 4%, and especially less than about 2%.

Ethylene / α-olefin Interpolymers

The ethylene / α-olefin interpolymers (also called “interpolymers of the invention” or “polymers of the invention”) used in the present invention are multiblocks or segments of two or more polymerized monomers having different chemical or physical properties ( Block interpolymers) (preferably multiblock copolymers) and polymerized forms of ethylene and at least one copolymerizable α-olefin copolymer. The ethylene / α-olefin interpolymers are characterized by one or more of the embodiments described below.

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

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

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

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

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

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

ΔT> -0.1299 (ΔH) + 62.81,

Preferably ΔT ≧ −0.1299 (ΔH) +64.38,

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

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

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

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

Re> 1481-1629 (d);

Preferably Re ≧ 1491-1629 (d);

More preferably Re ≧ 1501-1629 (d);

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

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

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

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

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

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

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

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

Comonomer content can be measured using any suitable technique using techniques based on preferred nuclear magnetic resonance ("NMR") spectroscopy. In addition, in the case of polymers or blends of polymers having a relatively wide TREF curve, first the TREF is used to fractionate the polymers into fractions each having an elution temperature range of 10 ° C. or less. That is, each eluted fraction has a collection temperature window of 10 ° C. or less. 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 polymerized forms of ethylene and one or more copolymerizable comonomers and having different chemical or physical properties ( That is, olefin interpolymers (blocked interpolymers) characterized by two or more blocks) or segments, most preferably multiblock copolymers, which block elution (individual fractions) which elute at 40 ° C. to 130 ° C. Collected and / or not isolated) peaks (not molecular fractions only), which peaks have comonomer content predicted by infrared spectroscopy at development using full width at half maximum (FWHM) area calculations, and average comonomer moles Average porosity of comparative random ethylene interpolymer peaks at the same elution temperature, with content developed using full width at half maximum (FWHM) area calculation Higher than the body molar content, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer has the same comonomer (s) as the blocked interpolymer and has a melt index, density and The comonomer molar content (based on the total polymer) is characterized by being within 10% of the block interpolymer. Preferably, M _w / M _n of the comparative interpolymer is also within 10% of M _w / M _n of the blocked interpolymer, and / or the total comonomer content of the comparative interpolymer is 10 in the case of block interpolymers. It is within%. The full width at half maximum (FWHM) calculation is based on the ratio of methyl to methylene reaction area [CH ₃ / CH ₂ ] from the ATREF infrared detector, where the highest (maximum) peak is identified from the baseline and thus the FWHM area is determined. In the distribution measured using the ATREF peak, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T ₁ and T ₂ are horizontal lines to the baseline after dividing the ATREF peak height by 2 (ATREF Traversing the left and right sides of the curve) to determine the left and right sides of the ATREF peak. A calibration curve for comonomer content is obtained by plotting the FWHM area ratio of comonomer content from NMR to TREF peak using a random ethylene / α-olefin copolymer. In this infrared method, a calibration curve is obtained for the same comonomer type of interest. The comonomer content of the TREF peak of the polymer of the present invention is measured with reference to the calibration curve as described above using the FWHM methyl: methylene area ratio [CH ₃ / CH ₂ ] of its TREF peak.

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

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

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

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

In addition to the foregoing aspects and properties described herein, the polymers of the present invention may be characterized as having one or more additional features. In one aspect, the polymers of the present invention preferably comprise ethylene and at least one copolymerizable comonomer in polymerized form and are characterized by a plurality of blocks or segments having at least two polymerized monomer units having different chemical or physical properties. Olefin interpolymers (blocked interpolymers), most preferably multiblock copolymers, wherein the block interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments. The 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% Above, wherein the comparative random ethylene interpolymer contains the same comonomer (s) as the blocked interpolymer. And preferably it characterized in that less than 10 percent 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, in the case of a copolymer in which M _w / M _n of the comparative interpolymer is also within 10% of M _w / M _n of the blocked interpolymer, and / or the total comonomer content of the comparative interpolymer is blocked Within 10%.

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

Preferably such interpolymers of ethylene and at least one alpha-olefin, in particular interpolymers having a total polymer density of from about 0.855 to about 0.935 g / cm 3, more specifically polymers having more than about 1 mol% comonomer In order to achieve this, the block interpolymer is at least (-0.2013) T + 20.07, more preferably at least (-0.2013) T + 21.07 (where T is the numerical value of the peak elution temperature of the TREF fraction measured and measured in ° C.). Comonomer content of the TREF fraction eluted at 40-130 ° C.

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

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

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

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

Measured by an infrared detector ATREF  peak Comonomer  Furtherance

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

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

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

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

The application of infrared spectroscopy to determine the comonomer content of polymers in this ATREF-infrared method is in principle similar to that of the GPC / FTIR system as described in the following references: Markovich, Ronald P .; Hazlitt, Lonnie G .; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers", Polymeric Materials Science and Engineering (1991), 65, 98-100 .; And Deslauriers, P. J .; Rohlfmg, 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 other embodiments, the ethylene / α-olefin interpolymers are characterized by an average block index (ABI) of greater than 0 and up to about 1.0, and a molecular weight distribution (M _w / M _n ) of greater than about 1.3. The average block index (ABI) is the 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.

Where T _X is the preparative ATREF elution temperature (preferably expressed in Kelvin) for the i-th fraction and P _X is the ethylene mole fraction for the i-th fraction, which can be measured by NMR or IR as follows. 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). As a first approximation, where the actual values for the "hard segments" are not available, the T _A and P _A values are set to the values 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 elution temperature for the random copolymer having the same composition (ethylene mole fraction is P _AB ) and molecular weight as the copolymer of the present invention. T _AB can be calculated using the following equation.

Ln P _AB = α / T _AB + β

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

Ln P = -237.83 / T _ATREF + 0.639

T _XO is the ATREF temperature for a random copolymer having the same composition (ie, the same comonomer type and content) and the same molecular weight and whose ethylene mole fraction is P _X. T _XO can be calculated from LnP _X = α / T _XO + β by the P _X mole fraction measurement. Conversely, P _XO is the ethylene mole fraction for a random copolymer having the same composition (ie, the same comonomer type and content) and the same molecular weight, and the ATREF temperature is T _X , which is determined using the T _X measurement using Ln P _XO = It can be calculated from α / T _X + β.

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

Another feature of the ethylene / α-olefin interpolymers of the present invention is that the ethylene / α-olefin interpolymers of the present invention have at least one polymer having a block index greater than about 0.1 up to about 1.0, which can be obtained by preparative TREF. Including a fraction, wherein the molecular weight distribution (M _w / M _n ) of the polymer is greater than about 1.3. In some embodiments, the polymer fraction has a block index greater than about 0.6 and up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In another embodiment, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0.5, or greater than about 0.4 and up to about 0.5. In another embodiment, the polymer fraction has a block index greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0.7, or greater than about 0.5 and up to about 0.6.

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

In addition, the polymers of the present invention have a storage modulus (G ′) at a temperature of 100 ° C. of which log (G ′) is at least 400 kPa, preferably at least 1.0 MPa, alone or in combination with any other properties. Can be. In addition, the polymers of the present invention have a relatively uniform storage modulus as a function of temperature in the range from 0 to 100 ° C. (shown in FIG. 6), which is a property of the block copolymers, which means that olefin copolymers, in particular ethylene and at least one C _The copolymer of _3-8 aliphatic α-olefins has not been known so far. (In this context, the term "relatively uniform" means that the log G '(Pa) is reduced to less than one digit range at 50 to 100 ° C, preferably 0 to 100 ° C.)

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

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

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

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

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

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

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

It comprises contacting with a catalyst composition comprising a.

Representative catalysts and chain transfer agents are as follows.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Suitable nonconjugated diene monomers may be straight, branched or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable nonconjugated dienes include straight chain acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes such as 5 -Methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyriene and dihydrooxyene, monocyclic alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and multicyclic alicyclic conjugated and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- ( 2,2,1) -hepta-2,5-diene; Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene Butene, 5-vinyl-2-norbornene and norbornadiene. Among the dienes typically used for EPDM preparation, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB ), 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

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

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

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

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

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

The amount of 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.

Second polymer

As discussed above, the second polymer component provided herein is included. The second polymer component is different from the ethylene / α-olefin interpolymer as the first polymer component. The second polymer may be a different ethylene / α-olefin interpolymer, polyolefin, polar polymer, elastomer, and the like. If a second ethylene / α-olefin interpolymer is used, the two ethylene / α-olefin interpolymers in the blend have different melt index, comonomer type, comonomer content and / or overall density. The amount of the second ethylene / α-olefin interpolymers in the polymer blends disclosed herein can be from about 5 to about 99.5 weight percent, from about 9 to about 99.5 weight percent, from about 10 to about 90 weight percent, from about 20 to about the total weight of the polymer blend. About 80%, about 30 to about 70%, about 10 to about 50%, about 50 to about 90%, about 60 to about 90%, or about 70 to about 90% by weight.

Bimodal physical blends of two ethylene / a-olefin interpolymers or blends in reactors have improved properties (e.g. compression set) and processability than single distribution ethylene / a-olefin interpolymers of the same melt index To provide.

Polyolefin

The polymer blend can include one or more polyolefins that can improve or modify the properties of the ethylene / α-olefin interpolymers. Polyolefins are polymers derived from one or more olefins. Olefins (ie, alkenes) are hydrocarbons containing one or more carbon-carbon double bonds. Some non-limiting examples of olefins include linear or branched, cyclic or bicyclic, alkenes having from 2 to about 20 carbon atoms. In some embodiments, alkenes have 2 to about 10 carbon atoms. In other embodiments, the alkenes contain two or more carbon-carbon double bonds, 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.

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

In some embodiments, the polyolefin is selected from LDPE, LLDPE, HDPE, EVA, EAA, EMA, ionomers thereof, metallocene LLDPE, impact grade propylene polymers, random grade propylene polymers, polypropylene, and combinations thereof.

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

Elastomer

In certain embodiments, the polymer blends provided herein comprise one or more thermoplastic vulcanizates (TPV), styrene block copolymers (e.g., BS, SEBS, SEEPS, etc.), neoprene, Engage®, AFFINITY , (Registered trademark), flexomer (trade name), VERSIFY (registered trademark), VistaMAXX (trade name), Exact (trade name), Exceed (trade name), functionalized elastomer (MAHg) , Silane modified, azide modified) polybutadiene rubber, butyl rubber or combinations thereof. The elastomer may be present in an amount ranging from about 1% to about 95%, about 5% to about 91%, about 10% to about 80%, or about 20% to about 50% of the total weight of the composition.

Thermoplastic elastomers, unlike conventional vulcanized rubbers, are rubbery materials that can be processed and reused, such as thermoplastics. If the thermoplastic elastomer contains vulcanized rubber, it may also be called thermoplastic vulcanizate (TPV). TPV is a thermoplastic elastomer that has a chemically crosslinked rubbery phase and is produced by dynamic vulcanization. The measurement of the rubber behavior will be stretched to twice the original length at room temperature and held for 1 minute before release, after which the material will shrink to less than 1.5 times the original length in one minute (ASTM D1566). Another measurement is found in ASTM D412 for the measurement of tension sets. The material is also characterized by high elastic recovery, which indicates a recovery rate after deformation and can be quantified as a recovery percentage after compression. Perfect elastic materials have a recovery rate of 100%, but perfect plastic materials do not have elastic recovery. Another measure is found in ASTM D395 for compressive strain measurements.

Thermoplastic vulcanizates containing butyl or halogenated butyl rubber as the rubber phase and thermoplastic polyolefins as the plastic or resin phase may be vulcanized with a mixture of polyurethane and chlorosulfonated polyethylene or chlorosulfonated polyethylene and chlorinated polyethylene. Dynamic vulcanization, containing% polyurethane and about 70-30% chlorosulfonate polyethylene or chlorosulfonated polyethylene and chlorinated polyethylene, wherein the ratio of chlorosulfonated polyethylene to chlorinated polyethylene is from about 3: 1 to 1: 3. Is manufactured by. Examples of thermoplastic vulcanizates include ethylene-propylene monomer rubber and ethylene-propylene-diene monomer rubber thermosets distributed in a crystalline polypropylene matrix.

One example of commercially available TPV is a mixture of SAtoprene® thermoplastic rubbers manufactured by Advanced Elastomer Systems and crosslinked EPDM particles in a crystalline polypropylene matrix. Another example is VYRAM, which consists of a mixture of polypropylene and natural rubber and is sold by Advanced Elastomer Systems. Other suitable elastomers are KRATON, a brand of styrene block copolymers (SBC) sold by Shell, and DYNAFLEX G 6725 (brand, thermoplastic elastomers sold by GLS), and Made of Kraton (brand) polymer).

Styrene block copolymer

In some embodiments, the polymer composition provided herein comprises one or more block copolymers. Block copolymers include block copolymers comprising one or more styrene block copolymers. The amount of styrene 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, and about 30 to about the total weight of the polymer blend. About 70%, about 5 to about 50%, about 50 to 95%, about 10 to about 50%, about 10 to about 30%, or about 50 to about 90% by weight. In some embodiments, the styrene block copolymer 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.

Generally speaking, the styrene block copolymer comprises two polystyrene blocks, preferably saturated polybutadiene blocks separated by two or more monoalkenyl arene blocks, preferably blocks of saturated conjugated dienes. Although branched or radial polymers or functionalized block copolymers produce useful compounds, preferred styrene block copolymers have a linear structure. The total number average molecular weight of the styrene block copolymer is preferably about 30,000 to about 250,000 if the copolymer has a linear structure. Such block copolymers may have an average polystyrene content of 10% to 40% by weight.

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

<Formula I>

A-B-R (-B-A) _n

or

<Equation II>

A _x- (BA-) _y -BA

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 the remainder 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 the production of useful block copolymers with unsaturated rubber monomer units include lithium-based catalysts, in particular lithium-alkyl. U. S. Patent 3,595, 942 describes a suitable method for the hydrogenation of block copolymers with unsaturated rubber monomers to form block copolymers with saturated rubber monomer units. The structure of the polymer is measured by their polymerization method. For example, linear polymers can be prepared by the sequential introduction of the desired rubber monomer into the reactor vessel when using an initiator such as lithium-alkyl or dithiostilbene or the like, or by coupling two segment block copolymers with a bifunctional coupling agent. Is generated. Branched structures, on the other hand, can be obtained by the use of suitable coupling agents having functionality on block copolymers having three or more unsaturated rubber monomer units. Coupling can be carried out with dihaloalkanes or polyfunctional coupling agents such as alkenes and divinylbenzenes, as well as esters of monohydric alcohols with certain polar compounds, for example silicon halides, siloxanes or carboxylic acids. The presence of any coupling moiety in the polymer can be ignored for a suitable 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 ), α-methylstyrene-butadiene-α-methylstyrene and α-methylstyrene-isoprene-α-methylstyrene.

The styrene portion of the block copolymer is preferably a polymer or interpolymer of styrene with analogs and homogeneous, 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 having unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene or they may comprise copolymers of one or both of the two dienes having small amounts of 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 having saturated rubber monomer units include one or more segments of styrene-based units and one or more segments of ethylene-butene or ethylene-propylene copolymers. Preferred examples of such block copolymers having 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.

The hydrogenation of block copolymers having unsaturated rubber monomer units is preferably nickel or cobalt carboxylate or under conditions that substantially hydrogenate at least 80% of the aliphatic double bonds while at least 25% of the styrenic aromatic double bonds are hydrogenated. By the use of a catalyst comprising the reaction product of an aluminum alkyl compound having an alkoxide. Preferred block copolymers are those in which at least 99% of the aliphatic double bonds are hydrogenated while 5% of the aromatic 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 of the styrenic block segment and 90 to 65 weight percent of the rubber monomer block segment based on the total weight of the block copolymer.

The average molecular weight of the individual blocks can vary within certain limits. In most instances, the styrene block segments will have a number average molecular weight in the range of 5,000 to 125,000, preferably 7,000 to 60,000, while the rubber monomer block segments range from 10,000 to 300,000, preferably 30,000 to 150,000. It will have an average molecular weight. The total average molecular weight of the block copolymers 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 according to embodiments of the present invention can be modified by any method well known in the art, for example, by grafting small amounts of functional groups such as maleic anhydride. .

Suitable block copolymers are Kraton ™ supplied by KRATON Polymers LLC, Houston, TX, USA, and Dexco Polymer, L. P., Houston, TX, USA. And commercially available ones such as Vector (VECTOR, trade name) supplied by Polymers, LP).

Polar polymer

In some embodiments, the polymer composition provided herein comprises one or more polar polymers. Polar polymers refer to thermoplastics, elastomers and heat-curable polymers having, or in other words, permanent dipole moments, resulting from polymerization by polyaddition or polycondensation. By way of example of such polar polymers, halogenated polymers such as vinyl chloride, vinylidene chloride and vinyl bromide polymers (homo- and copolymers), nitrile functional group containing polymers such as polyacrylonitrile and acrylonitrile / Styrene copolymers or acrylonitrile / butadiene / styrene (ABS) copolymers, cellulosic polymers, polyketones, aliphatic and aromatic polyesters, for example polymethyl or polyethyl acrylate and methacrylate and polyethylene terephthalate, Vinyl alcohol / ethylene copolymer (ie, o represents a vinyl acetate / ethylene copolymer wherein at least 90% of the acetate groups are converted to hydroxyl groups by hydrolysis or alcoholysis), aromatic polycarbonates, polyamides or Polywoo, which is both nylon, and also well-known polymers Mention may be burnt. In some embodiments, the polar polymer is nylon, polyamide, ethylene vinyl acetate, polyvinyl chloride, acrylonitrile / butadiene / styrene (ABS) copolymer, aromatic polycarbonate, ethylene / carboxylic acid copolymer or acrylic . The polar polymer may be present in the range of about 0.25% to about 90%, 1% to about 80%, 10% to about 50%, or 10% to about 40% by total weight of the blend.

In certain embodiments, the polar polymer in the polymer blend composition is an oleolefin / carboxylic acid interpolymer. Suitable carboxylic acid monomers include ethylenically unsaturated carboxylic acid monomers having 3 to 8 carbon atoms per molecule, alkyl esters, half esters, and the like, including anhydrides. Examples of ethylenically unsaturated carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, maleic acid and anhydrides, itaconic acid, fumaric acid, crotonic acid, citraconic acid and anhydrides, methyl hydrogen maleate, ethyl hydrogen maleate, and the like. It doesn't work. In addition, ethylenically unsaturated monomers other than hydrocarbons in total may also be used to prepare the interpolymers. Examples of this monomer include, but are not limited to, esters of ethylenically unsaturated carboxylic acids such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, isobutyl acrylate and methyl fumarate . They are also unsaturated esters of non-polymerizable carboxylic acids such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl halides such as vinyl and vinylidene chloride, vinyl esters, ethylenically unsaturated amides and nitriles, For example acrylamide, acrylonitrile, methacrylonitrile and fumaronitrile.

The olefin monomer should be present in the interpolymer in an amount of about 60% to about 90% by weight. The ethylenically unsaturated carboxylic acid monomer should be present from about 5 wt% to about 25 wt% interpolymer. Another type of ethylenically unsaturated carboxylic acid monomer may be present at 0 to about 20 weight percent of the interpolymer. The aforementioned interpolymers can be prepared by the methods and procedures described in US Pat. Nos. 3,436,363, 3,520,861, 4,599,392, and 4,988,781. The disclosure of this patent is incorporated herein by reference in its entirety. Those skilled in the art will appreciate that the properties of the polymer can be tailored by adjusting various parameters, for example the reaction time, temperature and pressure of the polymerization process or procedure. One parameter that can be adjusted to adjust the melt index of the polymer is hydrogen concentration. Higher hydrogen concentrations tend to produce polymers with higher melt indices, although these relationships are not necessarily linear.

Suitable interpolymers may be produced from non-acidic polymers preformed by subsequent chemical reactions carried out thereon. For example, carboxylic acid groups can be supplied by grafting acrylic acid or maleic acid to a polymer substrate, for example ethylene. In addition, interpolymers containing carboxyl anhydride, ester, amide, acyl halide and nitrile groups can be hydrolyzed to carboxylic acid groups.

In addition, the interpolymers can be modified by the methods described in US Pat. No. 5,384,373, which is incorporated herein by reference in its entirety. The resulting modified interpolymers can be used in embodiments of the present invention. α-methyl styrene, toluene, t-butyl styrene and the like. Suitable ethylenically unsaturated carboxylic acid monomers have 3 to 8 carbon atoms per molecule and include anhydrides, alkyl esters, half esters and the like. Examples of ethylenically unsaturated carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, maleic acid and anhydrides, ataconic acid, fumaric acid, crotonic acid, citraconic acid and anhydrides, methyl hydrogen maleate, ethyl hydrogen maleate, and the like. Do not. In addition, ethylenically unsaturated monomers other than hydrocarbons in total may also be used to produce the interpolymers. Examples of such monomers include, but are not limited to, ethylenically unsaturated carboxylic acids such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, isobutyl acrylate, and methyl fumarate. They are also unsaturated esters of non-polymerizable carboxylic acids such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl halides such as vinyl and vinylidene chloride, vinyl esters, ethylenically unsaturated amides and nitriles And, for example, acrylamide, acrylonitrile, methacrylonitrile and fumaronitrile.

Specific examples of olefin / carboxylic acid interpolymers include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-itaconic acid copolymers, ethylene-methyl hydrogen maleate copolymers, ethylene-maleic acid copolymers, ethylene acrylic acid Copolymer, Ethylene-Methacrylate Copolymer, Ethylene-Methacrylic Acid-Ethacrylate Copolymer, Ethylene-Itaconic Acid-Methacrylate Copolymer, Ethylene-Itaconic Acid-Methacrylate Copolymer, Ethylene-Methyl Hydrogen Male Eight-ethyl acrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid-vinyl alcohol copolymer, ethylene-acrylic acid-carbon monoxide copolymer, ethylene-propylene-acrylic acid copolymer, Ethylene-methacrylic acid-acrylonitrile copolymer, ethylene-fumaric acid-vinyl methyl ether copolymer, ethylene-vinyl Chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinyl fluoride-methacrylic acid copolymer and ethylene-chlorotrifluoroethylene-methacrylic acid Include coalescing.

Ionomers of olefin / carboxylic acid interpolymers generally contain copolymers containing pendant acid groups, for example carboxylic acid groups, with ionic metal compounds, for example groups I, II, IV-A and VIIIB of the Periodic Table of Elements. Ionically crosslinked thermoplastics obtained by neutralization with monovalent, divalent and / or trivalent metals of the group.

Preferred groups of the ionomer resin are derived from at least one alpha-olefin and at least one ethylenically unsaturated carboxylic acid and / or anhydride. Suitable alpha-olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 3-methylbutene, isobutene, butadiene, isoprene, α-methyl styrene, toluene, t-butyl styrene and styrene And the like. Suitable carboxylic acids and anhydrides include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, maleic anhydride, and the like. The preceding copolymer generally contains from about 0.2 to about 20 mole percent, and preferably from about 0.5 to about 10 mole percent carboxylic acid groups.

Preferred ionomers are obtained by reacting the preceding copolymer with a sufficient amount of metal ions to neutralize at least some of the acid groups present, preferably about 5% by weight, and preferably about 20 to about 100% by weight of the acid groups present. Suitable metal ions are Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Rb ⁺ , Hg ⁺ , Cu ⁺ , Be ⁺² , Mg ⁺² , Ca ⁺² , Sr ⁺² , Cu ⁺² , Cd ⁺² , Hg ⁺² , Sn ⁺² , Pb ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , Zn ⁺² , Al ⁺³ and Y ⁺³ . Preferred metals suitable for neutralizing the copolymers used herein are alkali metals, in particular cations such as sodium, lithium and potassium and alkaline earth metals, especially cations such as calcium, magnesium and zinc. Preferred ionomers include Surlyn (trade name) 1702, a zinc salt of ethylene and methacrylic acid copolymers, and suline (trade name) 8660, a sodium salt of ethylene and methacrylic acid copolymers. Both Suline ™ 1702 and Suline ™ 8660 are available from EI Dupont de Nemours & Company, Wilmington, Delaware, USA.

Ethylene / carboxylic acid interpolymers or ionomers may be found in the gasket compositions in the range of about 2% to about 15% by weight of the three component composition. Preferably, the ethylene / carboxylic acid interpolymer or ionomer is in the gasket composition in the range of about 4% to about 12%, about 2% to about 12%, or about 2% to about 10% by weight. Can be found. Most preferably, the ethylene / carboxylic acid interpolymer or ionomer may be found in the gasket composition in an amount in the range of about 4% to about 10%. The melt index of the interpolymers of ethylene and acrylic acid is from about 0.15 to about 400 g / 10 minutes. Preferably, the melt index is from about 1 to about 100 g / 10 minutes, most preferably from about 1 to about 30 g / 10 minutes.

In another embodiment of the present invention, the gasket composition may comprise the ethylene / alpha-olefin polymer and ethylene and acrylic acid interpolymers used in the present invention. Acrylic acid can be found in the interpolymer in the range of about 3% to about 50% by weight of the interpolymer. Preferably, acrylic acid may be found in the range of about 5% to 18%, and most preferably about 6.5% to about 15%.

Examples of suitable interpolymers of ethylene and acrylic acid are Primacor (trade name), available from The Dow Chemical Company (about 20% acrylic acid and a melt index of about 300 grams / 10 minutes (I2)). Examples of suitable interpolymers of ethylene and acrylic acid can be found in US Pat. Nos. 4,500,664, 4,988,781 and 4,599,392, incorporated herein by reference.

additive

Optionally, the polymer blends disclosed herein may include one or more additives to improve and / or control the processability, appearance, physical, chemical, and / or mechanical properties of the polymer blend. In some embodiments, the polymer blend does not include an additive. 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, oils or extenders, or deodorants 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), incorporated herein by reference in its entirety.

Slip

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 the sliding of the film surface on each other or on a different substrate. The slip performance of the film can be measured by the document ASTM D 1894 [Static and Kinetic Coefficients of Friction of Plastic Film and Sheeting], incorporated herein by reference. In general, slip agents can transfer slip properties by modifying the surface properties of the film and reducing friction between layers of the film and between the film and other surfaces that they contact. In some embodiments, the slip agent includes suitable wear resistance to enhance the additive as is known to those skilled in the art.

Any slip agent known to those skilled in the art can be added to the polymer blends disclosed herein. In some embodiments, the slip agent is one or more selected from hydroxide, aryl and substituted aryl, halogen, alkoxy, carboxylate, ester, carbon unsaturated, acrylate, oxygen, nitrogen, carboxyl, sulfate and phosphate It is a hydrocarbon which has a functional group. In some embodiments, the slip agent is selected from alcohols and acids of esters, amides, aromatic and aliphatic hydrocarbon oils. In another embodiment, the slip agent is carnauba wax, microcrystalline wax or polyolefin wax or any other conventional wax. The amount of wax ranges from about 2 to about 15 weight percent based on the total weight of the composition. Any conventional wax useful for thermoplastic films can be contemplated. In some embodiments, the slip agent is oxidized polyethylene.

In some embodiments, the slip agent is a silicone-based material such as high molecular weight polydialkyl siloxanes such as polydimethyl siloxane, silicone oil or gum additives; Some special materials that contain a combination of a wax material applied to the surface, such as erucamide, and a hard tough plastic, such as naronro with a surface active agent. In some embodiments, the amount of polydialkylsiloxane is sufficient to reduce friction when the film is formed or can be manipulated in a packaging device.

In certain embodiments, the slip agent for the polymer blends disclosed herein is an amide represented by formula (I):

Wherein each R ¹ and R ² is independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl; R ³ is alkyl or alkenyl, each of about 11 to about 39, about 13 to about 37, about 15 to about 35, about 17 to about 33, 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, and in other embodiments, R ³ is pentadecyl, heptadecyl, nonadecyl, henicosanyl, tri Cosanyl, pentacosanyl, heptacosanyl, nonacosanyl, hetriacontanil, tritricontanyl, nonatriacontanyl or combinations thereof. In a further embodiment, R ³ is pentadecenyl, heptadecenyl, nonadesenyl, henicosanenyl, tricosanenyl, pentacosadenyl, heptacosadenyl, nonylcosadenyl, gentriacontanenyl, tricona Tanenyl, nonatriacontanenyl or combinations thereof.

In a further embodiment, the slip agent for the polymer blends disclosed herein is an amide represented by formula (II)

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

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

Amides of formula (I) or (II) are amines of the formula H-NR ¹ R ² , wherein each of R ¹ and R ² is independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl And R ³ -CO ₂ H or CH _3- (CH ₂ ) _m- (CH = CH) _p- (CH ₂ ) _n -CO ₂ H, wherein R ³ is alkyl or alkenyl, each of 19 And at least about 39 carbon atoms; each of m and n is an integer from about 1 to about 37; and p is 0 or 1). The amine of the 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 and R ² Is H, or a secondary amine (ie, each of R ¹ and R ² is independently alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl). Some non-limiting examples of primary amines are methylamine, ethylamine, octadecylamine, behenylamine, tetracosanylamine, hexacosanylamine, octacosanylamine, triacontylamine, ditricontylamine, Tetratriacylamine, tetracontylamine, cyclohexylamine and combinations thereof. Some non-limiting examples of secondary amines are dimethylamine, diethylamine, dihexadecylamine, dioctadecylamine, diecosylamine, didocosylamine, diecetylamine, distearylamine, diarachidylamine, dibe Heylamine, dihydrogenated tallow amine, and combinations thereof. Primary and secondary amines are prepared by methods known to those skilled in the art, or by Aldrich Chemicals, Milwaukee, Wisconsin; ICC Chemicals, New York, NY; Chemos GmbH, Regenstauff, Germany; ABCR GmbH & Co. KG, Karlsruhe, Germany; And commercial suppliers such as Acros Organics, Gil, Belgium.

Primary or secondary amines may be prepared by reduction amination reactions. Reductive amination condenses ammonia or primary amines with aldehydes or ketones to form the corresponding imines which are subsequently reduced to amines. Subsequent reduction of the imine to the amine can be achieved by imine and hydrogen and suitable hydrogenation catalysts such as Raney nickel and platinum oxide, aluminum-mercury amalgam or hydrates such as linium aluminum hydrate, sodium cyanoborohydride, and sodium borohydride This can be accomplished by reacting the leads. 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; See, 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). These U.S. patents and documents 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, deicosanoic acid, heneic acid, docoic acid , Trichoic acid, tetracoic acid, pentacoic acid, hexacoic acid, heptacoic acid, octacoic acid, nonacoic acid, triacontanic acid, gentriaconic acid, dotriacontanic acid, tetratriconic acid, hexatriacon Carbonic acid, octatriconic acid and tetracontanic acid; Branched chain saturated fatty acids such as 16-methylheptadecanoic acid, 3-methyl-2-octylinanoic acid, 2,3-dimethyloctadecanoic acid, 2-methyltetraconic acid, 11-methyltetraconic acid, 2 Pentadecyl-heptadecanoic acid; Unsaturated fatty acids such as trans-3-octadecenoic acid, trans-11-decicocenic acid, 2-methyl-2-decicocenic acid, 2-methyl-2-hexacosenoic acid, β-eleostearic acid, α -Parinar acid, 9-nonadecenic acid and 22-tricosenoic acid, oleic acid and erucic acid. Carboxylic acids are prepared by methods known to those skilled in the art, or are available from Aldrich Chemicals, Milwaukee, Wisconsin; ICC Chemicals, New York, NY; Chemos Geembahasa, Regenstauff, Germany; ABCR Geembahasa, Karlsruhe, Germany; And commercial suppliers such as Acros Organics, Gil, Belgium. Some known methods for the preparation of carboxylic acids include oxidation of the corresponding primary alcohols with oxidizing agents, for example metal chromates, metal dichromates 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 (incorporated herein by reference). 1983).

The amidation reaction can occur 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 sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium acetate, ammonium acetate and the like, metal alkoxides such as sodium methoxide, sodium ethoxide and the like, amines such as Triethylamine, diisopropylethylamine, and the like. In some embodiments, the catalyst is an amine or metal alkoxide.

In some embodiments, the slip agent is a primary amine having a saturated aliphatic group having about 12 to about 40 carbon atoms or about 18 to about 40 carbon atoms (eg, stearamide and behenamide). In other embodiments, the slip agent is a primary amide (eg, erucamide and oleamide) having one or more carbon-carbon double bonds and unsaturated aliphatic groups containing 18 to about 30 carbon atoms. In further embodiments, the slip agent is a primary amide having at least 20 carbon atoms. In some embodiments, the slip agent is a secondary amide having about 18 to about 80 carbon atoms (eg, stearyl erucamide, behenyl erucamide, methyl erucamide and ethyl erucamide); Secondary-bis-amides having from about 18 to about 80 carbon atoms (eg, ethylene-bis-stearamide and ethylene-bis-oleamide); And combinations thereof. In further embodiments, the slip agent is erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearamide, ethylene-bis-oleamide, stearyl erucamide, behenyl erucamide, erucyl er Lucamide, oleyl palmitamide, stearyl stearamide, ilsyl stearamide, ethylene bisamide, for example, N, N-ethylenebis stearamide, N, N-ethylene bisolamide, 13-cis- Docosenamide or combinations thereof. In certain embodiments the slip agent is erucamide. In a further embodiment, the slip agent is trade name ATMER from Uniqema, Eberberg, Belgium, Akzo Nobel Polymer Chemicals, Chicago, Illinois, USA ARMOSLIP (registered trademark), KEMAMIDE (registered trademark) from Witco, Greenwich, Connecticut, USA, and Croy, Edison, New Jersey, USA Commercially available as CROD AMIDE® from Croda. When used, 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 the total weight of the polymer blend. 0.05 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), incorporated herein by reference. .

Blocking  Inhibitor

Optionally, the polymer blends disclosed herein can include an antiblocking agent. In some embodiments, the polymer blends disclosed herein may not include an antiblocking agent. Antiblocking agents are used to prevent undesired adhesion between the contacting layers of articles made from polymer blends, under suitable pressure and heat, in particular during storage, manufacture or use. Any antiblocking agent known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of antiblocking agents include minerals (eg, clays, chalk and calcium carbonate), synthetic silica gels (eg, SYLOBLOC, registered from Grace Davison, Columbia, MD, USA). Trademarks), natural silica (e.g. SUPER FLOSS® from Celite Corporation, Santa Barbara, Calif.), Talc (e.g., Centen, Colorado, USA) OPTIBLOC (R) from Luzenac, Nial (e.g., SIPERNAT (R) from Degussa, Farnoffy, NJ, USA) Nosilicates (eg, SILTON® from Mizusawa Industrial Chemicals, Tokyo, Japan), spherical polymer particles (eg , EPOSTAR® from Nippon Shokubai, Tokyo, Japan, poly (methyl methacrylate) particles, GE Silicones, Wilton, Connecticut, USA TOSPEARL® from waxes, amides (e.g. erucamides, oleamides, steteramides, behenamides, ethylene-bis-stearamides, ethylene-bis-oleamides, stearyls) Erucamide and other slip agents), molecular sieves, and combinations thereof Mineral particles can lower blocking by creating physical gaps between articles, while organic antiblocking agents migrate to the surface to limit surface adhesion If used, the amount of antiblocking agent in the polymer blend is greater than about 0 to about 3 weight percent, about 0.0001 to about 2 weight percent, and about 0.001 to about 1 of the total weight of the polymer blend. Amount, or from about 0.001 to about 0.5 weight percent 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).

Plasticizer

Optionally, the polymer blends disclosed herein can include a plasticizer. Generally, plasticizers are compounds that increase flexibility and lower the glass transition temperature of the polymer. 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 esters thereof, glutarates, hydrocarbon oils, isobutyrates, Oleate, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinolates, sebacates, sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates, difuran diesters, fluorine-containing plasticizers , Hydroxybenzoic acid esters, isocyanate adducts, polycyclic aromatic compounds, natural product derivatives, nitriles, siloxane plasticizers, tar based products, thioethers and combinations thereof.

In some embodiments, the plasticizers are olefin oligomers, low molecular weight polyolefins, such as liquid polybutenes, phthalates, mineral oils such as naphthenes, paraffins, or hydrogenated (white) oils (eg, Kaidol oils). ), Vegetable and animal oils and derivatives thereof, crude oil derived oils and combinations thereof. In some embodiments, the plasticizer comprises polypropylene, polybutene, hydrogenated polyisoprene, hydrogenated polybutadiene, polypiperylene and copolymers of piperylene and isoprene, etc. having an average molecular weight of about 350 to about 10,000. In other embodiments, the plasticizer comprises glyceryl esters of conventional fatty acids and their polymerization products.

In some embodiments, suitable poorly soluble plasticizers include dipropylene glycol dibenzoate, pentaerythritol tetrabenzoate; Polyethylene glycol 400-di-2-ethylhexate; 2-ethylhexyl diphenyl phosphate; And butyl benzyl phthalate, dibutyl phthalate, dioctyl phthalate, various substituted citrate and glycerate. Suitable dipropylene glycol dibenzoate and pentaerythritol tetrabenzoate can be purchased respectively from the Belsicol Chemical Company, Chicago, Illinois, under the trade names "Benzoflex 9-88 and S-552". have. In addition, suitable polyethylene glycol 400-di-2-ethylhexate can be found in C.P., Chicago, Illinois, USA. Commercially available from C.P. Hall Company under the trade name "Tegmer 809". Suitable 2-ethylhexyl diphenyl phosphate, and butyl benzyl phthalate can be purchased from Monsanto Industrial Chemical Company, St. Louis, Missouri. In some embodiments, Affinity® GA high flow polymers, such as Affinity® GA 1950 POP and Affinity® as extenders to improve processability without significantly reducing key performance characteristics. GA 1900 POP.

Some plasticizers are described in George Wypych, "Handbook of Plasticizers" ChemTec Publishing, Toronto-Scarborough, Ontario (2004), which is incorporated herein by reference. When used, the amount of plasticizer in the polymer blend is greater than 0 to about 65 weight percent, greater than 0 to about 50 weight percent, greater than 0 to about 25 weight percent, greater than 0 to about 15 weight percent, and about 0.5 to about 0 weight percent of the total weight of the polymer blend. About 10% by weight, or about 1 to about 5% by weight.

adhesive

In some embodiments, the compositions disclosed herein can comprise a tackifier or tackifying resin or tackifier resin. The tackifier can modify the properties of the composition, such as viscoelastic properties (eg, tan delta), rheological properties (eg, viscosity), tackiness (ie adhesion ability), pressure sensitivity, and wetting properties. In some embodiments, the tackifier is used to improve the tack of the composition. In some embodiments, the tackifier is used to reduce the viscosity of the composition. In a further embodiment, the tackifier is used to make the composition a pressure sensitive adhesive. In certain embodiments, the tackifier is used to wet the adhesive surface and / or improve adhesion to the adhesive surface.

Any tackifier known to those skilled in the art can be used in the adhesive compositions disclosed herein. Adhesives suitable for the compositions disclosed herein can be solid, semi-solid or liquid at room temperature. Non-limiting examples of tackifiers include (1) natural and modified rosin (eg gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin and polymerized rosin); (2) Glycerol and pentaerythritol esters of natural and modified rosins (eg, fail glycerol esters, wood rosin, glycerol esters of hydrogenated rosin, glycerol esters of polymerized rosin, pentaerythritol esters of hydrogenated rosin, and rosin) Phenol-modified pentaerythritol esters); (3) copolymers and terpolymers of natural terpenes (eg, styrene / terpenes and alpha methyl styrene / terpenes); (4) polyterpene resins and hydrogenated polyterpene resins; (5) phonol modified terpene resins and their hydrogenated derivatives (eg, resin products resulting from the condensation of bicyclic derpenes and phenols in acidic media); (6) aliphatic or cycloaliphatic hydrocarbon resins and their hydrogenated derivatives (for example, resins resulting from the polymerization of monomers consisting predominantly of olefins and diolefins); (7) aromatic hydrocarbon resins and their hydrogenated derivatives; (8) aromatic modified aliphatic or cycloaliphatic hydrocarbon resins and hydrogenated derivatives thereof; And combinations thereof. The amount of tackifier in the composition may be about 5 to about 70 weight percent, about 10 to about 65 weight percent, or about 15 to about 60 weight percent of the total weight of the composition.

In another embodiment, the tackifier is a rosin-based tackifier (e.g., AQUATAC® 9027, Aquatack® 4188, Syllite from Arizona Chemical, Jacksonville, FL, USA) (SYLVALITE®), SILVATAC® and SILLVAGUM® rosin esters). In other embodiments, the tackifier comprises a polyterpene or terpene resin (eg, SYLVARES® terpene resin from Arizona Chemical, Jacksonville, FL). In another embodiment, the tackifier is a resin resulting from the polymerization of monomers consisting of aliphatic hydrocarbons such as olefins and diolefins (e.g., ESCOREZ® from ExxonMobil Chemical Company, Texas, USA) 1310LC, Escores® 2596), and hydrogenated derivatives thereof (e.g., Escores® 5300 and 5400 series from ExxonMobil Chemical Company; Isman Chemicals, Kingsport, Tenn.) (EASTOTAC®) from Eastman Chemical. In a further embodiment, the tackifier is a tackifier including an aromatic compound (e.g., Escorez® 2596 from ExxonMobil) and a low softening point resin (Aquatack 5527 from Arizona Chemical, Jacksonville, FL). To be modified. In some embodiments, the tackifier is an aliphatic hydrocarbon resin having 5 or more carbon atoms. In other embodiments, the pressure sensitive adhesive has a Ring and Bell (R & B) softening point of at least 80 ° C. Ring and mouth (R & B) softening point can be measured by the method described in ASTM E28.

In some embodiments, the performance characteristics of the tackifiers in the compositions disclosed herein may be directly related to the compatibility with the ethylene / α-olefin interpolymers. Preferably, a composition having the desired adhesive properties can be obtained with an adhesive compatible with the interpolymer. Incompatible pressure sensitive adhesives may not produce the desired adhesive properties, but they may be used to effect other desired properties. For example, the properties of the composition may be fine tuned and / or increase the adhesive strength properties by the addition of an adhesive with limited usability that lowers the adhesion level.

Antioxidant

In some embodiments, the polymer blends disclosed herein optionally include antioxidants capable of preventing oxidation of organic additives in the polymer component and the polymer blend. Any known antioxidant known to those skilled in the art can be added to the polymer blends disclosed herein. Non-limiting examples of suitable antioxidants include aromatic or hindered amines such as alkyl diphenylamines, phenyl-α-naphthylamines, alkyl or aralkyl substituted phenyl-α-naphthylamines, alkylated p-phenylene diamines Tetramethyl-diaminodiphenylamine and 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; Tetrakis [(methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (e.g. IRGANOX from Ciba Geigy, NY, USA) A10)), acryloyl modified phenol, octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g. Irganox (trade name) 1076 available from Ciba Geigy Corporation); Phosphite and phosphonite; hydroxylamine; benzofuranone derivatives; and combinations thereof, when used, the amount of antioxidant in the polymer blend is greater than about 0 to about 5 weight percent of the total weight of the polymer blend, From about 0.0001 to about 2.5 weight percent, from about 0.001 to about 1 weight percent, or from about 0.001 to about 0.5 weight percent Some antioxidants are described in Zweifel Hans et ah, "Plastics Additives Handbook, incorporated herein by reference. , "Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001).

UV Stabilizer

In other embodiments, the polymer blends disclosed herein optionally include UV stabilizers that can prevent or reduce degradation of the polymer blend by UV irradiation. 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 benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidine, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants , Metal salts, zinc compounds and combinations thereof. When used, the amount of UV stabilizer in the polymer blend is greater than about 0 to about 5 weight percent, about 0.001 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. Can be. 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). It is.

Barrier resin

Barrier resins are all types of resins that not only preserve the contents of articles made from the polymer blends provided herein, but also prevent invasion of contaminants, leakage of taste, color, smell, and the like. Exemplary barrier resins include EVOH, PVDC, nylon, PET, PP, PCTFE, COC, LCP, nitrile (AN-MA) copolymers, thermoplastic polyesters, binding layer resins and gas-permeable resins, and combinations thereof. But is not limited thereto. The amount of barrier resin in the polymer blend can range from greater than 0% to about 10%, from about 0.001% to about 10%, from about 0.1% to about 8%, or from about 1% to about 5% of the total weight of the composition.

Pigment

In a further embodiment, the polymer blends disclosed herein optionally include colorants or pigments that can change the appearance of the polymer blend in 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 pigments such as anthraquinones, andanthrones, Azo and monoazo compounds, arylamides, benzimidazolone, bona (BONA) lakes, diketophyllo-pyrrole, dioxazines, disazo compounds, diarylide compounds, flavantrons, indanthrones, isoindolinones, Isoindolin, metal complex, monoazo salt, naphthol, b-naphthol, naphthol AS, naphthol lake, perylene, perinone, phthalocyanine, pyrantrone, quinacridone, and quinophthalone and combinations thereof . When used, the amount of colorant or pigment in the polymer blend may be greater than about 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 ah, "Plastics Additives Handbook" Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 15, pages 813-882 (2001).

Filler

Optionally, the 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 talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina, for example alumina Trihydrate, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, wood powder, glass fiber, carbon fiber, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanium Nates and combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, fiberglass, alumina, titanium dioxide, or mixtures thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fibers or mixtures thereof.

In some embodiments, the inclusion of adsorbent inorganic additives has been found to improve the fragrance properties of the foamed articles provided herein. Addition of about 0.1 to about 3 weight percent, or about 0.5 to about 2 weight percent of deodorant additives, such as charcoal, calcium carbonate, or magnesium oxide, based on the total composition, is effective for odor removal.

When used, the amount of filler in the polymer blend is greater than about 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 the total weight of the polymer blend. 10 to about 40 weight percent. 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. ].

slush

Optionally, the polymer blends disclosed herein can include a lubricant. In general, lubricants may be used, in particular, to modify the rheology of the molten polymer blend, 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 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 waxes, polyethylene waxes, poly Propylene waxes, natural and synthetic paraffin waxes, fluoropolymers, and combinations thereof. In some embodiments, the lubricant comprises organopolysiloxane. In one minute embodiment, the organopolysiloxane may have an average molecular weight of at least 40,000 and a viscosity of at least 50.000 cst.

When used, the amount of lubricant in the polymer blend can be greater than about 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 lubricants are described in Zweifel Hans et al., "Plastics Additives Handbook" Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001).

Antistatic

Optionally, the polymer blends disclosed herein may include an antistatic agent. In general, antistatic agents can increase the electrical conductivity of the polymer blend and prevent static charge accumulation. Any antistatic agent known to those skilled in the art can be added to the polymer blends disclosed herein. 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, alkyl phosphates, quaternary ammonium salts, alkylbetaines and combinations thereof. When used, the amount of antistatic agent in the polymer blend can be greater than about 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 blend. Some antistatic agents 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 10, pages 627-646, incorporated herein by reference. 2001).

Crosslinking agent

In further embodiments, the polymer blends disclosed herein can optionally include a crosslinking agent that can be used to increase the crosslinking density of the polymer blend. Any crosslinking agent known to those skilled in the art can be added to the polymer blends disclosed herein. Examples of suitable crosslinkers include organic peroxides (eg, alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacrylperoxides, peroxyketals, and cyclic peroxides) and silanes (eg For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, and 3-methacryloyloxypropyltrimeth Oxysilane). When used, the amount of crosslinking agent in the polymer blend may be greater than about 0 to about 20 weight percent, about 0.01 to about 15 weight percent, or about 1 to about 10 weight percent of the total weight of the polymer blend. Some crosslinkers 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 14, pages 725-812 (2001). )].

Crosslinking of the polymer blend may also be initiated by any known irradiation method, including but not limited to electron-beam irradiation, beta irradiation, gamma irradiation, corona irradiation, and UV irradiation, with or without a crosslinking catalyst. U.S. Patent No. 10 / 086,057 (published as US2002 / 0132923 Al) and U.S. Patent No. 6,803,014 disclose electron-beam irradiation methods 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 less than 70 megarad doses. The irradiator may be any electron beam generator that operates in the range of about 150 kilovolts to about 6 megavolts with a power output capable of supplying the desired dosage. The voltage may be adjusted to an appropriate level, which may be, for example, more than or less than 100,000, 300,000, 1,000,000 or 2,000,000 or 3,000,000 or 6,000,000. 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 Megarad to about 20 Megarad. In addition, high and low temperatures, such as 0 ° C. to about 60 ° C., may also be used, but irradiation may be readily performed at room temperature. Preferably, the irradiation is carried out after molding or manufacture of the article. Also in a preferred embodiment, the ethylene interpolymers incorporated with the pro-rad additives are irradiated with electron beam irradiation at about 8 to about 20 megarads.

Crosslinking can be promoted with a crosslinking catalyst, and any catalyst that will provide the function can be used. Suitable catalysts generally include organometallic compounds including organic bases, carboxylic acids, and organic titanates and complexes and carboxylates of lead, cobalt, iron, nickel, zinc and tin. Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, tin acetate, tin octoate, lead naphthenate, zinc caprylate, cobalt naphthenate, etc. are effective. to be. 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 are azo compounds, organic peroxides and polyfunctional vinyl or allyl compounds such as triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetramethacrylate, glutaraldehyde, ethylene glycol Dimethacrylate, diallyl maleate, dipropargyl maleate, dipropargyl 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 peroxide) hexane, lauryl peroxide, tert-butyl peracetate, azobis Isobutyl nitrite and the like and combinations thereof. Preferred pro-rad additives for use in the present invention are compounds having polyfunctional (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 (s) are introduced through 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 high, 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 introduced is from about 0.001 to about 5 weight percent, more preferably from about 0.005 to about 2.5 weight percent and most preferably from about 0.015 to about 1 weight percent (total weight of ethylene interpolymer Standard).

In addition to electron-beam irradiation, crosslinking can also be carried out by UV irradiation. U. S. Patent No. 6,709, 742 discloses a crosslinking method by UV irradiation that can be used in embodiments of the present invention. The method includes mixing the photoinitiator with the polymer 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 the photoinitiator to sufficient UV radiation. The photoinitiator used in the practice of the invention is an aromatic ketone, for example monoacetal of benzophenone or 1,2-diketone. The primary photoreaction of monoacetals is the homogeneous decomposition of the α-bonds providing acyl and dialkoxyalkyl 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 JT Banks, et al., J. Am. Chem. Soc 1993, 115, 2473 are known as Norrish type I reactions described in more detail. The synthesis of aromatic 1,2 diketone Ar—CO—C (OR) ₂ —Ar ′ monoacetals is described in US Pat. No. 4,190,602 and German Pat. 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 ₆ H ₅ available from Ciba-Gay Corporation as Irgacure 651. )to be. Examples of other aromatic ketones useful in the practice of the present invention as photoinitiators are Irgacure 184, 369, 819, 907 and 2959, all commercially available from Ciba-Gay.

In some embodiments of the invention, the photoinitiator is used in combination with a photocrosslinker. Any photocrosslinker that connects two or more polyolefin backbones together through the formation of covalent bonds with the backbone in the generation of free radicals can be used in the present invention. Preferably the photocrosslinker is multifunctional. That is, they include two or more sites that, upon activation, form covalent bonds with sites on the backbone of the copolymer. Representative photocrosslinkers are polyfunctional vinyl or allyl compounds such as triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetramethacrylate, ethylene glycol dimethacrylate, diallyl maleate, dipropargyl Maleate, dipropargyl monoallyl cyanurate, and the like. Preferred optical crosslinkers 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. The compound is characterized by the ability to generate two or more reactive species (eg free radicals, carbenes, nitrates, etc.) upon exposure to UV-light and then covalently bond with the two polymer chains. 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, the copolymer is carried out in addition to and in addition to secondary crosslinking, ie photocrosslinking. In this embodiment, the photoinitiator is used in combination with a non-photocrosslinker, for example silane, or undergoes a secondary crosslinking procedure in which the copolymer is exposed, for example, to E-beam irradiation. Representative examples of silane crosslinkers are described in USP 5,824,718 and crosslinking through exposure to E-beam irradiation is described in USP 5,525,257 and 5,324,576. The use of photocrosslinkers in the above embodiments is optional.

One or more photoadditives, ie photoinitiators and optional photocrosslinkers, can be copolymerized by any method known in the art. However, preferably the photoadditive (s) are introduced via a masterbatch concentrate comprising a base resin that is the same or different from the copolymer. Preferably, the concentration of photoadditive in the masterbatch is relatively high, 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).

The photoinitiator (s) and any photocrosslinker (s) may be added during different stages of the fiber or film manufacturing process. If the light additives withstand the extrusion temperature, the polyolefin polymer may 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 drawn without photoadditives and the photoinitiators and / or photocrosslinkers can be extruded through immersion in solutions containing kiss-rolls, sprays, additives or by using other industrial methods for post-treatment. Applied to the fibers. The resulting fiber with the optical additive (s) is then cured through electromagnetic irradiation in a continuous or batch process. The optical additives can be blended with the polyolefin via conventional compounding equipment, including single and double-screw extruders.

Electromagnetic radiation intensity and irradiation time are chosen to allow efficient crosslinking without polymer degradation and / or dimensional defects. Preferred processes are described in EP 0 490 854 Bl. The photoadditive (s) with sufficient thermal stability are premixed with the polyolefin resin, extruded into fibers, and irradiated in a continuous process using one energy source or multiple devices connected in series. There are a number of advantages to using a continuous process as compared to a batch process to cure a sheet of fiber or knit fabric collected on the bobbin.

Irradiation can be accomplished with the use of UV-irradiation. Preferably, UV-irradiation is used with an intensity of less than 100 J / cm 3. The irradiator may be any UV-light generator that operates in the range of about 50 watts to about 25000 watts with a 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 more. Many other devices for UV-irradiating polymeric materials are known in the art. The irradiation is usually carried out at an irradiation amount of about 3 J / cm 3 to about 500 J / cm 3, preferably about 5 J / cm 3 to about 100 J / cm 3. In addition, irradiation can also be used at higher and lower temperatures, for example 0 ° C. to 60 ° C., but can be easily carried out at room temperature. The photocrosslinking process is faster at high temperatures. Preferably the irradiation is carried out after molding or production of the article. In a preferred embodiment, the copolymer incorporating the photoadditive is subjected to UV radiation at about 10 J / cm 3 to about 50 J / cm 3.

blowing agent

Suitable blowing agents for use in the gaskets disclosed herein include physical blowing agents that function as gas sources through changes in physical state. Volatile liquids produce a gas by becoming gaseous in the liquid, but the compressed gas dissolves under pressure in the molten polymer. Chemical blowing agents produce gases by chemical reaction, pyrolysis or reaction between two components.

Suitable physical blowing agents are pentane (eg n-pentane, 2-methylbutane, 2,2-dimethylpropane, 1-pentane and cyclopentane), hexane (eg n-hexane, 2-methylpentane, 3 -Methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, 1-hexene, cyclohexane, heptane (eg n-heptane, 2-methylhexane, 2,2-dimethylpentane, 2 , 3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, 1-heptane), benzene, toluene, dichloromethane, trichloromethane, Trichloroethylene, tetrachloromethane, 1,2-dichloroethane, trichlorofluoromethane, 1,1,2-trichlorotrifluoroethane, methanol, ethanol, 2-propanol, ethyl ether, isopropyl ether, acetone, Methyl ethyl ketone, and methylene chloride. Suitable gas blowing agents are carbon dioxide and nitrogen.

Suitable chemical blowing agents are sodium bicarbonate, dinitrosopentamethylenetetramine, sulfonyl hydrazide, azodicarbonamide (e.g., Celogen (trade name) AZNP 130, manufactured by Uniroyal Chemical) , p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, diisopropylhydrazodicarboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one , And sodium borohydride.

The amount of blowing agent depends on the desired density reduction. The amount of blowing agent required can be calculated by finding the volume of gas produced per gram of blowing agent at a given temperature and the desired density reduction (or target density) for the desired application. In chemical blowing agents, the range is 0.1 to 4% by weight, and more preferably 0.25 to 2% by weight. This range can be controlled by the addition of activators (sometimes called auxiliaries) such as zinc oxide, zinc stearate.

Foams useful for making the gaskets claimed herein are described in US Pat. Nos. 5,288,762, 5,340,840, 5,369,136, 5,387,620, and 5,407,965, all of which are incorporated herein by reference. As prepared.

polymer Blend  Produce

The components of the polymer blend, ie the ethylene / α-olefin interpolymers, one or more other polymer components such as elastomers, polyolefins or polar polymers and optional additives are known to those skilled in the art, preferably ethylene / α-olefin interpolymers. It may be mixed or blended using a method that can provide a substantially uniform distribution of heavy polyolefins and / or additives. Non-limiting examples of suitable blending methods include melt blending, solvent blending, extrusion, 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, all solvents, if present, are heated to a suitable elevated temperature of from about 100 ° C. to about 200 ° C. or from about 150 ° C. to about 175 ° C. at a pressure between about 5 Torr (667 Pa) and about 10 Torr (1333 Pa) Remove from The polymer blend is then formed by heating the contents of the container in a molten state in the container at the desired rate in the desired proportions and stirring.

In some 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 the mixture is then mixed or blended. The solvent is then removed to provide a polymer blend.

In further embodiments, a physical blending device that provides for dispersive mixing, dispensing mixing or a combination of dispersing and dispensing mixing may be useful for producing uniform blends. Both batch or continuous physical blending methods can be used. A non-limiting example of a batch method is a Brabender® mixing device (e.g., Bra Bravenender Instruments, Inc., South Hägensachk, NJ, USA). How to use a BRABENDER PREP CENTER® or BANBURY® internal mixing and roll milling device (commercially available from Farrel Company, Ansonia, Connecticut) It includes. Non-limiting examples of continuous methods include single screw extrusion, double screw extrusion, disk extrusion, reciprocating single screw extrusion, and pin barrel single screw extrusion. In some embodiments, the additive 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).

If one or more additives are required for the polymer blend, the desired amount of additives may be added in one or multiple charges to the ethylene / α-olefin interpolymer, polyolefin or polymer blend. In addition, the addition may be in any order. In some embodiments, an additive is first added and mixed or blended with the ethylene / α-olefin interpolymer and then 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 the additive-containing polyolefin is then 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.

Alternatively, masterbatches containing high concentrations of additives can be used. In general, masterbatches can be prepared by blending ethylene / α-olefin interpolymers, polyolefins or polymer blends with high concentrations of additives. The masterbatch may have an additive concentration of 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 masterbatch 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 masterbatch 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 combinations thereof. In other embodiments, the masterbatch contains a slip agent, an antiblocking agent or a combination thereof. In other embodiments, the master batch contains a slip agent.

polymer Blend  Applications

The polymer blends disclosed herein can be used to make durable articles for the automotive, architectural, medical, food and beverage, electrical, consumer, office, and consumer markets. In some embodiments, the polymer blend is a toy, grip, soft tactile handle, bumper rub strip, flooring, car floor mats, wheels, castors, furniture and appliances feet, tags, sealants, gaskets, for example static and dynamic Selected from gaskets, car doors, bumper strips, grill parts, locker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, caps, stoppers, plunger tips, delivery systems, kitchenware, shoes, shoe bladder and shoe soles Used to make flexible durable parts or articles. In other embodiments, the polymer blends can be used to make durable parts or articles that require high tensile strength and low compressive strain. In further embodiments, the polymer blends can be used to make durable parts or articles that require a high use temperature upper limit and a low modulus.

Gasket shape

Gaskets have many different forms, including “o-rings” and flat seals (eg, “film like” gaskets having a thickness suitable for the intended use).

Suitable end uses include gaskets for metal and plastic closures as well as other gasket applications. Applications include beverage cap liners, hot fill juice cap liners, polypropylene cap liners, steel or aluminum cap liners, high density polyethylene cap liners, window glass liners, sealed containers, closure caps, medical device gaskets, filter elements, pressure Drain gasket, hot melt gasket, easy twist off cap, electrochemical cell gasket, refrigerator gasket, galvanic cell gasket, leakproof cell gasket, waterproof sheet, reusable gasket, synthetic cork material, thin film cell electrical membrane separator , Magnetic rubber materials, disc gaskets for alcoholic beverage bottle caps, freeze resistant seal rings, gaskets for plastic casting, expansion joints and waterstops, corrosion resistant conduit connectors, flexible magnetic plastics, pipe connecting seals, electrical sheathing Integrated weatherproof plastic caps and hinges, self-facing foams, jar rings, Urethane gasket, glass seal, tamper evident sealing liner, pressure applicator, combined bottle cap and straw structure, large condiment bottle liner, metal cap for apple sauce or salsa bottles, household canning bottle, "crowns ) "And the like.

Gaskets made from substantially linear or homogeneous linear ethylene polymers have many advantages, especially in the foodstuff sector. This includes improved taste and aroma compared to existing polymer gaskets such as ethylene / vinyl acetate; Low adhesion to polar substrates (eg polyethylene terephthalate, glass) useful for low torque removal of closures / caps; Low extracts (eg less than about 5.5% by weight) (also useful for foodstuffs, particularly in compliance with regulations); Good adhesion to nonpolar substrates (eg, polypropylene and high density polyethylene (linear homopolymer polyethylene or linear heterogeneous high density polyethylene)); Good adhesion in a cap or crown that can be described as fully adhered to the substrate. This type of adhesion is indicated when the gasket can only be removed in the tack failure mode. Adhesive to metals (eg beer crowns) requires a lacquer that is compatible with the polymer system and that binds to the metal. One such example that provides good adhesion is the modified polyester provided by Watson Standard, # 40-207. Modified epoxy lacquers also exhibit good adhesion. Additional benefits include adequate gas and water barrier properties; Higher melting point compared to existing polymers (eg ethylene / vinyl acetate); Good stress cracking resistance; Good chemical resistance; Various hardnesses (useful for certain packaging which may require some degree of gasket stiffness, depending on the torque required to seal the container and the internal pressure of the container).

In certain embodiments, the ethylene / alpha-olefin polymer used in the present invention is present in the three component composition used in the gasket in an amount ranging from about 80% to about 97.5% by weight based on the total weight of the three component composition. . Preferably, the ethylene / alpha-olefin polymer used in the present invention may be found in the three component gasket composition in the range of about 85% to about 97.5%. More preferably, the ethylene / alpha-olefin polymer used in the present invention may be found in the gasket composition in the range of about 90% to about 97.5%. The three component composition can be mixed with other materials, such as styrene / butadiene / styrene block polymer (“SBS”). Preferably, the three component composition constitutes about 50%, in particular about 80% to 100%, of the gasket based on the gasket weight.

The gasket comprising the ethylene / alpha-olefin polymer used in the present invention should be hard enough to withstand compression but still soft enough to form a suitable seal. Thus, the hardness of the polymer allows various gaskets to be produced depending on the application. Hardness is measured herein as "Shore A" hardness (measured using ASTM D-2240). In the ethylene / alpha-olefin polymers used in the present invention, which make up the gasket, Shore A hardness is typically in the range of about 50 to about 100 without the use of crude oil included to reduce the hardness of the polymer and the resulting gasket. have.

In some embodiments, the gaskets provided herein include an antioxidant (eg, hindered phenol (eg, Irganox. RTM. 1010, manufactured by Ciba Geigi), phosphite (eg, Irgafos.RTM. 168 manufactured by Ciba Keiji Co., Ltd.), adhesive additives (e.g. polyisobutylene (PIB)), slip agents (e.g. erucamide), antiblocking additives, pigments, etc. This may also be included in the gasket composition in an amount that does not interfere with the improved properties described herein.

Various gasket manufacturing techniques are described in US Pat. No. 5,215,578 (McConnellogue et al.); U.S. Patent 4,085,186 to Rainer; U.S. Patent 4,619,848 to Knight et al .; U.S. Patent 5,104,710 to Knight; U.S. Patent 4,981,231 to Knight; U.S. Patent 4,717,034 to Mumford; US Patent No. 3,786,954 (Shull); US Patent No. 3,779,965 (Lefforge et al.); U.S. Patent No. 3,493,453 (Ceresa et al.); US Patent No. 3,183,144 to Caviglia; US Patent No. 3,300,072 to Caviglia; U.S. Patent 4,984,703 to Burzynski; US Patent No. 3,414,938 to Caviglia; US Patent No. 4,939,859 to Bayer; US Patent No. 5,137,164 to Bayer; And those disclosed in US Pat. No. 5,000,992 to Kelch. The disclosures of each of these US patents are incorporated herein by reference in their entirety. Preferably, the gasket is prepared in a single step process by extruding a portion of the expanded ethylene / alpha-olefin polymer used in the present invention and then immediately compression molding into a gasket that is in particular adhered to a substrate such as phenol, epoxy or polyester lacquer. Can be.

The gasket claimed herein is different from a gasket made by extrusion sheet or film by conventional techniques such as blown, cast or extrusion coated film and made by stamping or cutting the gasket from the sheet or film. Because significant waste is suppressed and the gasket dimensions are better controlled with a one-step process, another benefit of the one-step process is to achieve a smaller gasket thickness (eg, about 5 mils to about 50 mils). .

Preferably, the one-step process for forming a gasket having a Shore A hardness of about 40 to about 95,

(a) combining at least one ethylene / alpha-olefin interpolymer, at least one ethylene / carboxylic acid interpolymer or ionomer thereof, at least one slip agent with at least one blowing agent having the properties specified herein to form a mixture and,

(b) extruding the mixture into pellets,

(c) cutting the extrusion mixture into pellets,

(d) place the cut extruded mixture into a closure,

(e) compression molding the mixture located in the closure

Steps. More preferably, for closures with a 28 mm diameter, the weight of the cut pellets is from about 120 mg to about 300 mg.

The multilayer film structure also produces the gaskets disclosed herein under the premise that at least one layer (preferably an inner layer located adjacent to the product) comprises uniformly branched linear or uniformly branched substantially linear ethylene interpolymers. Suitable for Foamed multilayer gaskets comprising uniformly branched linear or uniformly branched substantially linear ethylene interpolymers are also useful in the present invention.

In some embodiments, the polymer blends disclosed herein can be used to make gaskets with improved taste and flavor characteristics. The use of ethylene / α-olefin interpolymers provides low sensitivity to temperatures in the range of, for example, 40 ° F. to 158 ° F. for the physical properties of the core closure liner or gasket. Ethylene / α-olefin interpolymers exhibit reduced property changes at temperatures ranging from 40 ° F. to 158 ° F. compared to other polymer systems. Core polymer properties are relatively unaffected by temperature over the critical operating temperature range.

The sealing gasket composition of the present invention may also include various other ingredients known to those skilled in the art. Examples of other materials that may be included in the gasket composition are lubricants and colorants. Examples of suitable lubricants include, but are not limited to, stearates and fatty amides such as chemamide-E (tradename), available from Witco Corporation. Examples of suitable colorants include, but are not limited to, tallow blue, available from Quantum Chemical Corporation.

For closure liner products used in more extreme conditions, the addition of very high molecular weight elastomers, such as up to 30% SEBS polymers with a melt index of less than 0.1, to ethylene / α-ethylene interpolymers have physical properties similar to very high molecular weight elastomers. A composition having The blend composition provides advantages including improved processability and reduced cost over very high molecular weight elastomers. Very high molecular weight elastomers alone are too viscous to be processed in the production equipment used to produce the closure liners.

Ethylene / α-olefin interpolymers provide a unique and beneficial combination of processing and physical properties that unmodified elastomers do not have. Elastomers, in particular SEBS, must be very high molecular weight to exhibit the physical properties required in the closure liner product, but at this molecular weight the elastomer is impossible to process in a standard closure liner device. Typically the polymer should be modified with extenders and other polymers to obtain sufficient processability.

Blends of ethylene / a-olefin interpolymers with polyolefin polymers, such as LLDPE, SEBS, etc., have a synergistic effect at compression set.

Manufacture of articles

Polymer blends can be used to make durable parts by known polymer processing methods, such as extrusion (eg, sheet extrusion and profile extrusion), injection molding, molding, rotational molding and blow molding. In general, extrusion is a process where the polymer is continuously pushed through the hot and high pressure areas where the polymer is melted and compacted along the screw and finally passed through the die. The extruder can be a single screw extruder, a multiple screw extruder, a disk 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 polymers is described herein 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 in a variety of applications. In general, injection molding is a method wherein the polymer is melted and injected at high pressure into a mold that is opposite the desired shape to form a part of the desired shape and size. The mold can be made of 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 in which a polymer is melted and reinserted into a mold that is opposite the desired shape to form parts of the desired shape and size. Molding can be pressureless or pressure assisted. 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 process commonly used to produce hollow plastic products. By using additional post-molding operations, complex parts can be produced as effectively as other molding and extrusion techniques. Rotational molding is different from other processing methods in that the heating, melting, molding and cooling steps all take place after the polymer is placed in the mold, and therefore no external pressure applied during molding is applied. Rotational molding of polymers is described in Glenn Beall, "Rotational Molding: Design, Materials & Processing," Hanser Gardner Publications, Cincinnati, Ohio (1998), which is hereby incorporated by reference in its entirety.

Blow molding can be used to make hollow plastic containers. The process includes placing the softened polymer in the center of the mold, expanding the polymer against the mold wall with the blow pins, and solidifying the product by cooling. There are three general types of blow molding: extrusion blow molding, injection blow molding and extension 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 illustrate and illustrate embodiments of the present invention. All numerical values are approximate. Given a numerical range, it should be understood that embodiments outside of the described ranges may still fall within the scope of the present invention. The specific details described in each embodiment should not be construed as essential features of the invention.

Test method

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

For samples 1-4 and A-C GPC  Way

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

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

Standard CRYSTAF  Way

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

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

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

The results of the differential scanning calorimetry were measured using a TAI model Q10OO DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml / min was used. The sample was pressed into a thin film, 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 a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments were operated at 140 ° C. Three polymer Laboratories 10-micrometer Mixed-B columns were used. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples were prepared by gently stirring at 160 ° C. for 2 hours. The injection volume used was 100 microliters and the flow rate was 1.0 ml / min.

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

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

Compression set

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

density

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

curve/ secant Modulus /Save Modulus

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

Optical properties

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

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

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

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

Mechanical properties-tensile, Hysteresis ( Hysteresis ) And Tear

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

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

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

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

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

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

TMA

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

DMA

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

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

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

Melt index

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

ATREF

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

¹³ C NMR  analysis

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

TREF Polymer fractionation by

Large scale TREF fractionation was performed by dissolving 15-20 g of polymer at 160 ° C. for 4 hours and dissolving in 2 liters of 1,2,4-trichlorobenzene (TCB). The polymer solution is 30-40 mesh (600-425 μm) spherical technical quality glass beads (available from Potters Industries, Brownwood HC 30 Box 20, 76801, USA) and diameter 0.028 "( 0.7 mm) cut wire short with 60:40 (v: v) mixture of stainless steel (available from Pellets, Inc., Industrial Drive 63, North Towanda, NY, USA 14120). It was added by 15 psig (100 kPa) nitrogen on a packed 3 inch by 4 foot (7.6 cm by 12 cm) steel column, and the column was deposited in 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. The new TCB was introduced at about 65 ml / min while the temperature was increased to 0.167 ° C./min.

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

Melt strength

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

catalyst

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Example  1 to 4, Comparative example  A ^*  To C ^*

General high throughput parallel polymerization conditions

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

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

¹ per 1000 carbon C _6, or higher chain content

² Bimodal Molecular Weight Distribution

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

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

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

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

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

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

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

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

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

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

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

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

¹ standard cm ³ / min

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

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

⁴ molar ratio in reactor

⁵ Polymer Producing Rate

⁶ % conversion of ethylene in the reactor

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Property test

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

The data in Table 4 also demonstrate that the polymers according to embodiments of the invention have improved pellet blocking strength. In particular, Example 5 has a 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.

^1. Tested at 51 cm / min.

^2. Measured at 38 ° C. for 12 hours.

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

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

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

Table 5 also shows that the polymers of the 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  19A to F, continuous solution polymerization, catalyst A1 / B2 + DEZ

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

Process details and results are included in Table 8. Selected polymer properties are provided in Tables 9 and 9A.

¹ standard cm ³ / min

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

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

⁴ ppm in the final product calculated by mass balance

⁵ Polymer Producing Rate

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

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

¹ Further information on the measurement and calculation of the block index of various polymers is available on March 15, 2006 in Colin El. blood. And U.S. Patent No .--- (will be inserted at the time of publication), entitled "Ethylene / α-olefin Block Interpolymer", assigned to Dow Global Technologies in the name of Shan, Ronni Hazelt, et al. Which is hereby incorporated by reference in its entirety.

² mole ratio in the reactor, Zn / C ₂ * 1000 = (Zn feed flow rate of Mw * Zn concentration / 1000000 / Zn) (Total Ethylene feed flow rate * (1-fractional ethylene conversion rate) / M _w of ethylene) * 1000. Note that "Zn" in "Zn / C ₂ * 1000" represents the amount of zinc in diethyl zinc ("DEZ") used in the polymerization process, and "C ₂ " represents the amount of ethylene used in the polymerization process. box.

polymer Example  20 to 25 and comparison Example  A ^**  To E ^**

Various multiblock copolymers with different degrees of soft segment to hard segment weight ratios were compared to physical blends of metallocene polymers and Ziegler-Natta polymers in similar soft to hard segment ratios, so that the block structure of the backbone was similar to that of segments of the same type. It shows how different the blend and performance are. Various physical properties can be improved, including compression set and wear resistance. Maintaining low Shore hardness values is particularly useful in gasket and closure formation. The addition of carboxylic acid copolymers and / or amide slip agents improves some of these performance properties.

polymer Blend  Of composition Example

Polymer blend compositions comprising the ethylene / α-olefin interpolymers of Examples 26-28 and one or more other polymers were prepared, evaluated, and tested. The ethylene / α-olefin interpolymers of Examples 26-28 are prepared according to procedures similar to those described herein. Melt index and total density for the ethylene / α-olefin interpolymers are provided below.

Example number Overall density I2 Polymer Example 26 0.877 One Polymer Example 27 0.878 5 Polymer Example 28 0.878 15

The following method is used to determine the properties of the blend.

100% Modulus (MPa) Crosshead speed 500 mm / min according to ISO 37 Type 1 (1994), modulus at 100% elongation (measured in Mega Pascals) UTS MPa Crosshead speed 500 mm / min according to ISO 37 Type 1 (1994), final tensile strength (measured in mega pascals) Final elongation% Crosshead speed 500 mm / min, final elongation according to ISO 37 Type 1 (1994) Tear strength (kN / m) Crosshead speed 500 mm / min, tear strength (measured in kN / m) according to ISO 34 Method B (1994) Hardness Shore A durometer hardness measured at room temperature (23 ° C.) 15 sec., According to ISO 868 (1985) Compression set (%) Compressive permanent strain, measured as a percentage at 125 ° C. for 70 hours according to ISO 815 Type A, multiple samples (1991) Oil swelling (% by weight) Oil swell measured as a percentage for 70 hours at 125 ° C. using IRM903 according to ISO 1817 (1999) Gel content (%) After dipping ˜1 g of chopped (˜1 mm) pellets in ˜100 g of cyclohexane at 23 ° C. for 48 hours and weighing the dried residue, cyclohexane in addition to rubber, for example extender oil, anti-oxidant, light weight stabilizer Gel content% measured by subtracting the weight of the component dissolved in the, or crosslinked EPDM Shear viscosity Apparent viscosity measured at 230 ° C. with a capillary die 15 × 1 mm at an apparent shear rate of 500 seconds ⁻¹ according to ASTM D-3835 (1996)

Tables 12 and 13 provide the properties of the various components and blend compositions used in the blends.

As shown in the data provided in Table 12 and Table 13, various physical properties, including compression set and wear resistance, have been improved while maintaining low Shore hardness values in polymer blends comprising one or more ethylene / α-olefin interpolymers. Such properties are particularly useful in forming the gaskets and closures provided herein.

In some embodiments, the addition of carboxylic acid copolymers and / or amide slip agents improves some of these performance properties.

Another improvement is a more puncture resistant surface. Using a microscope and a metal probe, the puncture resistance of the surface on a series of closure liners is observed. The surface of the closure liner (containing saline® 1702) does not break until the probe penetrates about 4 mils into the liner. In contrast, the surface of the closure liner free of ethylene / carboxylic acid in the formulation is destroyed almost immediately upon penetration.

The ethylene / carboxylic acid copolymer containing liner surface always reacts differently to polarized light, indicating that the surface is more crystalline and / or more oriented, which results in a more punctured surface. The addition of these components improves the "stringing and scuffing" resistance of the liner because of the improved slip component and more perforated surface layer.

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

Claims (54)

(A) about 80 to about 97.5 weight percent of one or more ethylene / α-olefin interpolymers based on the total weight of the components (A), (B) and (C), (B) about 2 to about 15 weight percent of at least one ethylene / carboxylic acid interpolymer or ionomer thereof, based on the total weight of components (A), (B) and (C), and (C) at least one slip agent Wherein the ethylene / α-olefin interpolymer is a block interpolymer, (a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm 3), or Wherein the numerical values of T _m and d correspond to the following relation: T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ) (b) has a M _w / M _n of about 1.7 to about 3.5 and is characterized by a delta heat ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak Or 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 130 J / g) ΔT ≥ 48 ° C (if ΔH is greater than 130 J / g), CRYSTAF peak is measured using at least 5% of the cumulative polymer, and if less than 5% of the polymers have the same CRYSTAF peak, the CRYSTAF temperature is 30 ° C.) (c) is characterized by a 300% strain and an elastic recovery rate Re (%) in one cycle, measured with a compression-molded film of an ethylene / α-olefin interpolymer, having a density d (g / cm 3), or Wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinking phases: Re> 1481-1629 (d)) (d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, the fraction having a molar comonomer content of at least 5% higher than the comparative random ethylene interpolymer fraction eluting at the same temperature, wherein The comparative random ethylene interpolymers are characterized by having the same comonomer (s) and a melt index, density and comonomer molar content (based on the total polymer) within 10% of the ethylene / α-olefin interpolymers. Or (e) having a storage modulus G 'at 25 ° C. (25 ° C.), and a storage modulus G' at 100 ° C. (100 degrees) and having a ratio of G ′ (25 ° C.) to G ′ (100 ° C.) of about 1: 1 to about 9: 1 A gasket comprising or obtained from the composition. The gasket of claim 1, wherein the ethylene interpolymer of (A) comprises an ethylene / C ₃ -C ₂₀ alpha-olefin interpolymer. The method of claim 2, wherein the ethylene interpolymer of (A) (i) a density of about 0.85 g / cm 3 to about 0.96 g / cm 3, (ii) a molecular weight distribution of about 1.8 to about 2.8, (iii) a melt index of from about 0.15 g / 10 minutes to about 100 g / 10 minutes, and (iv) single melt peak measured using differential scanning calorimetry Having a gasket. 4. The gasket of claim 1 or 3, wherein the ethylene interpolymer of (A) is further blended with the heterogeneously branched ethylene polymer. The method of claim 1 or 3, wherein the ethylene interpolymer of (A) (i) a density of about 0.86 g / cm 3 to about 0.92 g / cm 3, and (ii) a melt index of from about 0.15 g / 10 minutes to about 100 g / 10 minutes A gasket further blended with a heterogeneously branched ethylene polymer having 4. The gasket of claim 1 or 3, wherein the ethylene interpolymer comprises from about 85% to about 97.5% by weight of the total composition based on the total weight of components (A), (B) and (C). 4. The gasket of claim 1 or 3 wherein the ethylene / carboxylic acid interpolymer or ionomer thereof constitutes about 4% by weight of the total composition based on the total weight of components (A), (B) and (C). . The gasket of claim 1 or 3, wherein the ethylene / carboxylic acid interpolymer has an acid content of about 3% to about 50% by weight of the interpolymer. The gasket of claim 1 or 3, wherein the ethylene / carboxylic acid interpolymer has a melt index of from about 0.15 g / 10 minutes to about 400 g / 10 minutes. The gasket of claim 1 or 3, wherein the slip agent comprises about 0.05% to about 5% by weight of the total composition. The gasket of claim 1 or 3, wherein the slip agent comprises a primary amide formulation and a secondary amide formulation together that constitute from about 0.05% to about 5% by weight of the total composition. The gasket of claim 11, wherein the primary amide formulation is present at at least twice the level of the secondary amide formulation. The gasket according to claim 1 or 3, wherein the components (A), (B) and (C) of claim 1 together constitute about 80% to 100% by weight of the gasket. The gasket of claim 1 or 3, wherein the gasket is foamed. 15. The foamed gasket of claim 14 wherein the blowing agent is selected from the group consisting of physical blowing agents, gas blowing agents, and chemical blowing agents. 15. The blowing agent of claim 14 wherein the blowing agent is sodium bicarbonate, dinitrosopentamethylenetetramine, sulfonyl hydrazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, 5-phenyltetrazol, diisopropylhydrazodi A foamed gasket which is a chemical blowing agent selected from the group consisting of carboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one, and sodium borohydride. 15. The foamed gasket of claim 14 wherein the blowing agent is a gas blowing agent selected from the group consisting of carbon dioxide and nitrogen. 15. The blowing agent of claim 14 wherein the blowing agent is pentane, hexane, heptane, benzene, toluene, dichloromethane, trichloromethane, trichloroethylene, tetrachloromethane, 1,2-dichloroethane, trichlorofluoromethane, 1,1, 2-trichlorotrifluoroethane, methanol, ethanol, 2-propanol, ethyl ether, isopropyl ether, acetone, methyl ethyl ketone, and methylene chloride; A foamed gasket which is a physical blowing agent selected from the group consisting of isobutane and n-butane, 1,1-difluoroethane. The method of claim 3, wherein the ethylene / carboxylic acid interpolymer has an acid content of about 3% to about 50% by weight of the interpolymer, and a melt index of about 0.15 g / 10 minutes to about 400 g / 10 minutes, The gasket comprises the primary and secondary amide formulations that together comprise about 0.05% to about 5% by weight of the total composition. 20. The gasket of claim 19 wherein the primary amide formulation is present at at least twice the level of the secondary amide formulation. (A) about 80 to about 97.5 weight percent of one or more ethylene / α-olefin interpolymers based on the total weight of the components (A), (B) and (C), (B) about 2 to about 15 weight percent of at least one ethylene / carboxylic acid interpolymer or ionomer thereof, based on the total weight of components (A), (B) and (C), and (C) at least one slip agent Wherein the ethylene / α-olefin interpolymer is a block interpolymer, (a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm 3), or Wherein the numerical values of T _m and d correspond to the following relation: T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ) (b) has a M _w / M _n of about 1.7 to about 3.5 and is characterized by a delta heat ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak Or     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 130 J / g)     ΔT ≥ 48 ° C (if ΔH is greater than 130 J / g),     CRYSTAF peak is measured using at least 5% of the cumulative polymer, and if less than 5% of the polymers have the same CRYSTAF peak, the CRYSTAF temperature is 30 ° C.) (c) is characterized by a 300% strain and an elastic recovery rate Re (%) in one cycle, measured with a compression-molded film of an ethylene / α-olefin interpolymer, having a density d (g / cm 3), or     Wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinking phases:     Re> 1481-1629 (d)) (d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fraction has a molar comonomer content of at least 5% higher than the comparative random ethylene interpolymer fraction eluting at the same temperature; The comparative random ethylene interpolymers are characterized by having the same comonomer (s) and a melt index, density and comonomer molar content (based on the total polymer) within 10% of the ethylene / α-olefin interpolymers. Or (e) having a storage modulus G '(25 ° C.) at 25 ° C., and a storage modulus G' (100 ° C.) at 100 ° C. with a ratio of G ′ (25 ° C.) to G ′ (100 ° C.) being about 1: From 1 to about 9: 1, A method of making a synthetic cork closure for a liquid container, wherein at least a portion is coated with a gas impermeable polymer, the method comprising providing a synthetic cork closure, and coating at least a portion thereof with a gas impermeable polymer. The method of claim 21, wherein the gas impermeable polymer is a vinylidene chloride polymer. 23. The method of claim 22, wherein the gas impermeable polymer comprises (1) about 80 to about 93 mol% of (a) vinylidene chloride and (b) about 20 to about 7 mol% of at least one copolymerizable monoethylenically unsaturated monomer. Or (2) a vinylidene chloride polymer which is (a) a copolymer of (a) about 65 to about 75 mole percent vinylidene chloride and about 35 to about 25 mole percent copolymer of at least one copolymerizable monoethylenically unsaturated monomer. . (A) at least one ethylene / α-olefin interpolymer and (B) at least one other polymer that is a different component from the ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer is a block interpolymer ego, (a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm 3), or Wherein the numerical values of T _m and d correspond to the following relation: T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ) (b) has a M _w / M _n of about 1.7 to about 3.5 and is characterized by a delta heat ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak Or 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 130 J / g) ΔT ≥ 48 ° C (if ΔH is greater than 130 J / g), CRYSTAF peak is measured using at least 5% of the cumulative polymer, and if less than 5% of the polymers have the same CRYSTAF peak, the CRYSTAF temperature is 30 ° C.) (c) is characterized by a 300% strain and an elastic recovery rate Re (%) in one cycle, measured with a compression-molded film of an ethylene / α-olefin interpolymer, having a density d (g / cm 3), or Wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinking phases: Re> 1481-1629 (d)) (d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fraction has a molar comonomer content of at least 5% higher than the comparative random ethylene interpolymer fraction eluting at the same temperature; The comparative random ethylene interpolymers are characterized by having the same comonomer (s) and a melt index, density and comonomer molar content (based on the total polymer) within 10% of the ethylene / α-olefin interpolymers. Or (e) having a storage modulus G '(25 ° C.) at 25 ° C., and a storage modulus G' (100 ° C.) at 100 ° C. with a ratio of G ′ (25 ° C.) to G ′ (100 ° C.) being about 1: 1 to about 9: 1, or (f) having one or more molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF, the fractions having a block index of at least 0.5 and up to about 1 and a molecular weight distribution M _w / M _n greater than about 1.3 Characterized in that, or (g) having an average block index greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3, Polymer Blend Compositions. The method of claim 24, wherein the other polymer is selected from a second ethylene / α-olefin interpolymer, an elastomer, a polyolefin, a polar polymer, and an ethylene / carboxylic acid interpolymer or ionomer thereof different from the first ethylene / α-olefin interpolymer. Wherein the second ethylene / α-olefin interpolymer is a block interpolymer, (a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm 3), or Wherein the numerical values of T _m and d correspond to the following relation: T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ) (b) has a M _w / M _n of about 1.7 to about 3.5 and is characterized by a delta heat ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak Or 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 130 J / g) ΔT ≥ 48 ° C (if ΔH is greater than 130 J / g), CRYSTAF peak is measured using at least 5% of the cumulative polymer, and if less than 5% of the polymers have the same CRYSTAF peak, the CRYSTAF temperature is 30 ° C.) (c) is characterized by a 300% strain and an elastic recovery rate Re (%) in one cycle, measured with a compression-molded film of an ethylene / α-olefin interpolymer, having a density d (g / cm 3), or Wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinking phases: Re> 1481-1629 (d)) (d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fraction has a molar comonomer content of at least 5% higher than the comparative random ethylene interpolymer fraction eluting at the same temperature; The comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on the total polymer) within 10% of the ethylene / α-olefin interpolymer , or (e) has a storage modulus G '(25 ° C.) at 25 ° C., and a storage modulus G' (100 ° C.) at 100 ° C., with a ratio of G ′ (25 ° C.) to G ′ (100 ° C.) being about 1 : 1 to about 9: 1, or (f) having one or more molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF, the fractions having a block index of at least 0.5 and up to about 1 and a molecular weight distribution M _w / M _n greater than about 1.3 Characterized in that, or (g) having an average block index greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3, Composition. The method of claim 24, wherein the first ethylene / α-olefin interpolymer is present in an amount from about 9% to 99.5% of the total weight of the composition, and the second ethylene / α-olefin interpolymer is A composition present in an amount from about 9% to 99.5%. The composition of claim 24 or 25, wherein the other polymer is selected from thermoplastic vulcanizates, styrene block copolymers, neoprene, functionalized elastomers, polybutadiene rubbers, butyl rubbers or combinations thereof. 27. The polymer of claim 24 or 25 wherein the other polymer is LLPE, LLDPE, HDPE, EVA, EAA, EMA, ionomers thereof, metallocene LLDPE, impact grade propylene polymer, random grade propylene polymer, polypropylene and combinations thereof. Composition selected from water. 26. The polymer of claim 24 or 25 wherein the other polymer is nylon, polyamide, ethylene vinyl acetate, polyvinyl chloride, acrylonitrile / butadiene / styrene (ABS) copolymer, aromatic polycarbonate, ethylene / carboxylic acid And a polar polymer selected from copolymers, polyacrylics, and combinations thereof. 26. The polymer of claim 24 or 25, wherein the other polymer is an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-itaconic acid copolymer, an ethylene-methyl hydrogen maleate copolymer, an ethylene-maleic acid copolymer. , Ethylene-acrylic acid copolymer, ethylene-methacrylate copolymer, ethylene-methacrylic acid- methacrylate copolymer, ethylene-itaconic acid-methacrylate copolymer, ethylene-itaconic acid-methacrylate copolymer, ethylene -Methyl hydrogen maleate-ethyl acrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid-vinyl alcohol copolymer, ethylene-acrylic acid-carbon monoxide copolymer, ethylene-propylene -Acrylic acid copolymer, ethylene-methacrylic acid-acrylonitrile copolymer, ethylene-fumaric acid-vinyl methyl ether copolymer, Ethylene-vinyl chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinyl fluoride-methacrylic acid copolymer and ethylene-chlorotrifluoroethylene-meta The composition is an olefin / carboxylic acid interpolymer selected from a krylic acid copolymer, or a combination thereof. The slip agent, antiblocking agent, plasticizer, antioxidant, UV stabilizer, colorant, filler, lubricant, invincible, flow aid, coupling agent, crosslinking agent, nucleating agent, surfactant, solvent, flame retardant according to claim 24 or 25. And an additive selected from antistatic agents, extenders, deodorants, barrier resins, and combinations thereof. 32. The composition of claim 31 wherein the slip agent is polymethylsiloxane, erucamide, oleamide or combinations thereof. 32. The composition of claim 31 wherein the deodorant is calcium carbonate, activated carbon, or a combination thereof. 32. The composition of claim 31 wherein the barrier resin is ethylene vinyl alcohol (EVOH) copolymer or polyvinylidene chloride (PVDC). 32. The composition of claim 31 wherein the extender is mineral oil, polybutene, siloxane or combinations thereof. A gasket comprising the composition of claim 24. The gasket of claim 36, wherein the ethylene / carboxylic acid interpolymer or ionomer thereof constitutes from about 4% to about 12% by weight of the total composition. 38. The gasket of claim 37, wherein the ethylene / carboxylic acid interpolymer has an acid content of about 3% to about 50% by weight of the interpolymer. 37. The gasket of claim 36, wherein the slip agent comprises a primary amide formulation and a secondary amide formulation together that constitute from about 0.05% to about 5% by weight of the total composition. 40. The gasket of claim 39 wherein the primary amide formulation is present at at least twice the level of the secondary amide formulation. The gasket of claim 36, wherein the slip agent comprises a silane compound. 37. The gasket of claim 36 foamed using a blowing agent. 43. The gasket of claim 42 wherein the blowing agent is selected from the group consisting of physical blowing agents, gas blowing agents, and chemical blowing agents. 43. The blowing agent of claim 42 wherein the blowing agent is sodium bicarbonate, dinitrosopentamethylenetetramine, sulfonyl hydrazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, 5-phenyltetrazol, diisopropylhydrazodi A gasket which is a chemical blowing agent selected from the group consisting of carboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one, and sodium borohydride. 43. The gasket of claim 42 wherein the blowing agent is a gas blowing agent selected from the group consisting of carbon dioxide and nitrogen. 44. The blowing agent of claim 43 wherein the blowing agent is pentane, hexane, heptane, benzene, toluene, dichloromethane, trichloromethane, trichloroethylene, tetrachloromethane, 1,2-dichloroethane, trichlorofluoromethane, 1,1, 2-trichlorotrifluoroethane, methanol, ethanol, 2-propanol, ethyl ether, isopropyl ether, acetone, methyl ethyl ketone, and methylene chloride; A gasket which is a physical blowing agent selected from the group consisting of isobutane and n-butane and 1,1-difluoroethane. The composition of claim 36, wherein the ethylene / α-olefin interpolymer constitutes about 25% to about 35% by weight of the composition, the other polymer comprises about 55% to about 65% by weight of the composition, and the slip agent comprises about A gasket comprising from 1 to about 3 weight percent. The gasket of claim 36, wherein the composition has a static coefficient of friction or a coefficient of dynamic friction or less than about one. The gasket of claim 36, wherein the composition has a static coefficient of friction or a coefficient of dynamic friction or less than about 0.6. The gasket of claim 36, wherein the composition has a melt index of at least about 5 g / 10 minutes and a 70 ° C. compression set of less than 70% and a compression set change of less than 55% at 23 ° C. to 70 ° C. 37. The composition of claim 31, wherein the gasket made of the composition is odorless. 32. The composition of claim 31, wherein the extender is a substantially linear ethylene polymer having a melt index I ₂ of about 100 to about 1,000. The composition of claim 27 wherein the styrene block copolymer is a SEBS block copolymer having a melt index of less than 0.1. (A) about 80 to about 97.5 weight percent of at least one ethylene / α-olefin interpolymer based on the total weight of components (A), (B) and (C), wherein the ethylene / α-olefin interpolymer Is a block interpolymer, (a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point T _m (° C.), and a density d (g / cm 3), or Wherein the numerical values of T _m and d correspond to the following relations; T _m > -2002.9 + 4538.5 (d)-2422.2 (d) ² ) (b) has a M _w / M _n of about 1.7 to about 3.5 and is characterized by a delta heat ΔT (° C.) defined by the heat of fusion ΔH (J / g) and the temperature difference between the largest DSC peak and the largest CRYSTAF peak Or     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 130 J / g)     ΔT ≥ 48 ° C (if ΔH is greater than 130 J / g),     CRYSTAF peak is measured using at least 5% of the cumulative polymer, and if less than 5% of the polymers have the same CRYSTAF peak, the CRYSTAF temperature is 30 ° C.) (c) is characterized by a 300% strain and an elastic recovery rate Re (%) in one cycle, measured with a compression-molded film of an ethylene / α-olefin interpolymer, having a density d (g / cm 3), or Wherein the numerical values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers are substantially free of crosslinking phases:     Re> 1481-1629 (d)) (d) having a molecular fraction eluting at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fraction has a molar comonomer content of at least 5% higher than the comparative random ethylene interpolymer fraction eluting at the same temperature; The comparative random ethylene interpolymer has the same comonomer (s) and has a melt index, density and comonomer molar content (based on the total polymer) within 10% of the ethylene / α-olefin interpolymer , or (e) has a storage modulus G '(25 ° C.) at 25 ° C., and a storage modulus G' (100 ° C.) at 100 ° C., with a ratio of G ′ (25 ° C.) to G ′ (100 ° C.) being about 1 : 1 to about 9: 1, or (f) having one or more molecular fractions eluted at 40 ° C. to 130 ° C. when fractionated using TREF, the fractions having a block index of at least 0.5 and up to about 1 and a molecular weight distribution M _w / M _n greater than about 1.3 Characterized in that, or (g) having an average block index greater than 0 and up to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3 Comprising a composition, A method of making a synthetic cork closure for a liquid container, wherein at least a portion is coated with a gas impermeable polymer, the method comprising providing a synthetic cork closure, and coating at least a portion thereof with a gas impermeable polymer.

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