WO2006034382A1 - Cation-neutralized ionomers and foams thereof - Google Patents

Cation-neutralized ionomers and foams thereof Download PDF

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Publication number
WO2006034382A1
WO2006034382A1 PCT/US2005/033915 US2005033915W WO2006034382A1 WO 2006034382 A1 WO2006034382 A1 WO 2006034382A1 US 2005033915 W US2005033915 W US 2005033915W WO 2006034382 A1 WO2006034382 A1 WO 2006034382A1
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ethylene
carbon atoms
carboxylic acid
neutralized
weight percent
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English (en)
French (fr)
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David M. Dean
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to JP2007532657A priority Critical patent/JP2008513583A/ja
Priority to EP05800481A priority patent/EP1791897A1/en
Priority to BRPI0515669-6A priority patent/BRPI0515669A/pt
Publication of WO2006034382A1 publication Critical patent/WO2006034382A1/en
Anticipated expiration legal-status Critical
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/425Porous materials, e.g. foams or sponges
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/44Preparation of metal salts or ammonium salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/04Foams characterised by their properties characterised by the foam pores
    • C08J2205/05Open cells, i.e. more than 50% of the pores are open
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00Foams characterised by their intended use
    • C08J2207/12Sanitary use, e.g. diapers, napkins or bandages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/14Water soluble or water swellable polymers, e.g. aqueous gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876Salts thereof, i.e. ionomers

Definitions

  • This invention relates to trivalent cation-neutralized ionomers with melt strength and viscosity properties suitable for preparing extruded open cell foams.
  • Open cell polymeric foams have generated considerable interest for commercial use in absorbent articles such as disposable diapers, adult incontinence pads and briefs, and sanitary napkins.
  • U.S. Patent Nos. 5,650,222, 5,741 ,581 and 5,744,506 describe low density absorbent foams made by polymerizing high internal phase emulsions where the volume to weight ratio of the water phase to the oil phase is in the range of from about 55:1 to about 100:1.
  • Open cell foams based on polyolefins are particularly useful in these applications because of their outstanding chemical resistance and recyclability.
  • Polyolefin open cell foams are often lightly crosslinked in order to control and stabilize the size of the foam cells.
  • Foams can be crosslinked by several methods, including, for example, irradiation and free-radical catalysis, such as by peroxides.
  • Ionomers which are copolymers having ionizable comonomers that are at least partially neutralized (ionized) to yield carboxylate salts, are also useful as components of open cell foams.
  • Ionomers based on ethylene-acid copolymers are typically prepared by copolymerization of ethylene with an unsaturated carboxylic acid, followed by neutralization of some portion of the acid groups. The ionized groups can act as meltable crosslinks. For example, U.S.
  • Patent No. 4,102,829 describes low density extruded foams prepared from a mixture of from about 5 to 65% polyolefin and from about 35 to 95% ionomer, the ionomer being a zinc salt.
  • U.S. Patent No. 4,091 ,136 describes a fine closed cell foam produced by extrusion in rod form of a foamable mixture of polyolefin and a foaming agent together with an ethylene/methacrylic acid copolymer based ionomer resin.
  • U.S. Patent No. 4,102,829 there is described a foamed thermoplastic mixture of ionomers and polyolefin polymer produced by extruding the mix together with a volatile blowing agent at elevated temperature and pressure. The foams are said to have a good balance of properties, and are indicated to be useful as insulation covering on pipes for air conditioning.
  • Japanese Laid Open Patent Application H 10-279724/1998 describes a foam made from 0 to 50 parts by weight of polyolefin resin and 100 to 50 parts of an ionomer resin.
  • the extrusion pressure is high, leading to severe heat generation at the die. This makes it very difficult to obtain good open cell extruded foams have a high expansion ratio and high thickness.
  • stable manufacture is difficult because the foaming temperature must be regulated within a narrow range during extrusion foaming in order to obtain open cell extruded foam.
  • PCT International Publication No. WO 02/27905 teaches that ionomer present in a polyethylene resin at a level of from about 1 to about 40% by weight of the resin produces superior continuously extruded foam sheet products that approach the pore size and resiliency of foams prepared from chemical blowing agents.
  • Japanese Patent Publication No. 56-55442 describes a resin composition comprising a copolymer of ethylene and ⁇ ,/?-ethylenically unsaturated carboxylic acid and optionally an ⁇ ,/?-unsatu rated ester, partially or completely ionically crosslinked by ions, and a polyamide resin having a melting point of not more than 16O 0 C.
  • Ten percent or more of the ⁇ ,/?-unsaturated carboxylic acid component is described to be neutralized by Na + , Mg +2 , Zn +2 , Al +3 and the like.
  • the examples describe only ionomers neutralized with magnesium, zinc and sodium ions.
  • U.S. Patent No. 4,766,174 describes melt processible blends of aluminum ionomers of ethylene/ ⁇ ,/?-ethylenically unsaturated carboxylic acid copolymers and thermoplastic resins or elastomers. From about 1 to about 100% of the carboxylic acid groups of the ethylene copolymer are neutralized with aluminum ions.
  • the ionomers used in the art for preparation of open cell foams typically contain divalent ions such as calcium or zinc. As indicated in the documents cited above, it has been very difficult to manufacture an open cell extruded foam exhibiting a high expansion ratio and a high open cell foaming ratio, in a stable process using calcium or zinc ionomers alone, or using blends of these ionomers and polyolefin resins. Consequently, there is a need in the art for ionomer-based open cell foam compositions with improved rheological properties, specifically, high melt strength, high viscosity and minimal sensitivity of viscosity to temperature, in order to achieve optimum processibility and extruded foam properties.
  • This invention is directed to an ionomer composition
  • an ionomer composition comprising at least one direct or graft copolymer of ethylene, ⁇ ,/?-ethylenically unsaturated carboxylic acid having from 3 to 8 carbon atoms, and softening comonomer selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have from 2 to 10 carbon atoms, alkyl vinyl ethers wherein the alkyl group contains from 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains from 1 to 10 carbon atoms; wherein the unsaturated carboxylic acid content is from about 1 to about 25 weight percent, the softening comonomer content is from 0 to about 60 weight percent; the remainder being ethylene, such that the ethylene content is greater than about 30 weight percent; further wherein the acid groups derived from the ⁇ ,/?-ethylenically unsaturated carboxylic acid are
  • This invention is also directed to a multilayer structure comprising at least one layer of the foamed composition in contact with at least one layer of superabsorbent polymer. Also provided are an article comprising the ionomer composition of the invention, an article comprising the multilayer structure of the invention, and a process for preparing the ionomer composition of the invention.
  • (meth)acrylic as used herein, alone or in combined form, such as “(meth)acrylate”, refers to acrylic and/or methacrylic, for example, acrylic acid and/or methacrylic acid, or alkyl acrylate and/or alkyl methacrylate.
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such.
  • the ionomer compositions of the invention comprise at least one direct or graft copolymer of ethylene, an a, ⁇ - ethylenically unsaturated carboxylic acid, and an optional softening comonomer selected from the group consisting of vinyl esters, alkyl vinyl ethers, and alkyl (meth)acrylates.
  • an optional softening comonomer selected from the group consisting of vinyl esters, alkyl vinyl ethers, and alkyl (meth)acrylates.
  • the ⁇ ,/?-ethylenically unsaturated carboxylic acid is selected from the group consisting of (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and half esters of maleic, fumaric and itaconic acids. More preferably the ⁇ , ⁇ -unsatu rated carboxylic acid is (meth)acrylic acid, and still more preferably the acid is methacrylic acid.
  • the optional softening comonomer when present, is selected from vinyl esters, alkyl vinyl ethers, and alkyl (meth)acrylates.
  • suitable softening monomers are, for example, vinyl acetate, butyl vinyl ether, methyl vinyl ether, methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
  • the softening comonomer is alkyl (meth)acrylate or alkyl vinyl ether, and more preferably the softening comonomer is butyl acrylate.
  • the ethylene content of the ethylene/acid copolymer preferably is greater than about 50 weight percent, and more preferably greater than about 60 weight percent.
  • the ethylene/acid copolymer preferably contains from 0 to about 40 weight percent of softening comonomer. More preferably the copolymer contains from about 5 to about 15 weight percent of unsaturated carboxylic acid and from 0 to about 30 weight percent of softening monomer; the remainder being ethylene, such that the ethylene content is greater than about 60 weight percent.
  • the ionomers of the present invention from about 3 to about 50% of the carboxylic acid groups are neutralized with trivalent cations.
  • the percent neutralization data are presented using the assumption that each cation will react with the maximum number of carboxylic acid groups calculated from its ionic charge. That is, it is assumed, for example, that Al +3 will react with three carboxylic acid groups, that Mg +2 and Zn +2 will react with two, and that Na + will react with one.
  • the trivalent cation can be any positively charged ion capable of reacting with three carboxylic acid groups.
  • the trivalent cations are selected from the group consisting of trivalent lanthanide metal cations, aluminum cation, chromium cation, and iron cation.
  • the most preferred trivalent cation is aluminum cation.
  • the source of trivalent cation may be any convenient derivative such as carboxylates, alkoxides, chelated compounds and hydroxides.
  • the preferred sources are aluminum acetate, aluminum isopropoxide and aluminum acetylacetonate. It is preferred that from about 20% to about 80% of the ionomer carboxylic acid groups are neutralized by trivalent cations (from about 3 to about 50%), and, if present, monovalent and/or divalent cations.
  • the reaction of the ion sources with the carboxylic acid containing polymers is carried out by melt blending at temperatures in the range from about 150° to about 300 0 C.
  • some of the carboxylic acid groups of the ionomers may optionally be neutralized with mono- or divalent cations.
  • monovalent cations if present, are selected from the group consisting of sodium, potassium, and lithium
  • divalent cations if present, are selected from the group consisting of zinc, magnesium and calcium. More preferably the monovalent cation will be sodium, and the divalent cation will be zinc.
  • Mono- and divalent ion sources are typically formates, acetates, hydroxides, nitrates, carbonates and bicarbonates.
  • a finite amount up to about 70% of the carboxylic acid groups are neutralized with mono- or divalent cations.
  • the trivalent cation containing ionomers of the invention exhibit surprising properties. For example, the melt strength and melt viscosity are higher, and the sensitivity of melt viscosity to temperature is lower, compared to ionomer compositions that contain the same base resin and are neutralized with monovalent or divalent cations only. Moreover, the aluminum-containing ionomers are characterized by having a flex modulus of less than about 15,000 psi in the solid, non-foamed state.
  • melt strength and melt viscosity properties are expected when the aluminum-containing ionomers are blended with other thermoplastic polymers. That is, the melt strength and melt viscosity are expected to be higher than the same blends based on the same ionomer copolymer but neutralized only with mono- or divalent cations and the sensitivity of melt viscosity to temperature lower than the same blends based on the same ionomer copolymer but neutralized only with mono- or divalent cations.
  • Blends of thermoplastic polymers with the ionomer compositions of the invention are particularly useful in preparing extruded foams.
  • Preferred thermoplastic polymers for blending with the ionomers of the invention are polyethylene, polypropylene and copolymers thereof, polybutene-1 , poly(4-methylpentene-1 ), polystyrene and copolymers thereof.
  • a more preferred blending polymer is polyethylene, and a still more preferred blending polymer is linear, low-density polyethylene.
  • the polymer blend containing at least one thermoplastic polymer may further comprise at least one elastomer selected from the group consisting of styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butadiene block copolymer, ethylene- propylene rubber and ethylene-propylene-diene monomer rubber (EPDM).
  • elastomer selected from the group consisting of styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butadiene block copolymer, ethylene- propylene rubber and ethylene-propylene-diene monomer rubber (EPDM).
  • Preferred blends comprise preferred ionomer compositions described above.
  • the amount of thermoplastic polymer used in blends with the trivalent cation-containing ionomer will be from 0 to about 85 weight percent, more preferably from 0 to about 75 weight percent, and still more preferably from about 0 to about 65 weight percent.
  • Blends of trivalent cation-containing ionomer and thermoplastic polymer(s) can be prepared by mixing the ionomer and polymer(s) at a temperature in the range from about 15O 0 C to about 300 0 C, preferably from about 18O 0 C to about 295 0 C, and most preferably from about 200 0 C to about 29O 0 C.
  • the thermoplastic polymer may be blended with the ethylene/ ⁇ ,/?-ethylenically unsaturated carboxylic acid copolymer, and then the resulting blend can be treated with the neutralizing ion sources.
  • the mixing of the polymers and neutralization may be carried out simultaneously.
  • the foamed compositions of the present invention can be obtained by taking the base composition(s) discussed above, e.g., at least partially neutralized ionomer or at least partially neutralized ionomer and thermoplastic polymer, together with any additives used to control foam properties, supplying these to an extruder, subjecting these materials to melting under heating and kneading, then supplying a foaming agent and forming a foaming molten resin mixture, then regulating processing parameters such as the extrusion temperature, pressure inside the extrusion die, discharge volume, etc., and extruding the mixture from the die into a low pressure region and causing foaming.
  • the base composition(s) discussed above e.g., at least partially neutralized ionomer or at least partially neutralized ionomer and thermoplastic polymer, together with any additives used to control foam properties
  • supplying these to an extruder subjecting these materials to melting under heating and kneading
  • the foaming agents used in the manufacture of the foams of the present invention can be either physical foaming agents or decomposing- type chemical foaming agents, but the use of physical foaming agents is preferred in order to obtain extruded open cell foam.
  • physical foaming agents low boiling hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, etc., chlorinated hydrocarbons such as methyl chloride and ethyl chloride, fluorocarbons such as 1 ,1 ,1 ,2-tetrafluoroethane and 1 ,1-difluoroethane, and other materials such as carbon dioxide, nitrogen and water may be utilized.
  • decomposing-type foaming agents azodicarbonamide and the like may be employed.
  • the foaming agents can be used in mixtures of two or more, and a decomposing type may be used together with a physical type and thus serve to regulate cell diameter
  • the extrusion temperature preferably will be within the range from about 100 0 C to about 25O 0 C and more preferably from about 15O 0 C to about 23O 0 C.
  • the extrusion temperature is below about 100 0 C, the elastic forces of the polymeric components will be too strong, and thus it may not be possible to obtain a foam with a high expansion ratio.
  • the temperature exceeds about 25O 0 C, on the other hand, the foam may tend to shrink or giant cells may be produced.
  • relative insensitivity of the viscosity to temperature on the part of the trivalent cation neutralized ionomers will minimize the effects of temperature on the foaming process and properties.
  • the foams of the invention may be open or closed cell foams or mixtures thereof, with densities of from about 10 to about 200 kg/m 3 , more preferably from about 20 to about 150 kg/m 3 .
  • Preferably about 50% of the foam cells in a foamed composition are open cells.
  • the term "open cell” in this context means that an individual cell of the foam is incompletely sealed, providing unobstructed communication with at least one adjoining cell.
  • the cells in open celled foam structures have at least one intercellular opening or "window" that is large enough to permit fluid transfer from one cell to another within the foam structure.
  • the foams of the invention comprise a substantial proportion of open cells.
  • Substantially open cell foams are desirable in articles used for disposable product applications such as diapers, adult incontinence pads, sanitary napkins and the like.
  • open cell foams often are used in conjunction with superabsorbent polymer that is present in such products in contact with the open cell foam.
  • the superabsorbent polymer may be present at the surface of the cell walls of the foam.
  • this invention also provides a multilayer structure comprising at least one layer of the foam composition in contact with at least one layer of superabsorbent polymer.
  • a multilayer structure comprising at least one layer of the foam composition in contact with at least one layer of superabsorbent polymer.
  • the foam composition in the multilayer structure at least 50% of the foam cells are open cells.
  • the multilayer structure may comprise one or more layers of superabsorbent polymer between layers of the extruded open cell foam.
  • superabsorbent polymer are those based on sodium salts of poly(acrylic acid), such as AQUAKEEP J550 available from the Sumitomo Seiko Chemicals Co., Ltd., of Osaka, Japan.
  • Preferred multilayer structures comprise preferred compositions described above.
  • This invention also provides articles comprising the compositions described above, particularly foamed compositions. These articles include disposable product applications such as diapers, adult incontinence pads, sanitary napkins and the like. Preferred articles comprise preferred compositions described above.
  • the ionomer composition is a foamed composition having a density of from about 10 to about 200 kg/m 3 .
  • the foam composition at least 50% of the foam cells are open cells.
  • articles comprising a multilayer structure comprising at least one layer of the foam composition in contact with at least one layer of superabsorbent polymer.
  • the multilayer structure in such articles may comprise a layer of superabsorbent polymer between two layers of the extruded open cell foam.
  • the formulations shown in Table 1 were compounded using a 30 mm BUSS-KNEADER extruder. Extruder zones from the feed to the die were set at temperatures of 13O 0 C, 140 0 C, 145°C, and 15O 0 C respectively. The temperatures of the cross-head and die were set at 165°C. The materials were compounded at 5 pounds/hour and 150 RPM. The components were premixed by tumble mixing ingredients in a polyethylene bag and were then fed to the BUSS-KNEADER extruder.
  • Temperatures of the melt streams exiting the extruder were measured with a handheld thermocouple and were in the range of from 180 to 200 0 C.
  • the calculated percent of methacrylic acid that was neutralized by the aluminum cations is given in Table 1.
  • Table 3 presents viscosity data obtained from Comparative Example 1 and Example 5 as a function of temperature.
  • the benefit provided by introducing the aluminum component can be seen when comparing the low temperature data (200 0 C) to the high temperature data (230 0 C) for a given shear rate.
  • the introduction of the trivalent aluminum provides a material that has a melt viscosity that is less sensitive to temperature changes at lower shear rates.
  • Comparative Example 1 has a change in viscosity of 82% (2501.4/1377.4); however, Example 3 only shows a change of 38% in viscosity between these two temperature extremes (4443.2/3218.8).
  • Table 4 presents melt tension and flexural modulus data obtained for Comparative Examples 1 and 2 and Example 5.
  • the flexural moduli of the materials were measured according to ASTM D790 on 1/8-inch thick bars that were die-cut from solid plaques formed by compression molding, at 200 0 C, the pellets produced in the BUSS-KNEADER operation.
  • melt tension data were obtained using a GOFFERT RHEOTENS in connection with the KAYENESS GALAXY 5 CAPILLARY RHEOMETER described above.
  • the materials were also dried for 18 hours at 50 0 C. They were then tested for melt strength by extruding a melt strand of the polymer at 220 0 C through the 30 L/D capillary die. The strand was extruded through the die using a constant head speed on the capillary rheometer of 6.35 mm/min while the take-up speed of the RHEOTENS equipment was varied from 0 to 120 cm/s. Average melt tension (a measure of melt strength) data were recorded as the maximum force required to break the molten polymer strand. The maximum draw ratio of the strand was also recorded at this failure point defined as the ratio of the take-up speed to the strand extrusion speed.
  • Example 5 has over 10 times the melt strength of the material of the control, Comparative Example 1 (125.3 cN versus 10.3 cN). Furthermore, the increase in viscosity and melt strength provided by incorporating the aluminum cations into the material has only a limited effect on room temperature flexural modulus. This provides for a polymeric material that has the improved melt properties, important for manufacturing extrudable foams, while maintaining a high degree of softness and flexibility.
  • Comparative Example 2 shows that while a slight increase in melt strength can be accomplished by removing the acrylate comonomer, increasing the methacrylic acid level, and introducing additional Zn +2 cations, this increase comes at the expense of a dramatic increase in flex modulus. Comparative Example 2 has a 31% increase in melt strength relative to Comparative Example 1 (13.5 versus 10.3 cN), but the material also is nearly 10 times as stiff (38,000 psi flex modulus versus 4,000 psi).

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Hematology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
PCT/US2005/033915 2004-09-21 2005-09-21 Cation-neutralized ionomers and foams thereof Ceased WO2006034382A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2007532657A JP2008513583A (ja) 2004-09-21 2005-09-21 陽イオン中和アイオノマー及びその発泡体
EP05800481A EP1791897A1 (en) 2004-09-21 2005-09-21 Cation-neutralized ionomers and foams thereof
BRPI0515669-6A BRPI0515669A (pt) 2004-09-21 2005-09-21 composição de ionÈmero, mistura polimérica, composições de espuma, estrutura de multicamadas, artigo, processo para a preparação de uma mistura processável por fusão e produto

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61177004P 2004-09-21 2004-09-21
US60/611,770 2004-09-21

Publications (1)

Publication Number Publication Date
WO2006034382A1 true WO2006034382A1 (en) 2006-03-30

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US (1) US20060063888A1 (enExample)
EP (1) EP1791897A1 (enExample)
JP (1) JP2008513583A (enExample)
KR (1) KR20070067094A (enExample)
CN (1) CN101023125A (enExample)
BR (1) BRPI0515669A (enExample)
WO (1) WO2006034382A1 (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007297573A (ja) * 2006-04-06 2007-11-15 Du Pont Mitsui Polychem Co Ltd メチルペンテン系重合体樹脂組成物、そのフィルム又はシート、該樹脂組成物層を含む積層体
CN104418980A (zh) * 2013-08-29 2015-03-18 合肥杰事杰新材料股份有限公司 一种马来酸镍接枝聚丙烯离聚物及其制备方法与应用

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
WO2020000339A1 (en) 2018-06-29 2020-01-02 Dow Global Technologies Llc Foam bead and sintered foam structure
JP7374984B2 (ja) * 2018-07-31 2023-11-07 ダウ グローバル テクノロジーズ エルエルシー アイオノマー組成物
US12338335B2 (en) * 2018-09-28 2025-06-24 Dow Global Technologies Llc Polyamide foam preparation

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GB1113409A (en) * 1966-05-31 1968-05-15 Bayer Ag Mouldable plastics compositions based on ethylene copolymer salts
US4102829A (en) * 1975-06-21 1978-07-25 Asahi-Dow Limited Foamed thermoplastic resin comprising a mixture of ionomer and polyolefin
US4766174A (en) * 1986-01-02 1988-08-23 E. I. Du Pont De Nemours And Company Process for preparing melt-processible aluminum ionomer blends
US6197884B1 (en) * 1997-01-16 2001-03-06 Acushnet Company Golf ball compositions containing high crystalline acid copolymers and their ionomer derivatives

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US4091136A (en) * 1976-05-17 1978-05-23 Shaw Plastics Corporation Synthetic cork-like material and method of making same
US5567772A (en) * 1994-03-07 1996-10-22 E. I. Du Pont De Nemours And Company High flow ionomer resin compositions useful for golf ball covers
US5650222A (en) * 1995-01-10 1997-07-22 The Procter & Gamble Company Absorbent foam materials for aqueous fluids made from high internal phase emulsions having very high water-to-oil ratios
CN100577724C (zh) * 2001-03-29 2010-01-06 纳幕尔杜邦公司 柔软且富有回弹性的乙烯共聚物及其在高尔夫球上的应用
US20040229966A1 (en) * 2003-05-13 2004-11-18 Eastman Kodak Company Manufacturing process and use for open celled microcellular foam

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
GB1113409A (en) * 1966-05-31 1968-05-15 Bayer Ag Mouldable plastics compositions based on ethylene copolymer salts
US4102829A (en) * 1975-06-21 1978-07-25 Asahi-Dow Limited Foamed thermoplastic resin comprising a mixture of ionomer and polyolefin
US4766174A (en) * 1986-01-02 1988-08-23 E. I. Du Pont De Nemours And Company Process for preparing melt-processible aluminum ionomer blends
US6197884B1 (en) * 1997-01-16 2001-03-06 Acushnet Company Golf ball compositions containing high crystalline acid copolymers and their ionomer derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007297573A (ja) * 2006-04-06 2007-11-15 Du Pont Mitsui Polychem Co Ltd メチルペンテン系重合体樹脂組成物、そのフィルム又はシート、該樹脂組成物層を含む積層体
CN104418980A (zh) * 2013-08-29 2015-03-18 合肥杰事杰新材料股份有限公司 一种马来酸镍接枝聚丙烯离聚物及其制备方法与应用

Also Published As

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JP2008513583A (ja) 2008-05-01
US20060063888A1 (en) 2006-03-23
EP1791897A1 (en) 2007-06-06
KR20070067094A (ko) 2007-06-27
CN101023125A (zh) 2007-08-22
BRPI0515669A (pt) 2008-07-29

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