WO2009029476A1 - ADHESIVES MADE FROM INTERPOLYMERS OF ETHYLENE/α-OLEFINS - Google Patents
ADHESIVES MADE FROM INTERPOLYMERS OF ETHYLENE/α-OLEFINS Download PDFInfo
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- WO2009029476A1 WO2009029476A1 PCT/US2008/073831 US2008073831W WO2009029476A1 WO 2009029476 A1 WO2009029476 A1 WO 2009029476A1 US 2008073831 W US2008073831 W US 2008073831W WO 2009029476 A1 WO2009029476 A1 WO 2009029476A1
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- 0 COC1C2C=CC=CC2CCC1*C(CCC*)(Cc1ccccc11)C1ON Chemical compound COC1C2C=CC=CC2CCC1*C(CCC*)(Cc1ccccc11)C1ON 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/08—Low density, i.e. < 0.91 g/cm3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/11—Melt tension or melt strength
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/19—Shear ratio or shear ratio index
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/20—Activation energy or enthalpy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
Definitions
- This invention relates to adhesive compositions comprising at least one ethylene/ ⁇ -olefin interpolymer, methods of making the compositions, and methods of using the compositions in applications, such as hot melt adhesives, pressure sensitive adhesives, and thermoplastic marking compositions.
- An adhesive is a substance capable of holding solid materials (e.g., adherents or substrates) together by surface attachment. Adhesives have been widely used since ancient times. Archaeologists have found evidence of substances being used as adhesives in Arabic dating back to 4000 B.C. and in Egypt between 1500-1000 B.C. The first adhesive patent was issued in about 1750 in England for a glue made from fish. Later, patents were issued for adhesives using natural rubber, animal bones, fish, starch, milk protein or casein.
- Hot-melt adhesives at ambient temperature are generally solid materials that can be heated to a melt to hold adherents or substrates together upon cooling and solidifying. In some applications, the bonded substrates can be detached by remelting the hot melt adhesive if the substrates can withstand the heat.
- the hot melt adhesives can be used in paper products, packaging materials, laminated wood panels, kitchen countertops, vehicles, tapes, labels, and a variety of disposable goods, particularly in health and hygiene applications, such as disposable diapers, hospital pads, feminine sanitary napkins, and surgical drapes. These hot melt adhesives are generally based on a polymer, tackifier, and a wax.
- hot melt adhesives are based on polymer components including ethylene based semi-crystalline polymers such as ethylene-vinyl acetate copolymer (EVA) and linear low density polyethylene (LLDPE), styrene block copolymers (SBC) such as styrene-isoprene-styrene (SIS) copolymer and styrene-butadiene-styrene (SBS) copolymer, ethylene ethyl acrylate copolymers (EEA), and polyurethane reactive adhesives (PUR).
- EVA ethylene-vinyl acetate copolymer
- LLDPE linear low density polyethylene
- SBC styrene block copolymers
- SIS styrene-isoprene-styrene
- SBS styrene-butadiene-styrene
- ESA ethylene ethyl acrylate copolymers
- the invention provides an adhesive composition comprising:
- T m melting point
- d density
- ⁇ T > -0.1299( ⁇ H) + 62.81 for ⁇ H greater than zero and up to 130 J/g, ⁇ T > 48°C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 0 C; or
- (e) has a storage modulus at 25°C, G'(25°C), and a storage modulus at 100 0 C, C(IOO 0 C), wherein the ratio of G'(25°C) to C(IOO 0 C) is in the range of about 1:1 to about 9:1; or (f) has a molecular fraction which elutes between 40 0 C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 ; or
- the invention further provides a method of applying the inventive composition to a substrate comprising: applying the composition to the substrate via spiral spray in non-contact mode at a temperature in the range of from about 100 0 C to about 150 0 C.
- the invention further provides a method of applying the inventive composition to a substrate comprising: applying the composition to the substrate via slot die coating in contact mode at a temperature in the range of from about 100 0 C to about 150 0 C.
- Figure 1 shows the melting point/density relationship for the inventive polymers (represented by diamonds) as compared to traditional random copolymers (represented by circles) and Ziegler-Natta copolymers (represented by triangles).
- Figure 2 shows plots of delta DSC-CRYSTAF as a function of DSC Melt Enthalpy for various polymers.
- the diamonds represent random ethylene/octene copolymers; the squares represent polymer examples 1-4; the triangles represent polymer examples 5-9; and the circles represent polymer examples 10-19.
- the "X" symbols represent polymer examples A* -F*.
- Figure 3 shows the effect of density on elastic recovery for unoriented films comprising inventive interpolymers (represented by the squares and circles) and traditional copolymers (represented by the triangles which are various AFFINITY polymers (The Dow Chemical Company)).
- inventive interpolymers represented by the squares and circles
- traditional copolymers represented by the triangles which are various AFFINITY polymers (The Dow Chemical Company)
- the squares represent inventive ethylene/butene copolymers
- the circles represent inventive ethylene/octene copolymers.
- Figure 4 is a plot of octene content of TREF fractionated ethylene/ 1-octene copolymer fractions versus TREF elution temperature of the fraction for the polymer of Example 5 (represented by the circles) and Comparative Examples E* and F* (represented by the "X" symbols).
- the diamonds represent traditional random ethylene/octene copolymers.
- Figure 5 is a plot of octene content of TREF fractionated ethylene/ 1-octene copolymer fractions versus TREF elution temperature of the fraction for the polymer of Example 5 (curve 1) and for Comparative Example F* (curve T).
- the squares represent Example F*; and the triangles represent Example 5.
- Figure 6 is a graph of the log of storage modulus as a function of temperature for comparative ethylene/1-octene copolymer (curve 2) and propylene/ ethylene- copolymer (curve 3) and for two ethylene/1-octene block copolymers of the invention made with differing quantities of chain shuttling agent (curves 1).
- FIG. 7 shows a plot of TMA (lmm) versus flex modulus for some inventive polymers (represented by the diamonds), as compared to some known polymers.
- the triangles represent various VERSIFY polymers (The Dow Chemical Company); the circles represent various random ethylene/styrene copolymers; and the squares represent various AFFINITY ® polymers (The Dow Chemical Company).
- Figure 8 is a plot of natural log ethylene mole fraction for random ethylene/ ⁇ -olefin copolymers as a function of the inverse of DSC peak melting temperature or ATREF peak temperature.
- the filled squares represent data points obtained from random homogeneously branched ethylene/ ⁇ -olefin copolymers in ATREF; and the open squares represent data points obtained from random homogeneously branched ethylene/ ⁇ -olefin copolymers in DSC.
- P is the ethylene mole fraction;
- T is the temperature in Kelvin.
- Figure 9 is a plot constructed on the basis of the Flory equation for random ethylene/ ⁇ -olefin copolymers to illustrate the definition of "block index.”
- "A” represents the whole, perfect random copolymer;
- “B” represents a pure "hard segment”; and
- "C” represents the whole, perfect block copolymer having the same comonomer content as “A”.
- A, B, and C define a triangular area within which most TREF fractions would fall.
- Polymer means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
- the generic term “polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as “interpolymer.”
- Interpolymer means a polymer prepared by the polymerization of at least two different types of monomers.
- the generic term “interpolymer” includes the term “copolymer” (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term “terpolymer” (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
- ethylene/ ⁇ -olefin interpolymer generally refers to polymers comprising ethylene and an ⁇ -olefin having 3 or more carbon atoms.
- ethylene comprises the majority mole fraction of the whole polymer, i.e., ethylene comprises at least about 50 mole percent of the whole polymer. More preferably ethylene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial remainder of the whole polymer comprising at least one other comonomer that is preferably an ⁇ -olefin having 3 or more carbon atoms.
- the preferred composition comprises an ethylene content greater than about 80 mole percent of the whole polymer and an octene content of from about 10 to about 15, preferably from about 15 to about 20 mole percent of the whole polymer.
- the ethylene/ ⁇ -olefin interpolymers do not include those produced in low yields or in a minor amount or as a by-product of a chemical process. While the ethylene/ ⁇ - olefin interpolymers can be blended with one or more polymers, the as-produced ethylene/ ⁇ - olefin interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
- the ethylene/ ⁇ -olefin interpolymers comprise ethylene and one or more copolymerizable ⁇ -olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/ ⁇ -olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers.
- the terms "interpolymer” and copolymer” are used interchangeably herein.
- the multi-block copolymer can be represented by the following formula:
- n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher
- A represents a hard block or segment
- B represents a soft block or segment.
- As and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion.
- a blocks and B blocks are randomly distributed along the polymer chain.
- the block copolymers usually do not have a structure as follows. AAA- AA-BBB- BB
- the block copolymers do not usually have a third type of block, which comprises different comonomer(s).
- each of block A and block B has monomers or comonomers substantially randomly distributed within the block.
- neither block A nor block B comprises two or more sub-segments (or sub- blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
- the multi-block polymers typically comprise various amounts of "hard” and
- “soft” segments refer to blocks of polymerized units in which ethylene is generally present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer.
- the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, and preferably less than about 2 weight percent based on the weight of the polymer.
- the hard segments comprises all or substantially all ethylene.
- Soft segments refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer.
- the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
- the soft segments can often be present in a block interpolymer from about 1 weight percent to about 99 weight percent of the total weight of the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer.
- the hard segments can be present in similar ranges.
- the soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR.
- Such methods and calculations are disclosed in a concurrently filed U.S. Patent Application Serial No. 11/376,835, entitled “Ethylene/ ⁇ - Olefin Block Interpolymers", filed on March 15, 2006, in the name of Colin L.P. Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclosure of which is incorporated by reference herein in its entirety.
- multi-block copolymer or “segmented copolymer” refers to a polymer comprising two or more chemically distinct regions or segments (referred to as “blocks”) preferably joined in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion.
- the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property.
- the multi -block copolymers are characterized by unique distributions of both polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique process of making the copolymers.
- the polymers when produced in a continuous process, desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1.
- the polymers When produced in a batch or semi-batch process, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
- R R L +k*(R u -R L ), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
- k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
- any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
- Embodiments of the invention provide compositions that comprise an ethylene/ ⁇ -olefin interpolymer, a tackifier resin and an oil or a low molecular weight polymer.
- the compositions possess unique properties that are suitable for a variety of applications, particularly where a certain level of adhesion is required. Some non-limiting examples of suitable applications include hot melt adhesives, pressure sensitive adhesives, hot melt pressure sensitive adhesives, thermoplastic marking compositions, and the like.
- the ethylene/ ⁇ -olefin interpolymers are a multi-block copolymer comprising at least one soft block and at least one hard block.
- the adhesive compositions generally have a low melt viscosity so that it is easy to process the compositions .
- the melt viscosities of the compositions can be measured by a Brookfield viscometer using appropriate spindles as by ASTM D3236 at about 350 0 F (177°C), which is incorporated herein by reference.
- the composition has a melt viscosity of less than 4,600 cPs at about 177°C, or less than about 3,000 cPs at 177°C, or less than about 2,000 cPs at 177°C, or less than about 1,000 cPs at 177°C measured according to ASTM D3236.
- ventive interpolymer (also referred to as “inventive interpolymer” or “inventive polymer”) comprise ethylene and one or more copolymerizable ⁇ -olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably a multi-block copolymer.
- block interpolymer preferably a multi-block copolymer.
- the ethylene/ ⁇ -olefin interpolymers are characterized by one or more of the aspects described as follows.
- the ethylene/ ⁇ -olefin interpolymers used in embodiments of the invention have a M w /M n from about 1.7 to about 3.5 and at least one melting point, T m , in degrees Celsius and density, d, in grams/cubic centimeter, wherein the numerical values of the variables correspond to the relationship:
- inventive interpolymers represented by diamonds
- the melting point of such polymers are in the range of about 110 0 C to about 130 0 C when density ranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, the melting point of such polymers are in the range of about 115 0 C to about 125 0 C when density ranges from 0.875 g/cc to about 0.945 g/cc.
- the ethylene/ ⁇ -olefin interpolymers comprise, in polymerized form, ethylene and one or more ⁇ -olefins and are characterized by a ⁇ T, in degree Celsius, defined as the temperature for the tallest Differential Scanning Calorimetry (“DSC”) peak minus the temperature for the tallest Crystallization Analysis Fractionation (“CRYSTAF”) peak and a heat of fusion in J/g, ⁇ H, and ⁇ T and ⁇ H satisfy the following relationships:
- ⁇ T > -0.1299( ⁇ H) + 62.81, and preferably ⁇ T > -0.1299( ⁇ H) + 64.38, and more preferably ⁇ T ⁇ -0.1299( ⁇ H) + 65.95, for ⁇ H up to 130 J/g.
- ⁇ T is equal to or greater than 48 0 C for ⁇ H greater than 130 J/g.
- the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (that is, the peak must represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 0 C, and ⁇ H is the numerical value of the heat of fusion in J/g.
- the highest CRYSTAF peak contains at least 10 percent of the cumulative polymer.
- the ethylene/ ⁇ -olefin interpolymers have a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using Temperature Rising Elution Fractionation ("TREF"), characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein the comparable random ethylene interpolymer contains the same comonomer(s), and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the block interpolymer.
- TEZ Temperature Rising Elution Fractionation
- the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the block interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the block interpolymer.
- the ethylene/ ⁇ -olefin interpolymers are characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured on a compression-molded film of an ethylene/ ⁇ -olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/ ⁇ -olefin interpolymer is substantially free of a cross-linked phase: Re >1481-1629(d); and preferably Re >1491-1629(d); and more preferably Re >1501-1629(d); and even more preferably Re ⁇ 1511-1629(d).
- Figure 3 shows the effect of density on elastic recovery for unoriented films made from certain inventive interpolymers and traditional random copolymers.
- inventive interpolymers For the same density, the inventive interpolymers have substantially higher elastic recoveries.
- the ethylene/ ⁇ -olefin interpolymers have a tensile strength above 10 MPa, preferably a tensile strength > 11 MPa, more preferably a tensile strength > 13MPa and/or an elongation at break of at least 600 percent, more preferably at least 700 percent, highly preferably at least 800 percent, and most highly preferably at least 900 percent at a crosshead separation rate of 11 cm/minute.
- the ethylene/ ⁇ -olefin interpolymers have (1) a storage modulus ratio, G'(25°C)/G'(100°C), of from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70 0 C compression set of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent, down to a compression set of 0 percent.
- the ethylene/ ⁇ -olefin interpolymers have a 70 0 C compression set of less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent.
- the 70 0 C compression set of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and may go down to about 0 percent.
- the ethylene/ ⁇ -olefin interpolymers have a heat of fusion of less than 85 J/g and/or a pellet blocking strength of equal to or less than 100 pounds/foot 2 (4800 Pa), preferably equal to or less than 50 lbs/ft 2 (2400 Pa), especially equal to or less than 5 lbs/ft 2 (240 Pa), and as low as 0 lbs/ft 2 (0 Pa).
- the ethylene/ ⁇ -olefin interpolymers comprise, in polymerized form, at least 50 mole percent ethylene and have a 70 0 C compression set of less than 80 percent, preferably less than 70 percent or less than 60 percent, most preferably less than 40 to 50 percent and down to close to zero percent.
- the multi-block copolymers possess a PDI fitting a Schultz-Flory distribution rather than a Poisson distribution.
- the copolymers are further characterized as having both a polydisperse block distribution and a polydisperse distribution of block sizes and possessing a most probable distribution of block lengths.
- Preferred multi- block copolymers are those containing 4 or more blocks or segments including terminal blocks. More preferably, the copolymers include at least 5, 10 or 20 blocks or segments including terminal blocks.
- Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred.
- the polymer desirably is first fractionated using TREF into fractions each having an eluted temperature range of 10 0 C or less. That is, each eluted fraction has a collection temperature window of 10 0 C or less.
- said block interpolymers have at least one such fraction having a higher molar comonomer content than a corresponding fraction of the comparable interpolymer.
- the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks (i.e., at least two blocks) or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a peak (but not just a molecular fraction) which elutes between 40 0 C and 130 0 C (but without collecting and/or isolating individual fractions), characterized in that said peak, having a comonomer content estimated by infra-red spectroscopy when expanded using a full width/half maximum (FWHM) area calculation, has an average molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer peak at the same elution temperature
- the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer.
- the full width/half maximum (FWHM) calculation is based on the ratio of methyl to methylene response area [CH 3 /CH 2 ] from the ATREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined.
- the FWHM area is defined as the area under the curve between T 1 and T 2 , where T 1 and T 2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
- a calibration curve for comonomer content is made using random ethylene/ ⁇ -olefin copolymers, plotting comonomer content from NMR versus FWHM area ratio of the TREF peak. For this infra-red method, the calibration curve is generated for the same comonomer type of interest.
- the comonomer content of TREF peak of the inventive polymer can be determined by referencing this calibration curve using its FWHM methyl: methylene area ratio [CH3/CH 2 ] of the TREF peak.
- Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy preferred. Using this technique, said blocked interpolymers have higher molar comonomer content than a corresponding comparable interpolymer.
- NMR nuclear magnetic resonance
- the block interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 0 C greater than or equal to the quantity (- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T+ 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in 0 C.
- Figure 4 graphically depicts an embodiment of the block interpolymers of ethylene and 1-octene where a plot of the comonomer content versus TREF elution temperature for several comparable ethylene/1-octene interpolymers (random copolymers) are fit to a line representing (- 0.2013) T + 20.07 (solid line). The line for the equation (-
- T + 21.07 is depicted by a dotted line. Also depicted are the comonomer contents for fractions of several block ethylene/1-octene interpolymers of the invention (multi-block copolymers). All of the block interpolymer fractions have significantly higher 1-octene content than either line at equivalent elution temperatures. This result is characteristic of the inventive interpolymer and is believed to be due to the presence of differentiated blocks within the polymer chains, having both crystalline and amorphous nature.
- Figure 5 graphically displays the TREF curve and comonomer contents of polymer fractions for Example 5 and Comparative Example F* to be discussed below.
- the peak eluting from 40 to 130 0 C, preferably from 6O 0 C to 95°C for both polymers is fractionated into three parts, each part eluting over a temperature range of less than 10 0 C.
- Example 5 Actual data for Example 5 is represented by triangles.
- an appropriate calibration curve may be constructed for interpolymers containing different comonomers and a line used as a comparison fitted to the TREF values obtained from comparative interpolymers of the same monomers, preferably random copolymers made using a metallocene or other homogeneous catalyst composition.
- Inventive interpolymers are characterized by a molar comonomer content greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent greater, more preferably at least 10 percent greater.
- the above interpolymers are interpolymers of ethylene and at least one ⁇ -olefin, especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm 3 , and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 0 C greater than or equal to the quantity (- 0.1356) T + 13.89, more preferably greater than or equal to the quantity (-0.1356) T+ 14.93, and most preferably greater than or equal to the quantity (-0.2013)T + 21.07, where T is the numerical value of the peak ATREF elution temperature of the TREF fraction being compared, measured in 0 C.
- the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 0 C greater than or equal to the quantity (- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T+ 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in °C.
- the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 40 0 C and 130 0 C, when fractionated using TREF increments, characterized in that every fraction having a comonomer content of at least about 6 mole percent, has a melting point greater than about 100 0 C.
- every fraction has a DSC melting point of about HO 0 C or higher. More preferably, said polymer fractions, having at least 1 mol percent comonomer, has a DSC melting point that corresponds to the equation:
- the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 40 0 C and 130 0 C, when fractionated using TREF increments, characterized in that every fraction that has an ATREF elution temperature greater than or equal to about 76 0 C, has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation:
- the comonomer composition of the TREF peak can be measured using an IR4 infra-red detector available from Polymer Char, Valencia, Spain (http://www.polymerchar.com/).
- the "composition mode" of the detector is equipped with a measurement sensor (CH 2 ) and composition sensor (CH 3 ) that are fixed narrow band infra-red filters in the region of 2800-3000 cm “1 .
- the measurement sensor detects the methylene (CH 2 ) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH 3 ) groups 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 measured polymer in solution and its response is calibrated with known ethylene alpha-olefin copolymer standards.
- the area of the peaks can be calculated using a full width/half maximum
- FWHM FWHM calculation after applying the appropriate baselines to integrate the individual signal responses from the TREF chromatogram.
- the full width/half maximum calculation is based on the ratio of methyl to methylene response area [CH 3 /CH 2 ] from the ATREF infra- red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined.
- the FWHM area is defined as the area under the curve between Tl and T2, where Tl and T2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
- the inventive ethylene/ ⁇ -olefin interpolymer is characterized by an average block index, ABI, which is greater than zero and up to about 1.0 and a molecular weight distribution, M w /M n , greater than about 1.3.
- the average block index, ABI is the weight average of the block index ("BI") for each of the polymer fractions obtained in preparative TREF from 20 0 C and 110 0 C, with an increment of 5°C : where BI 1 is the block index for the ith fraction of the inventive ethylene/ ⁇ -olefin interpolymer obtained in preparative TREF, and W 1 is the weight percentage of the ith fraction.
- BI is defined by one of the two following equations
- T x is the preparative ATREF elution temperature for the ith fraction (preferably expressed in Kelvin)
- P x is the ethylene mole fraction for the ith fraction, which can be measured by NMR or IR as described above.
- P AB is the ethylene mole fraction of the whole ethylene/ ⁇ -olefin interpolymer (before fractionation), which also can be measured by NMR or IR.
- T A and P A are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer).
- T A and P A values are set to those for high density polyethylene homopolymer, if the actual values for the "hard segments" are not available.
- T A is 372 0 K
- P A is 1.
- T AB is the ATREF temperature for a random copolymer of the same composition and having an ethylene mole fraction of P AB - T AB can be calculated from the following equation:
- ⁇ and ⁇ are two constants which can be determined by calibration using a number of known random ethylene copolymers. It should be noted that ⁇ and ⁇ may vary from instrument to instrument. Moreover, one would need to create their own calibration curve with the polymer composition of interest and also in a similar molecular weight range as the fractions. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, such effect would be essentially negligible.
- random ethylene copolymers satisfy the following relationship:
- the weight average block index, ABI for the whole polymer can be calculated.
- ABI is greater than zero but less than about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.3 and up to about 1.0. Preferably, ABI should be in the range of from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9.
- ABI is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABI is in the range of from about 0.4 to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, from about 0.8 to about 1.0, or from about 0.9 to about 1.0.
- the inventive ethylene/ ⁇ -olefin interpolymer comprises at least one polymer fraction which can be obtained by preparative TREF, wherein the fraction has a block index greater than about 0.1 and up to about 1.0 and a molecular weight distribution, M w /M n , greater than about 1.3.
- 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.
- the polymer fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In still other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0.5, or greater than about 0.4 and up to about 0.5.
- 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.
- the inventive polymers preferably possess (1) a PDI of at least 1.3, more preferably at least 1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, up to a maximum value of 5.0, more preferably up to a maximum of 3.5, and especially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g or less; (3) an ethylene content of at least 50 weight percent; (4) a glass transition temperature, T g , of less than -25°C, more preferably less than -30 0 C, and/or (5) one and only one T m .
- the inventive interpolymers may be further characterized by a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 90 0 C as well as a flexural modulus of from 3 kpsi (20 MPa) to 13 kpsi (90 MPa).
- the inventive interpolymers can have a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 104 0 C as well as a flexural modulus of at least 3 kpsi (20 MPa).
- the ethylene/ ⁇ -olefin interpolymers have a melt index, I 2 , from 0.01 to 10 g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes, from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes.
- the melt index for the ethylene/ ⁇ -olefin polymers is lg/10 minutes, 3 g/10 minutes or 5 g/10 minutes.
- the polymers can have molecular weights, M w , from 1,000 g/mole to 5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, more preferably from 10,000 g/mole to 500,000 g/mole, and especially from 10,000 g/mole to 300,000 g/mole.
- the density of the inventive polymers can be from 0.80 to 0.99 g/cm 3 and preferably for ethylene containing polymers from 0.85 g/cm 3 to 0.97 g/cm 3 .
- the density of the ethylene/ ⁇ -olefin polymers ranges from 0.860 to 0.925 g/cm 3 or 0.867 to 0.910 g/cm 3 .
- one such method comprises contacting ethylene and optionally one or more addition polymerizable monomers other than ethylene under addition polymerization conditions with a catalyst composition comprising: the admixture or reaction product resulting from combining: a. a first olefin polymerization catalyst having a high comonomer incorporation index, b.
- a second olefin polymerization catalyst having a comonomer incorporation index less than 90 percent, preferably less than 50 percent, most preferably less than 5 percent of the comonomer incorporation index of catalyst (A), and c. a chain shuttling agent.
- Representative catalysts and chain shuttling agent are as follows.
- Catalyst (Al) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2- isopropylphenyl)( ⁇ -naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10/429,024, filed May 2, 2003, and WO 04/24740.
- Catalyst (A2) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2- methylphenyl)(l ,2-phenylene-(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10/429,024, filed May 2, 2003, and WO 04/24740.
- Catalyst (A3) is bis[N,N' "-(2,4,6- tri(methylphenyl)amido)ethylenediamine]hafnium dibenzyl
- Catalyst (A4) is bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl>
- Catalyst (Bl) is l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(l- methylethyl)immino)methyl)(2-oxoyl) zirconium dibenzyl
- Catalyst (B2) is l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(2-methylcyclohexyl)- immino)methyl)(2-oxoyl) zirconium dibenzyl
- Catalyst (Cl) is (t-butylamido)dimethyl(3-N-pyrrolyl-l,2,3,3a,7a- ⁇ -inden-l- yl)silanetitanium dimethyl prepared substantially according to the techniques of USP 6,268,444:
- Catalyst (C2) is (t-butylamido)di(4-methylphenyl)(2-methyl-l,2,3,3a,7a- ⁇ - inden-l-yl)silanetitanium dimethyl prepared substantially according to the teachings of US- A-2003/004286:
- Catalyst (C3) is (t-butylamido)di(4-methylphenyl)(2-methyl-l,2,3,3a,8a- ⁇ -s- indacen-l-yl)silanetitanium dimethyl prepared substantially according to the teachings of US- A-2003/004286:
- Catalyst (Dl) is bis(dimethyldisiloxane)(indene-l-yl)zirconium dichloride available from Sigma-Aldrich:
- shuttling agents include 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-octylaluminum bis(2,6-di-t-butylphenoxide, n- octylaluminum di(ethyl(l-naphthyl) amide), ethylalum
- the foregoing process takes the form of a continuous solution process for forming block copolymers, especially multi-block copolymers, preferably linear multi-block copolymers of two or more monomers, more especially ethylene and a C 3 _ 2 o olefin or cycloolefin, and most especially ethylene and a C 4 _ 2 o ⁇ -olefin, using multiple catalysts that are incapable of intercon version. That is, the catalysts are chemically distinct.
- the process is ideally suited for polymerization of mixtures of monomers at high monomer conversions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes advantaged compared to chain growth, and multi -block copolymers, especially linear multi- block copolymers are formed in high efficiency.
- inventive interpolymers may be differentiated from conventional, random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition, fluxional catalysts, anionic or cationic living polymerization techniques.
- inventive interpolymers compared to a random copolymer of the same monomers and monomer content at equivalent crystallinity or modulus, the inventive interpolymers have better (higher) heat resistance as measured by melting point, higher TMA penetration temperature, higher high- temperature tensile strength, and/or higher high-temperature torsion storage modulus as determined by dynamic mechanical analysis.
- the inventive interpolymers Compared to a random copolymer containing the same monomers and monomer content, the inventive interpolymers have lower compression set, particularly at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, faster setup due to higher crystallization (solidification) temperature, higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better oil and filler acceptance.
- the inventive interpolymers also exhibit a unique crystallization and branching distribution relationship.
- the inventive interpolymers have a relatively large difference between the tallest peak temperature measured using CRYSTAF and DSC as a function of heat of fusion, especially as compared to random copolymers containing the same monomers and monomer level or physical blends of polymers, such as a blend of a high density polymer and a lower density copolymer, at equivalent overall density. It is believed that this unique feature of the inventive interpolymers is due to the unique distribution of the comonomer in blocks within the polymer backbone.
- the inventive interpolymers may comprise alternating blocks of differing comonomer content (including homopolymer blocks).
- inventive interpolymers may also comprise a distribution in number and/or block size of polymer blocks of differing density or comonomer content, which is a Schultz-Flory type of distribution.
- inventive interpolymers also have a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus, and morphology.
- the microcrystalline order of the polymers demonstrates characteristic spherulites and lamellae that are distinguishable from random or block copolymers, even at PDI values that are less than 1.7, or even less than 1.5, down to less than 1.3.
- inventive interpolymers may be prepared using techniques to influence the degree or level of blockiness. That is the amount of comonomer and length of each polymer block or segment can be altered by controlling the ratio and type of catalysts and shuttling agent as well as the temperature of the polymerization, and other polymerization variables.
- a surprising benefit of this phenomenon is the discovery that as the degree of blockiness is increased, the optical properties, tear strength, and high temperature recovery properties of the resulting polymer are improved. In particular, haze decreases while clarity, tear strength, and high temperature recovery properties increase as the average number of blocks in the polymer increases.
- shuttling agents and catalyst combinations having the desired chain transferring ability high rates of shuttling with low levels of chain termination
- other forms of polymer termination are effectively suppressed. Accordingly, little if any ⁇ -hydride elimination is observed in the polymerization of ethylene/ ⁇ -olefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, possessing little or no long chain branching.
- Polymers with highly crystalline chain ends can be selectively prepared in accordance with embodiments of the invention.
- reducing the relative quantity of polymer that terminates with an amorphous block reduces the intermolecular dilutive effect on crystalline regions.
- This result can be obtained by choosing chain shuttling agents and catalysts having an appropriate response to hydrogen or other chain terminating agents. Specifically, if the catalyst which produces highly crystalline polymer is more susceptible to chain termination (such as by use of hydrogen) than the catalyst responsible for producing the less crystalline polymer segment (such as through higher comonomer incorporation, regio-error, or atactic polymer formation), then the highly crystalline polymer segments will preferentially populate the terminal portions of the polymer.
- the ethylene ⁇ -olefin interpolymers used in the embodiments of the invention are preferably interpolymers of ethylene with at least one C3-C20 ⁇ -olefin. Copolymers of ethylene and a C3-C2O ⁇ -olefin are especially preferred.
- the interpolymers may further comprise C4-C18 diolefin and/or alkenylbenzene.
- Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes, etc. Examples of such comonomers include C3-C20 ⁇ -olefins such as propylene, isobutylene, 1-butene, 1-hexene,
- 1- Butene and 1-octene are especially preferred.
- Other suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1 ,4-hexadiene, 1,7-octadiene, and naphthenics (e.g., cyclopentene, cyclohexene and cyclooctene).
- ethylene/ ⁇ -olefin interpolymers are preferred polymers, other ethylene/olefin polymers may also be used.
- Olefins as used herein refer to a family of unsaturated hydrocarbon-based compounds with at least one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention.
- suitable olefins are C3-C2O aliphatic and aromatic compounds containing vinylic unsaturation, as well as cyclic compounds, such as cyclobutene, cyclopentene, dicyclopentadiene, and norbornene, including but not limited to, norbornene substituted in the 5 and 6 position with C1-C20 hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefin compounds.
- olefin monomers include, but are not limited to 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, C4-C40 dienes, including but not limited to 1,3 -butadiene, 1,3-pentadiene, 1,4-hexa
- the ⁇ -olefin is propylene, 1-butene, 1- pentene, 1-hexene, 1-octene or a combination thereof.
- any hydrocarbon containing a vinyl group potentially may be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.
- polystyrene polystyrene
- olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, and the like.
- interpolymers comprising ethylene and styrene can be prepared by following the teachings herein.
- copolymers comprising ethylene, styrene and a C3-C20 alpha olefin, optionally comprising a C4-C2O diene, having improved properties can be prepared.
- Suitable non-conjugated diene monomers can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.
- suitable non-conjugated dienes include, but are not limited to, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5 -methyl- 1,4-hexadiene; 3,7-dimethyl-l,6-octadiene; 3,7-dimethyl-l,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and multi-
- the 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).
- the especially preferred dienes are 5- ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
- One class of desirable polymers that can be made in accordance with embodiments of the invention are elastomeric interpolymers of ethylene, a C3-C2O ⁇ -olefin, especially propylene, and optionally one or more diene monomers.
- suitable ⁇ -olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- 1-pentene, and 1-octene.
- a particularly preferred diene is 5-ethylidene-2-norbornene.
- the diene containing polymers comprise alternating segments or blocks containing greater or lesser quantities of the diene (including none) and ⁇ -olefin (including none)
- the total quantity of diene and ⁇ -olefin may be reduced without loss of subsequent polymer properties. That is, because the diene and ⁇ -olefin monomers are preferentially incorporated into one type of block of the polymer rather than uniformly or randomly throughout the polymer, they are more efficiently utilized and subsequently the crosslink density of the polymer can be better controlled.
- Such crosslinkable elastomers and the cured products have advantaged properties, including higher tensile strength and better elastic recovery.
- the inventive interpolymers made with two catalysts incorporating differing quantities of comonomer have a weight ratio of blocks formed thereby from 95:5 to 5:95.
- the elastomeric polymers desirably have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an ⁇ -olefin content of from 10 to 80 percent, based on the total weight of the polymer.
- the multi-block elastomeric polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an ⁇ -olefin content of from 10 to 40 percent, based on the total weight of the polymer.
- the ethylene/ ⁇ -olefin interpolymers can be functionalized by incorporating at least one functional group in its polymer structure.
- exemplary functional groups may include, for example, ethylenically unsaturated mono- and di-functional carboxylic acids, ethylenically unsaturated mono- and di-functional carboxylic acid anhydrides, salts thereof and esters thereof.
- Such functional groups may be grafted to an ethylene/ ⁇ -olefin interpolymer, or it may be copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene, the functional comonomer and optionally other comonomer(s).
- the amount of the functional group present in the functional interpolymer can vary.
- the functional group can typically be present in a copolymer-type functionalized interpolymer in an amount of at least about 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent.
- the functional group will typically be present in a copolymer-type functionalized interpolymer in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.
- the composition can comprise at least two other components, in addition to the interpolymer, for the purposes of improving and/or controlling the viscosity, adhesive properties, shelf-life, stability and cost.
- the composition comprises a tackifier and an oil or a low molecular weight polymer in addition to the interpolymer.
- additional components include waxes, antioxidants, UV stabilizers, colorants or pigments, fillers, flow aids, coupling agents, crosslinking agents, surfactants, solvents, and combinations thereof.
- the tackifier of the composition may modify the properties of the composition such as viscoelastic properties (e.g., storage modulus, viscous modulus, tan delta), rheological properties (e.g., viscosity), tackiness (i.e., ability to stick), pressure sensitivity, and wetting property.
- the tackifier is used to improve the tackiness of the composition.
- the tackifier is used to reduce the viscosity of the composition.
- the tackifier is used to render the composition a pressure-sensitive adhesive.
- the tackifier is used to wet out adherent surfaces and/or improve the adhesion to the adherent surfaces.
- Tackifiers suitable for the compositions disclosed herein can be solids, semi-solids, or liquids at room temperature.
- Non-limiting examples of tackifiers include (1) natural and modified rosins (e.g., 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 (e.g., the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin); (3) copoly
- the tackifiers include rosin-based tackifiers (e.g.
- the tackifiers include polyterpenes or terpene resins (e.g., SYLV ARES® terpene resins from Arizona Chemical, Jacksonville, FL).
- the tackifiers include aliphatic hydrocarbon resins such as resins resulting from the polymerization of monomers consisting of olefins and diolefins (e.g., ESCOREZ® 1310LC, ESCOREZ® 2596 from ExxonMobil Chemical Company, Houston, Tex.
- the tackifiers include hydrogenated cyclic hydrocarbon resins (e. g. REGALREZ® and REGALITE® resins from Eastman Chemical Company).
- the tackifiers are modified with tackifier modifiers including aromatic compounds (e.g., ESCOREZ® 2596 from
- the tackifier is an aliphatic hydrocarbon resin having at least five carbon atoms.
- the tackifier has a Ring and Ball (R&B) softening point equal to or greater than 8O 0 C.
- the Ring and Ball (R&B) softening point can be measured by the method described in ASTM E28, which is incorporated herein by reference.
- the performance characteristics of the tackifier in the composition disclosed herein can be directly related to its compatibility with the ethylene/ ⁇ - olefin interpolymer.
- compositions with desirable adhesive properties can be obtained with tackifiers that are compatible with the interpolymer.
- desirable tack properties can be produced.
- incompatible tackifiers may not produce desirable tack properties, they may be used to impact other desirable properties.
- the properties of the composition can be fine-tuned by the addition of a tackifier having limited compatibility to reduce the tack level and/or increase the cohesive strength characteristics.
- compositions disclosed herein comprise a plasticizer or plasticizing oil or an extender oil that may reduce viscosity and/or improve tack properties.
- plasticizers include olefin oligomers, low molecular weight polyolefins such as liquid polybutene, low molecular weight non-aromatic polymers (e.g. REGALREZ® 1018 from Eastman Chemical Company), phthalates, mineral oils such as naphthenic, paraffinic, or hydrogenated (white) oils (e.g. Kaydol oil or ParaLuxTM oils (Chevron U.S.A.
- Low molecular weight polyolefins may include those with Mw as low as 100, in particular, those in the range of from about 100 to 3000, in the range of from about 250 to about 2000 and in the range of from about 300 to about 1000. Paraffinic oils are especially preferred.
- the plasticizers include polypropylene, polybutene, hydrogenated polyisoprene, hydrogenated polybutadiene, polypiperylene and copolymers of piperylene and isoprene, and the like having average molecular weights between about 350 and about 10,000.
- the plasticizers include glyceryl esters of the usual fatty acids and polymerization products thereof.
- a suitable insoluble plasticizer may be selected from the group which includes dipropylene glycol dibenzoate, pentaerythritol tetrabenzoate; polyethylene glycol 400-di-2-ethylhexoate; 2-ethylhexyl diphenyl phsophate; butyl benzyl phthalate, dibutyl phthalate, dioctyl phthalate, various substituted citrates, and glycerates.
- Suitable dipropylene glycol dibenzoate and pentaerythritol tetrabenzoate may be purchased from Velsicol Chemical Company of Chicago, 111.
- Benzoflex 9- 88 and S-552 respectively.
- a suitable polyethylene glycol 400-di-2-ethylhexoate may be purchased from CP. Hall Company of Chicago, 111. under the trade designation “Tegmer 809”.
- a suitable 2-ethylhexyl diphenyl phosphate, and a butyl benzyl phthalate may be purchased from Monsanto Industrial Chemical Company of St. Louis, Mo. under the trade designation "Santicizer 141 and 160", respectively.
- Benzoflex is used as a plasticizer in an adhesive composition, it can delay the crystallization in diaper core stabilization adhesives, which are used to stabilize the thinner cores of diapers and adult incontinence products.
- the compositions disclosed herein optionally can comprise a wax that may reduce the melt viscosity in addition to reducing costs.
- a wax that may reduce the melt viscosity in addition to reducing costs.
- Any wax known to a person of ordinary skill in the art can be used in the adhesion composition disclosed herein.
- suitable waxes include petroleum waxes, polyolefin waxes such as low molecular weight polyethylene or polypropylene , synthetic waxes, paraffin and microcrystalline waxes having melting points from about 55 to about 110 0 C, Fischer- Tropsch waxes and combinations thereof.
- the wax is a low molecular weight polyethylene homopolymer or interpolymer having a number average molecular weight of about 400 to about 6,000 g/mole.
- the inventive interpolymer having such an average molecular weight can be used as a wax, in addition to the higher molecular weight inventive polymer being used as a polymeric component.
- the amount of the wax in the composition can be from greater than 0 to about 50 wt %, from about 10 to about 45 wt %, or from about 25 to about 40 wt % of the total weight of the composition.
- the tackifier to ethylene/ ⁇ -olefin block copolymer ratio is in the range of from about 3.2:1 to about 10:1, preferably about 3.5:1 to about 8:1, and more preferably about 4.0:1 to about 6.0:1.
- the oil or low molecular weight polymer to ethylene/ ⁇ -olefin block copolymer ratio may be an amount in the range of from about 1.2: 1 to about 3.0:1, preferably about 1.3:1 to about 2.5: 1, and more preferably in the range of from about 1.5:1 to about 2.0:1.
- compositions disclosed herein optionally can comprise an antioxidant or a stabilizer.
- Any antioxidant known to a person of ordinary skill in the art may be used in the adhesion composition disclosed herein.
- suitable antioxidants include amine-based antioxidants such as alkyl diphenylamines, phenyl- ⁇ - naphthylamine, alkyl or aralkyl substituted phenyl- ⁇ -naphthylamine, alkylated p- phenylene diamines, tetramethyl-diaminodiphenylamine and the like; and hindered phenol compounds such as 2,6-di-t-butyl-4-methylphenol; l,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl- 4'-hydroxybenzyl)benzene; tetrakis[(methylene(3,5-di-t-butyl-4- hydroxyhydrocinnamate
- the amount of the antioxidant in the composition can be from about greater than 0 to about 1 wt %, from about 0.05 to about 0.75 wt %, or from about 0.1 to about 0.5 wt % of the total weight of the composition.
- the compositions disclosed herein optionally can comprise an UV stabilizer that may prevent or reduce the degradation of the compositions by UV radiation.
- Any UV stabilizer known to a person of ordinary skill in the art may be used in the adhesion composition disclosed herein.
- suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, Formamidine carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, metallic salts, zinc compounds and combinations thereof.
- the amount of the UV stabilizer in the composition can be from about greater than 0 to about 1 wt %, from about 0.05 to about 0.75 wt %, or from about 0.1 to about 0.5 wt % of the total weight of the composition.
- compositions disclosed herein optionally can comprise a colorant or pigment.
- a colorant or pigment Any colorant or pigment known to a person of ordinary skill in the art may be used in the adhesion composition disclosed herein.
- suitable colorants or pigments include inorganic pigments such as titanium dioxide and carbon black, phthalocyanine pigments, and other organic pigments such as IRGAZIN®, CROMOPHT AL®, MONASTRAL®, CINQUASIA®, IRGALITE®, ORASOL®, all of which are available from Ciba Specialty Chemicals, Tarrytown, NY.
- the amount of the colorant or pigment in the composition can be from about greater than 0 to about 10 wt %, from about 0.1 to about 5 wt %, or from about 0.5 to about 2 wt % of the total weight of the composition.
- compositions disclosed herein may also optionally comprise a fragrance such as a perfume or other odorant.
- a fragrance such as a perfume or other odorant.
- Such fragrances may be contained in release agents such as microcapsules that may, for example, release fragrance upon removal of a release liner from the composition.
- the compositions disclosed herein optionally can comprise a filler.
- a filler Any filler known to a person of ordinary skill in the art may be used in the adhesion composition disclosed herein.
- suitable fillers include sand, talc, dolomite, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass bead, glass microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood flour, and combinations thereof.
- the amount of the filler in the composition can be from about greater than 0 to about 60 wt %, from about 1 to about 50 wt %, or from about 5 to about 40 wt % of the total weight of the composition.
- the Hildebrand solubility parameter for a copolymer may be calculated using a volume fraction weighting of the individual Hildebrand solubility parameters for each monomer comprising the copolymer, as described for binary copolymers in Barton A. F.
- Hildebrand solubility parameter for polymeric materials is also known to be weakly dependent upon the molecular weight of the polymer, as noted in Barton, pages 446-448. Therefore, there will be a preferred molecular weight range for a given ethylene/ ⁇ -olefin interpolymer, and adhesive strength may be additionally controlled by manipulating the molecular weight of the ethylene/ ⁇ -olefin interpolymer or the additives such as the tackifier.
- the cloud point is usually close to the melting point of the wax.
- the lower the cloud point temperature the greater the compatibility.
- the cloud point measurement is disclosed in "Adhesives and Coatings Manual” by National Distillers and Chemical Corporation (1983), which is incorporated herein by reference.
- Dynamic mechanical analysis can be another technique to identify compatibility characteristics of the additives with the ethylene/ ⁇ -olefin interpolymer.
- an additive such as the tackifier having a first glass transition temperature (Tg)
- Tg first glass transition temperature
- DMA generally reveals one single glass transition zone but with the second Tg shift to a different temperature due to the contribution of the first Tg. This indicates an intimate mix (solubility) between the tackifier and the ethylene/ ⁇ -olefin interpolymer.
- DMA can detect a separate phase transition for each of the tackifier and the ethylene/ ⁇ -olefin interpolymer.
- the ingredients of the compositions are melt blended by a method as described by Guerin et al. in U.S. Patent No. 4,152,189. That is, all solvent
- Physical blending devices that provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing can be useful in preparing homogenous blends. Both batch and continuous methods of physical blending can be used. Non- limiting examples of batch methods include those methods using BRABENDER® mixing equipment (e.g., BRABENDER PREP CENTER®, available from C. W. Brabender Instruments, Inc., Southhackensack, N. J.), Sigma blade mixing, or B ANBURY® internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment.
- BRABENDER® mixing equipment e.g., BRABENDER PREP CENTER®, available from C. W. Brabender Instruments, Inc., Southhackensack, N. J.
- Sigma blade mixing e.g., Sigma blade mixing, or B ANBURY® internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment.
- the mixing time required for blending the formulation is in the range of from 5 min to 20 min, and preferably in the range of from 10 min to 15 minutes.
- continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding.
- An aqueous dispersion of the ethylene/ ⁇ -olefin interpolymer may also be used in the formulation of various compositions.
- U.S. Patent No. 5,574,091, incorporated by reference herein in its entirety teaches the preparation of aqueous dispersions of olefin copolymers in the presence of a stabilizing and an emulsifying amount of a suitable surfactant, such as sulfate of an ethoxylated phenol, e.g., poly(oxy-l,2-ethanediyl) ⁇ -sulfo- ⁇ (nonylphonoxy) ammonium salt.
- a suitable surfactant such as sulfate of an ethoxylated phenol, e.g., poly(oxy-l,2-ethanediyl) ⁇ -sulfo- ⁇ (nonylphonoxy) ammonium salt.
- Such methods can also be used to make aqueous dispersions of the ethylene/
- compositions disclosed herein can be used as hot melt adhesives, pressure sensitive adhesives, hot melt pressure sensitive adhesives or as thermoplastic marking compositions. It can be applied to manufacture any article that requires or comprises a hot melt adhesive or a pressure sensitive adhesive.
- suitable articles include paper products, packaging materials, laminated wood panels, kitchen countertops, vehicles, labels, disposable diapers, hospital pads, feminine sanitary napkins, surgical drapes, tapes, cases, cartons, trays, medical devices, and bandages.
- the adhesive composition can be used in tapes, cases, cartons, trays, medical devices, and bandages.
- the compositions are used as hot melt adhesives.
- hot melt adhesive compositions can be used in industrial applications including packaging, particularly for low temperature use such as for dairy products or for freezer packaging of food products, and in sanitary disposable consumer articles, for example, diapers, feminine care pads, napkins, and the like. Some other suitable applications include book-binding, wood working and labeling.
- compositions disclosed herein may be used as PSAs.
- PSA compositions can be applied to sheeting products (e.g., decorative, reflective, and graphical), labelstock, and tape backings.
- the substrate can be any suitable type of material depending on the desired application.
- the substrate comprises a nonwoven, paper, polymeric film (e.g., polypropylene (e.g., biaxially oriented polypropylene (BOPP)), polyethylene, polyurea, polybutylene or a polyethylene-polypropylene copolymer, but may also be wholly or partly polyamide such as nylon, polyester such as polyethylene terephthalate, polyvinylidene fluoride, polyacrylate such as poly(methyl methacry late) (only in blends) and the like or polyester (e.g., polyethylene terephthalate (PET)), and blends thereof, or release liner (e.g., siliconized liner).
- polypropylene e.g., biaxially oriented polypropylene (BOPP)
- POPP biaxially oriented polypropylene
- polyethylene polyurea
- polyamide such as nylon
- polyester such as polyethylene terephthalate,
- the compositions can be utilized to form tape.
- the PSA or hot melt adhesive composition is applied to at least one side of the backing of the tape.
- the adhesive composition may then be crosslinked to further improve its shear strength. Any suitable crosslinking method (e.g., exposure to radiation, such as ultraviolet or electron beam) or crosslinker additive (e.g., phenolic and silane curatives) may be utilized.
- the adhesive compositions disclosed herein may be applied to the desired substrate or adhered in any manner known in the art, particularly those methods used traditionally for making tapes, cases, cartons, trays, medical devices, health and hygiene applications and bandages.
- the adhesive compositions can be applied by a coating head or nozzle, with associated equipment.
- the adhesive compositions can be applied as fine lines, dots or spray coatings, in addition to other traditional forms as desired.
- the adhesive compositions may be applied via spiral spray techniques.
- the compositions of the present invention may be applied at lower temperatures as compared to conventional such adhesive compositions.
- the composition may be applied at temperatures in the range of from about 110 0 C to about 150 0 C, preferably in the range of from about 115 0 C to 140 0 C, and more preferably in the range of from about
- the substrate is a polyethylene backing sheet.
- the method further comprises forming a laminate by applying a nonwoven sheet onto the adhesive on the substrate after applying the adhesive.
- the nonwoven sheet comprises a spunbond polypropylene sheet.
- the adhesive compositions can be applied using melt extrusion techniques.
- the adhesive composition can be applied by either continuous or batch processes.
- An example of a batch process is the placement of a portion of the adhesive composition between a substrate to which the adhesive composition is to be adhered and a surface capable of releasing the adhesive to form a composite structure.
- An example of a continuous forming method includes drawing the adhesive composition out of a heated film die and subsequently contacting the drawn composition to a moving plastic web or other suitable substrate.
- the adhesive compositions can be coated using a solvent-based method.
- the solvent-based adhesive composition can be coated by such methods as knife coating, roll coating, gravure coating, rod coating, curtain coating, and air knife coating.
- the coated solvent-based adhesive composition is then dried to remove the solvent.
- the applied solvent-based adhesive composition is subjected to elevated temperatures, such as those supplied by an oven, to expedite drying.
- the compositions disclosed herein are used as thermoplastic marking compositions for marking roads.
- the filler will be provided to the thermoplastic marking composition in an amount of from 40 to 90 weight percent, preferably from 50 to 90 weight percent.
- the filler will comprise a combination of the following: 0 to 60 weight percent sand, 0 to 100 percent dolomite or talc, 0 to 50 weight percent glass microspheres, and 1 to 20 weight percent pigment.
- thermoplastic coating composition When it is desired that the thermoplastic coating composition have reflective attributes, a reflective inorganic filler will be employed.
- One particularly preferred reflective inorganic filler is glass microspheres.
- a reflective inorganic filler When a reflective inorganic filler is employed, it will typically be provided to the thermoplastic coating composition in an amount of at least 5 weight percent, preferably at least 10 weight percent, and more preferably at least 20 weight percent.
- the reflective inorganic filler will be provided to the thermoplastic coating composition in an amount of no more than 70, preferably no more than 50 weight percent, and most preferably no more than 40 weight percent.
- thermoplastic marking compositions are advantageous in that they may be readily designed to be applied by the various techniques used in the industry. For instance, it is now possible to develop a single formulation, which may be usefully applied by extrusion, screed, or spray techniques.
- the thermoplastic marking compositions will preferably exhibit an adhesion, as measured in accordance with the techniques set forth in Example Two of U.S. Patent No. 6,552,110, of at least 1.0 N/mm 2 , preferably at least 1.2 N/mm 2 , more preferably at least 1.3 N/mm , and most preferably at least 1.5 N/mm .
- U.S. Patent No. 6,552,110 is incorporated herein by reference.
- thermoplastic marking compositions will preferably exhibit a luminance factor, as measured in accordance with the techniques set forth in Example Two of U.S. Patent No. 6,552,110, of at least 70, preferably at least 75, more preferably at least 76, and most preferably at least 78.
- thermoplastic marking compositions further exhibit good low temperature abrasion resistance.
- the subject formulations exhibit improved low temperature flexibility and low temperature adhesion, and exhibit improved smoke and low odor properties at high temperatures.
- the subject formulations exhibit a broad potential range of application temperatures, particularly at temperatures of from 150 0 C to 250 0 C, which makes them suitable for application by different means. For instance, the ability of the compositions to be applied at lower application temperatures, that is, temperatures of about 150 to 170 0 C, makes them suitable for application by extrusion coating techniques; while the ability of the compositions to be applied at higher application temperatures, that is, temperatures of 200 0 C to 250 0 C makes them suitable for application by spray coating techniques.
- the subject formulations are preferably resistant to dirt pick-up, and further preferably exhibit less viscosity variability relative to systems which lack the homogeneous ethylene polymer.
- the subject formulations are usefully applied via spray, screed, and extrusion techniques.
- the subject formulations may be provided as preformed tapes, which are laid upon the surface and bonded to it by heating with, for example, a gas flame, optionally under some applied pressure, as by rolling.
- thermoplastic marking compositions are in hot melt extrusion road marking; hot melt spray road marking; hot melt hand applied road markings; colored hot melt marked bicycle lanes applied by spray or extrusion; marking of simulation/training roads for icy surface driving; preformed extruded traffic symbols (such as arrows, letters, etc.) and tapes (such as for traffic safety, information, decoration, etc.) (also called premarks or hot melt tapes); marking of flexible and soft sports/playground surfaces, such as tartan (for instance, in the marking of tennis courts, outdoor and indoor sports floorings, etc.); safety markings on ships, oil rigs, etc.; and reflecting traffic safety coatings for tunnels, concrete, metals with glass beads or other reflecting/self-glowing pigments.
- preformed extruded traffic symbols such as arrows, letters, etc.
- tapes such as for traffic safety, information, decoration, etc.
- marking of flexible and soft sports/playground surfaces such as tartan (for instance, in the marking of tennis courts, outdoor and indoor sports floorings, etc
- the subject thermoplastic marking compositions will be employed in embossed road markings.
- Embossed road markings are formed by extrusion of a marking composition onto a surface; applying reflective particles, such as glass beads, to the extruded marking; and embossing the extruded marking such as to create channels or other ridges.
- Such embossed markings are desirable, in that they provide enhanced water drainage and improve nighttime reflective properties, particularly in rainy weather.
- the thermoplastic marking compositions of the invention are advantageous in embossed road marking applications, as they provide the requisite degree of flexibility, adhesion, and abrasion, even under cold temperature conditions.
- An adhesive composition comprising:
- (a) has a M w /M n from about 1.7 to about 3.5, at least one melting point, T m , in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of T m and d correspond to the relationship: T m > -2002.9 + 4538.5(d) - 2422.2(d) 2 , or
- (b) has a M w /M n from about 1.7 to about 3.5, and is characterized by a heat of fusion, ⁇ H in J/g, and a delta quantity, ⁇ T, in degrees Celsius, defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ⁇ T and ⁇ H have the following relationships: ⁇ T > -0.1299( ⁇ H) + 62.81 for ⁇ H greater than zero and up to 130 J/g,
- ⁇ T > 48°C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 0 C; or (c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/ ⁇ - olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/ ⁇ -olefin interpolymer is substantially free of a cross-linked phase: Re >1481-1629(d); or
- (d) has a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ -olefin interpolymer; or
- (e) has a storage modulus at 25°C, G'(25°C), and a storage modulus at 100 0 C, G' (100 0 C), wherein the ratio of G' (25°C) to G' (100 0 C) is in the range of about 1:1 to about 9:1; or
- (f) has a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1; or (g) has an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; and,
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer has a M w /M n from about 1.7 to about 3.5, at least one melting point, T m , in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of T m and d correspond to the relationship: T m > 858.91 - 1825.3(d) + 1112.8(d) 2 .
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer has a M w /M n from about 1.7 to about 3.5 and is characterized by a heat of fusion, ⁇ H in J/g, and a delta quantity, ⁇ T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ⁇ T and ⁇ H have the following relationships: ⁇ T > -0.1299( ⁇ H) + 62.81 for ⁇ H greater than zero and up to 130 J/g, ⁇ T > 48°C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 0 C.
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/ ⁇ -olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/ ⁇ -olefin interpolymer is substantially free of a cross-linked phase:
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer has a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ -olefin interpolymer.
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer has a storage modulus at 25°C, G'(25°C), and a storage modulus at 100 0 C, G'(100°C), wherein the ratio of G'(25°C) to G'(100°C) is in the range of about 1: 1 to about 9:1.
- the composition is a hot melt adhesive composition, a pressure sensitive adhesive composition or a thermoplastic marking composition.
- composition of embodiment 1, wherein the ⁇ -olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-l-pentene, norbornene, 1-decene, 1,5-hexadiene, or a combination thereof.
- composition of embodiment 1, wherein the tackifier has a R&B softening point equal to or greater than 8O 0 C. 14. The composition of embodiment 1, wherein the oil is present in an amount in the range of between 0 wt% to about 30 wt%, by weight of the total composition.
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer has a density of about 0.86 to about 0.875 g/cc.
- composition of embodiment 1, wherein the ethylene/ ⁇ -olefin interpolymer has a melt index of about 5 to about 50 g/10 minutes.
- a method of applying the composition of embodiment 1 to a substrate comprising: applying the composition to the substrate at a temperature in the range of from about 100 0 C to about 150 0 C.
- T m > 858.91 - 1825.3(d) + 1112.8(d) 2 .
- the ethylene/ ⁇ -olefin interpolymer has a M w /M n from about 1.7 to about 3.5 and is characterized by a heat of fusion, ⁇ H in J/g, and a delta quantity, ⁇ T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ⁇ T and ⁇ H have the following relationships:
- the ethylene/ ⁇ -olefin interpolymer has a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ -olefin interpolymer.
- composition is a hot melt adhesive composition, a pressure sensitive adhesive composition or a thermoplastic marking composition.
- ⁇ -olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-l-pentene, norbornene, 1-decene, 1,5- hexadiene, or a combination thereof.
- the tackifier is present in the range from about 15 wt% to about 75 wt %, by weight of the total composition.
- An automated liquid-handling robot equipped with a heated needle set to 16O 0 C is used to add enough 1,2,4-trichlorobenzene stabilized with 300 ppm Ionol to each dried polymer sample to give a final concentration of 30 mg/mL.
- a small glass stir rod is placed into each tube and the samples are heated to 16O 0 C for 2 hours on a heated, orbital- shaker rotating at 250 rpm.
- the concentrated polymer solution is then diluted to 1 mg/ml using the automated liquid-handling robot and the heated needle set to 16O 0 C.
- a Symyx Rapid GPC system is used to determine the molecular weight data for each sample.
- a Gilson 350 pump set at 2.0 ml/min flow rate is used to pump helium- purged 1,2-dichlorobenzene stabilized with 300 ppm Ionol as the mobile phase through three Plgel 10 micrometer ( ⁇ m) Mixed B 300mm x 7.5mm columns placed in series and heated to 16O 0 C.
- a Polymer Labs ELS 1000 Detector is used with the Evaporator set to 25O 0 C, the Nebulizer set to 165 0 C, and the nitrogen flow rate set to 1.8 SLM at a pressure of 60-80 psi (400-600 kPa) N 2 .
- the polymer samples are heated to 16O 0 C and each sample injected into a 250 ⁇ l loop using the liquid-handling robot and a heated needle. Serial analysis of the polymer samples using two switched loops and overlapping injections are used. The sample data is collected and analyzed using Symyx EpochTM software. Peaks are manually integrated and the molecular weight information reported uncorrected against a polystyrene standard calibration curve.
- Branching distributions are determined by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from
- PolymerChar Valencia, Spain.
- the samples are dissolved in 1,2,4 trichlorobenzene at 160 0 C (0.66 mg/mL) for 1 hr and stabilized at 95 0 C for 45 minutes.
- the sampling temperatures range from 95 to 30 0 C at a cooling rate of 0.2°C/min.
- An infrared detector is used to measure the polymer solution concentrations.
- the cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased.
- the analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.
- the CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF Software (Version 200 Lb, PolymerChar, Valencia, Spain).
- the CRYSTAF peak finding routine identifies a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve.
- the preferred processing parameters are with a temperature limit of 70 0 C and with smoothing parameters above the temperature limit of 0.1, and below the temperature limit of 0.3.
- DSC Standard Method Excluding Samples 1-4 and A-C
- the DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30 0 C and end of melting.
- the heat of fusion is measured as the area under the melting curve between -30 0 C and the end of melting using a linear baseline.
- the gel permeation chromatographic system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument.
- the column and carousel compartments are operated at 140 0 C.
- Three Polymer Laboratories 10- micron Mixed-B columns are used.
- the solvent is 1,2,4 trichlorobenzene.
- the samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxy toluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160 0 C.
- the injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.
- the narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation.
- the polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, L Polvm. ScL, Polvm. Let., 6, 621 (1968)):
- Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B. Flexural/Secant Modulus/ Storage Modulus
- Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D 1746.
- E f is the strain taken for cyclic loading
- ⁇ s is the strain where the load returns to the baseline during the 1 st unloading cycle.
- L 0 is the load at 50% strain at 0 time and L 12 is the load at 50 percent strain after 12 hours.
- DMA Dynamic Mechanical Analysis
- a 1.5mm plaque is pressed and cut in a bar of dimensions 32xl2mm.
- the sample is clamped at both ends between fixtures separated by 10mm (grip separation ⁇ L) and subjected to successive temperature steps from -100 0 C to 200 0 C (5 0 C per step).
- the torsion modulus G' is measured at an angular frequency of 10 rad/s, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.
- Analytical temperature rising elution fractionation (ATREF) analysis is conducted according to the method described in USP 4,798,081 and Wilde, L.; RyIe, T.R.; Knobeloch, D.C.; Peat, LR. ; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. ScL, 20, 441-455 (1982), which are incorporated by reference herein in their entirety..
- the composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20 0 C at a cooling rate of 0.1°C/min.
- the samples are prepared by adding approximately 3g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube.
- the samples are dissolved and homogenized by heating the tube and its contents to 15O 0 C.
- the data are collected using a JEOL EclipseTM 400MHz spectrometer or a Varian Unity PlusTM 400MHz spectrometer, corresponding to a 13C resonance frequency of 100.5 MHz.
- the data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together.
- the spectral width is 25,000 Hz with a minimum file size of 32K data points.
- the samples are analyzed at 130 0 C in a 10 mm broad band probe.
- the comonomer incorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which is incorporated by reference herein in its entirety.
- TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of 1 ,2,4-trichlorobenzene (TCB) by stirring for 4 hours at 16O 0 C.
- the polymer solution is forced by 15 psig (100 kPa) nitrogen onto a 3 inch by 4 foot (7.6 cm x 12 cm) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 ⁇ m) spherical, technical quality glass beads (available from Potters Industries, HC 30 Box 20, Brownwood, TX, 76801) and stainless steel, 0.028" (0.7mm) diameter cut wire shot (available from Pellets, Inc., 63 Industrial Drive, North Tonawanda, NY, 14120).
- the column is immersed in a thermally controlled oil jacket, set initially to 160 0 C.
- the column is first cooled ballistically to 125 0 C, then slow cooled to 20 0 C at 0.04 0 C per minute and held for one hour.
- Fresh TCB is introduced at about 65 ml/min while the temperature is increased at 0.167 0 C per minute.
- Approximately 2000 ml portions of eluant from the preparative TREF column are collected in a 16 station, heated fraction collector.
- the polymer is concentrated in each fraction using a rotary evaporator until about 50 to 100 ml of the polymer solution remains.
- the concentrated solutions are allowed to stand overnight before adding excess methanol, filtering, and rinsing (approx. 300-500 ml of methanol including the final rinse).
- the filtration step is performed on a 3 position vacuum assisted filtering station using 5.0 ⁇ m polytetrafluoroethylene coated filter paper (available from Osmonics Inc., Cat
- Melt Strength is measured by using a capillary rheometer fitted with a 2.1 mm diameter, 20:1 die with an entrance angle of approximately 45 degrees. After equilibrating the samples at 190 0 C for 10 minutes, the piston is run at a speed of 1 inch/minute (2.54 cm/minute). The standard test temperature is 190 0 C. The sample is drawn uniaxially to a set of accelerating nips located 100 mm below the die with an acceleration of 2.4 mm/sec 2 . The required tensile force is recorded as a function of the take-up speed of the nip rolls. The maximum tensile force attained during the test is defined as the melt strength. In the case of polymer melt exhibiting draw resonance, the tensile force before the onset of draw resonance was taken as melt strength. The melt strength is recorded in centiNewtons ("cN").
- catalyst (Bl) is conducted as follows. a) Preparation of (l-methylethyl)(2-hvdroxy-3,5-di(t-butyl)phenyl)methylimine
- catalyst (B 2) is conducted as follows. a) Preparation of (l-(2-methylcvclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine [166] 2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25°C for 12 hrs.
- shuttling agents include diethylzinc (DEZ, SAl), 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 (SAlO), i-butylaluminum bis (di(n-pentyl) amide) (SAI l), n-octylaluminum bis(2,6-di
- a series of polymerizations are conducted in a parallel pressure reactor (PPR) contained of 48 individual reactor cells in a 6 x 8 array that are fitted with a pre-weighed glass tube.
- the working volume in each reactor cell is 6000 ⁇ L.
- Each cell is temperature and pressure controlled with stirring provided by individual stirring paddles.
- the monomer gas and quench gas are plumbed directly into the PPR unit and controlled by automatic valves.
- Liquid reagents are robotically added to each reactor cell by syringes and the reservoir solvent is mixed alkanes.
- the order of addition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, and catalyst or catalyst mixture.
- the reagents are premixed in a small vial immediately prior to addition to the reactor.
- a reagent is omitted in an experiment, the above order of addition is otherwise maintained. Polymerizations are conducted for approximately 1-2 minutes, until predetermined ethylene consumptions are reached. After quenching with CO, the reactors are cooled and the glass tubes are unloaded.
- Examples 1-4 demonstrate the synthesis of linear block copolymers by the present invention as evidenced by the formation of a very narrow MWD, essentially monomodal copolymer when DEZ is present and a bimodal, broad molecular weight distribution product (a mixture of separately produced polymers) in the absence of DEZ. Due to the fact that Catalyst (Al) is known to incorporate more octene than Catalyst (Bl), the different blocks or segments of the resulting copolymers of the invention are distinguishable based on branching or density. Table 1
- the DSC curve for the polymer of example 1 shows a 115.7°C melting point (Tm) with a heat of fusion of 158.1 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 34.5°C with a peak area of 52.9 percent.
- the difference between the DSC Tm and the Tcrystaf is 81.2°C.
- the DSC curve for the polymer of example 2 shows a peak with a 109.7 0 C melting point (Tm) with a heat of fusion of 214.0 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 46.2°C with a peak area of 57.0 percent.
- the difference between the DSC Tm and the Tcrystaf is 63.5 0 C.
- the DSC curve for the polymer of example 3 shows a peak with a 120.7 0 C melting point (Tm) with a heat of fusion of 160.1 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 66.1°C with a peak area of 71.8 percent.
- the difference between the DSC Tm and the Tcrystaf is 54.6°C.
- the DSC curve for the polymer of example 4 shows a peak with a 104.5 0 C melting point (Tm) with a heat of fusion of 170.7 J/g.
- the corresponding CRYSTAF ⁇ curve shows the tallest peak at 30 0 C with a peak area of 18.2 percent.
- the difference between the DSC Tm and the Tcrystaf is 74.5 0 C.
- the DSC curve for Comparative Example A* shows a 90.0 0 C melting point (Tm) with a heat of fusion of 86.7 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 48.5°C with a peak area of 29.4 percent. Both of these values are consistent with a resin that is low in density.
- the difference between the DSC Tm and the Tcrystaf is 41.8°C.
- the DSC curve for Comparative Example B* shows a 129.8°C melting point (Tm) with a heat of fusion of 237.0 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 82.4°C with a peak area of 83.7 percent. Both of these values are consistent with a resin that is high in density.
- the difference between the DSC Tm and the Tcrystaf is 47.4°C.
- the DSC curve for Comparative Example C* shows a 125.3°C melting point (Tm) with a heat of fusion of 143.0 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 81.8 0 C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 0 C.
- the separation between the two peaks is consistent with the presence of a high crystalline and a low crystalline polymer.
- the difference between the DSC Tm and the Tcrystaf is 43.5 0 C.
- the DSC curve for the polymer of example 5 shows a peak with a 119.6 0 C melting point (Tm) with a heat of fusion of 60.0 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 47.6°C with a peak area of 59.5 percent.
- the delta between the DSC Tm and the Tcrystaf is 72.0 0 C.
- the DSC curve for the polymer of example 6 shows a peak with a 115.2 0 C melting point (Tm) with a heat of fusion of 60.4 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 44.2°C with a peak area of 62.7 percent.
- the delta between the DSC Tm and the Tcrystaf is 71.0 0 C.
- the DSC curve for the polymer of example 7 shows a peak with a 121.3 0 C melting point with a heat of fusion of 69.1 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 49.2°C with a peak area of 29.4 percent.
- the delta between the DSC Tm and the Tcrystaf is 72.1 0 C.
- the DSC curve for the polymer of example 8 shows a peak with a 123.5 0 C melting point (Tm) with a heat of fusion of 67.9 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 80.1 0 C with a peak area of 12.7 percent.
- the delta between the DSC Tm and the Tcrystaf is 43.4°C.
- the DSC curve for the polymer of example 9 shows a peak with a 124.6 0 C melting point (Tm) with a heat of fusion of 73.5 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 80.8 0 C with a peak area of 16.0 percent.
- the delta between the DSC Tm and the Tcrystaf is 43.8°C.
- the delta between the DSC Tm and the Tcrystaf is 83.2°C.
- the DSC curve for the polymer of example 13 shows a peak with a 114.4 0 C melting point (Tm) with a heat of fusion of 49.4 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 33.8 0 C with a peak area of 7.7 percent.
- the delta between the DSC Tm and the Tcrystaf is 84.4°C.
- the DSC for the polymer of example 14 shows a peak with a 120.8 0 C melting point (Tm) with a heat of fusion of 127.9 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 72.9 0 C with a peak area of 92.2 percent.
- the delta between the DSC Tm and the Tcrystaf is 47.9°C.
- the DSC curve for the polymer of example 15 shows a peak with a 114.3 0 C melting point (Tm) with a heat of fusion of 36.2 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 32.3 0 C with a peak area of 9.8 percent.
- the delta between the DSC Tm and the Tcrystaf is 82.0 0 C.
- the DSC curve for the polymer of example 17 shows a peak with a 116.0 0 C melting point (Tm) with a heat of fusion of 47.0 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 43.1 0 C with a peak area of 56.8 percent.
- the delta between the DSC Tm and the Tcrystaf is 72.9°C.
- the DSC curve for the polymer of example 18 shows a peak with a 120.5 0 C melting point (Tm) with a heat of fusion of 141.8 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 70.0 0 C with a peak area of 94.0 percent.
- the delta between the DSC Tm and the Tcrystaf is 50.5 0 C.
- the DSC curve for the polymer of example 19 shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 174.8 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 79.9 0 C with a peak area of 87.9 percent.
- the delta between the DSC Tm and the Tcrystaf is 45.0 0 C.
- the DSC curve for the polymer of Comparative Example E* shows a peak with a 124.0 0 C melting point (Tm) with a heat of fusion of 179.3 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 79.3°C with a peak area of 94.6 percent. Both of these values are consistent with a resin that is high in density.
- the delta between the DSC Tm and the Tcrystaf is 44.6°C.
- the DSC curve for the polymer of Comparative Example F* shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 90.4 J/g.
- the corresponding CRYSTAF curve shows the tallest peak at 77.6°C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of both a high crystalline and a low crystalline polymer.
- the delta between the DSC Tm and the Tcrystaf is 47.2°C.
- Comparative Example G* is a substantially linear ethylene/1-octene copolymer (AFFINITY®, available from The Dow Chemical Company)
- Comparative Example H* is an elastomeric, substantially linear ethylene/ 1-octene copolymer (AFFINITYOEG8100, available from The Dow Chemical Company)
- Comparative Example I* is a substantially linear ethylene/1-octene copolymer (AFFINIT Yd)PL 1840, available from The Dow Chemical Company)
- Comparative Example J* is a hydrogenated styrene/butadiene/styrene triblock copolymer (KRATONTM G1652, available from KRATON Polymers LLC)
- Comparative Example K* is a thermoplastic vulcanizate (TPV, a polyolefin blend containing dispersed therein a crosslinked elastomer). Results are presented in Table 4. Table 4 High Temperature Mechanical Properties
- Comparative Example F* (which is a physical blend of the two polymers resulting from simultaneous polymerizations using catalyst Al and Bl) has a 1 mm penetration temperature of about 70 0 C, while Examples 5-9 have a 1 mm penetration temperature of 100 0 C or greater. Further, examples 10-19 all have a 1 mm penetration temperature of greater than 85°C, with most having 1 mm TMA temperature of greater than 90 0 C or even greater than 100 0 C. This shows that the novel polymers have better dimensional stability at higher temperatures compared to a physical blend.
- Comparative Example J* (a commercial SEBS) has a good 1 mm TMA temperature of about 107 0 C, but it has very poor (high temperature 70 0 C) compression set of about 100 percent and it also failed to recover (sample broke) during a high temperature (80 0 C) 300 percent strain recovery.
- the exemplified polymers have a unique combination of properties unavailable even in some commercially available, high performance thermoplastic elastomers.
- Table 4 shows a low (good) storage modulus ratio
- Example 5 has a pellet blocking strength of 0 MPa, meaning it is free flowing under the conditions tested, compared to Comparatives F and G which show considerable blocking. Blocking strength is important since bulk shipment of polymers having large blocking strengths can result in product clumping or sticking together upon storage or shipping, resulting in poor handling properties.
- High temperature (70 0 C) compression set for the inventive polymers is generally good, meaning generally less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent.
- Comparatives F, G, H and J all have a 70 0 C compression set of 100 percent (the maximum possible value, indicating no recovery). Good high temperature compression set (low numerical values) is especially needed for applications such as gaskets, window profiles, o-rings, and the like.
- Table 5 shows results for mechanical properties for the new polymers as well as for various comparison polymers at ambient temperatures. It may be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 mm 3 , preferably less than about 80 mm 3 , and especially less than about 50 mm 3 . In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance.
- Tear strength as measured by tensile notched tear strength of the inventive polymers is generally 1000 mJ or higher, as shown in Table 5. Tear strength for the inventive polymers can be as high as 3000 mJ, or even as high as 5000 mJ. Comparative polymers generally have tear strengths no higher than 750 mJ.
- Table 5 also shows that the polymers of the invention have better retractive stress at 150 percent strain (demonstrated by higher retractive stress values) than some of the comparative samples.
- Comparative Examples F*, G* and H* have retractive stress value at 150 percent strain of 400 kPa or less, while the inventive polymers have retractive stress values at 150 percent strain of 500 kPa (Ex. 11) to as high as about 1100 kPa (Ex. 17).
- Polymers having higher than 150 percent retractive stress values would be quite useful for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics. Other applications include diaper, hygiene, and medical garment waistband applications, such as tabs and elastic bands.
- Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for the inventive polymers as compared to, for example, Comparative Example G*.
- Lower stress relaxation means that the polymer retains its force better in applications such as diapers and other garments where retention of elastic properties over long time periods at body temperatures is desired.
- optical properties reported in Table 6 are based on compression molded films substantially lacking in orientation. Optical properties of the polymers may be varied over wide ranges, due to variation in crystallite size, resulting from variation in the quantity of chain shuttling agent employed in the polymerization. Extractions of Multi-Block Copolymers
- the ether in the flask is evaporated under vacuum at ambient temperature, and the resulting solids are purged dry with nitrogen. Any residue is transferred to a weighed bottle using successive washes of hexane. The combined hexane washes are then evaporated with another nitrogen 66202
- a second clean round bottom flask charged with 350 mL of hexane is then connected to the extractor.
- the hexane is heated to reflux with stirring and maintained at reflux for 24 hours after hexane is first noticed condensing into the thimble. Heating is then stopped and the flask is allowed to cool. Any hexane remaining in the extractor is transferred back to the flask.
- the hexane is removed by evaporation under vacuum at ambient temperature, and any residue remaining in the flask is transferred to a weighed bottle using successive hexane washes.
- the hexane in the flask is evaporated by a nitrogen purge, and the residue is vacuum dried overnight at 40 0 C.
- Continuous solution polymerizations are carried out in a computer controlled well-mixed reactor.
- Purified mixed alkanes solvent IsoparTM E available from ExxonMobil Chemical Company
- ethylene, 1-octene, and hydrogen where used
- the feeds to the reactor are measured by mass-flow controllers.
- the temperature of the feed stream is controlled by use of a glycol cooled heat exchanger before entering the reactor.
- the catalyst component solutions are metered using pumps and mass flow meters.
- the reactor is run liquid-full at approximately 550 psig pressure.
- water and additive are injected in the polymer solution.
- the water hydrolyzes the catalysts, and terminates the polymerization reactions.
- the post reactor solution is then heated in preparation for a two- stage devolatization.
- the polymer melt is pumped to a die for underwater pellet cutting.
- Zn/C 2 *1000 (Zn feed flow*Zn concentration/1000000/Mw of Zn)/(Total Ethylene feed flow*(l-fractional ethylene conversion rate)/Mw of Ethylene)* 1000.
- Zn in “Zn/C 2 *1000” refers to the amount of zinc in diethyl zinc (“DEZ”) used in the polymerization process
- C2 refers to the amount of ethylene used in the polymerization process.
- Continuous solution polymerization is carried out in a computer controlled well-mixed reactor.
- Purified mixed alkanes solvent (ISOPARTM E available from ExxonMobil Chemical Company), ethylene, 1-octene, and hydrogen (if applicable) is combined and fed to a 102 L reactor.
- the feeds to the reactor are measured by mass-flow controllers.
- the temperature of the feed stream is controlled by use of a glycol cooled heat exchanger before entering the reactor.
- the catalyst component solutions are metered using pumps and mass flow meters.
- the reactor is run liquid-full at approximately 550 psig pressure.
- water and additive are injected in the polymer solution. The water hydrolyzes the catalysts, and terminates the polymerization reactions.
- Example 20 The post reactor solution is then heated in preparation for a two-stage devolatilization. The solvent and unreacted monomers are removed during the devolatilization process. The polymer melt is pumped to a die for underwater pellet cutting. Process details and results are contained in Tables 8 and 9. Testing of Example 20
- the CRYSTAF peak temperature and area were identified by the peak analysis module included in the CRYSTAF Software (Version 2001. b, PolymerChar, Valencia, Spain).
- the CRYSTAF peak finding routine identified a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve.
- the preferred processing parameters were with a temperature limit of 70 0 C and with smoothing parameters above the temperature limit of 0.1 , and below the temperature limit of 0.3.
- the CRYSTAF peak temperature and the peak area of each example are listed in Table 9 below. 66202
- the sample was then cooled to -4O 0 C at 10°C/min cooling rate and held at -4O 0 C for 3 minutes.
- the sample was then heated to 150 0 C at 10°C/minute heating rate.
- the cooling and second heating curves were recorded.
- the melting peak (T m ) and cooling peak (T c ) were determined.
- T m2 or T c2 The heat of fusion, T m and T c of each example are listed in Table 9 below.
- the gel permeation chromatographic system consisted of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL- 220 instrument. The column and carousel compartments were operated at 140 0 C. Three Polymer Laboratories 10-micron Mixed-B columns were used. The solvent was 1 ,2,4-trichlorobenzene. The 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 agitating lightly for 2 hours at 160 0 C. The injection volume used was 100 microliters and the flow rate was 1.0 ml/minute.
- Example 20 Various Physical Properties of Example 20
- the sample is placed in the chamber, which is in turn inserted into a Brookfield Thermosel and locked into place with bent needle-nose pliers.
- the sample chamber has a notch on the bottom that fits in the bottom of the Brookfield Thermosel to ensure that the chamber is not allowed to turn when the spindle is inserted and spinning.
- the sample is heated to the desired temperature (170°C/338°F).
- the viscometer apparatus is lowered and the spindle submerged into the sample chamber. Lowering is continued until brackets on the viscometer align on the Thermosel.
- the viscometer is turned on, and set to a shear rate which leads to a torque reading in the range of 40 to 70 percent. Readings are taken every minute for about 15 minutes, or until the values stabilize, and then the final reading is recorded.
- Formulation 1 may be applied at a significantly lower temperature with equal or better results than that of Formulation A, which could not be applied at 250 0 F.
- the initial peel strength of Formulation 1 is 5.5 pounds per linear inch and increases with aging to 15.2 pli and 14.2 pli. All of which would be useful in a diaper construction or similar such personal hygiene article.
- compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of, any compounds or steps not enumerated herein. Variations and modifications from the described embodiments exist. Finally, any number disclosed herein should be construed to mean approximate, regardless of whether the word "about” or “approximately” is used in describing the number. The appended claims intend to cover all those modifications and variations as falling within the scope of the invention.
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Abstract
Description
Claims
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EP08798344.1A EP2185601B1 (en) | 2007-08-24 | 2008-08-21 | Adhesives made from interpolymers of ethylene/alpha-olefins |
CN2008801132725A CN101835815B (en) | 2007-08-24 | 2008-08-21 | Adhesives made from interpolymers of ethylene/alpha-olefins |
JP2010522017A JP2010537002A (en) | 2007-08-24 | 2008-08-21 | Adhesives made from ethylene / α-olefin interpolymers |
BRPI0815310-8A BRPI0815310B1 (en) | 2007-08-24 | 2008-08-21 | ADHESIVE COMPOSITION, ARTICLE AND METHOD OF APPLICATION OF AN ADHESIVE COMPOSITION |
US12/674,198 US8222339B2 (en) | 2007-08-24 | 2008-08-21 | Adhesives made from interpolymers of ethylene/alpha-olefins |
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Also Published As
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JP2015014000A (en) | 2015-01-22 |
JP6334334B2 (en) | 2018-05-30 |
EP2185601B1 (en) | 2019-02-27 |
JP2017020037A (en) | 2017-01-26 |
BRPI0815310A2 (en) | 2015-02-10 |
JP2010537002A (en) | 2010-12-02 |
EP2185601A1 (en) | 2010-05-19 |
US20110262747A1 (en) | 2011-10-27 |
BRPI0815310B1 (en) | 2019-05-14 |
CN101835815A (en) | 2010-09-15 |
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US8222339B2 (en) | 2012-07-17 |
CN101835815B (en) | 2013-01-30 |
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