US20150376310A1 - Ethylene acid copolymers, their ionomers, and their use in packaging films and injection molded articles - Google Patents

Ethylene acid copolymers, their ionomers, and their use in packaging films and injection molded articles Download PDF

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US20150376310A1
US20150376310A1 US14/560,663 US201414560663A US2015376310A1 US 20150376310 A1 US20150376310 A1 US 20150376310A1 US 201414560663 A US201414560663 A US 201414560663A US 2015376310 A1 US2015376310 A1 US 2015376310A1
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ethylene
acid
ionomer
copolymer
carboxylic acid
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Shannon D. MEERSCHEIDT
Steven C. Pesek
W Alexander Shaffer
Charles Anthony Smith
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Performance Materials NA Inc
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EI Du Pont de Nemours and Co
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Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SMITH, CHARLES ANTHONY, MEERSCHEIDT, Shannon D., PESEK, STEVEN C., SHAFFER, W. ALEXANDER
Publication of US20150376310A1 publication Critical patent/US20150376310A1/en
Priority to US15/617,253 priority patent/US10377840B2/en
Assigned to PERFORMANCE MATERIALS NA, INC. reassignment PERFORMANCE MATERIALS NA, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E.I. DU PONT DE NEMOURS AND COMPANY
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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
    • C08F210/02—Ethene
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers 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
    • C08L23/0876—Salts thereof, i.e. ionomers
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/0023—Covers
    • A63B37/0024—Materials other than ionomers or polyurethane
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
    • A63B37/0039—Intermediate layers, e.g. inner cover, outer core, mantle characterised by the material
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/005—Cores
    • A63B37/0051—Materials other than polybutadienes; Constructional details
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols

Definitions

  • novel ethylene acid copolymers ionomers of the ethylene acid copolymers, and the use of these copolymers and ionomers in various materials, including packaging films and injection molded articles. These copolymers and ionomers show improved optical properties when compared to conventional ethylene acrylic or methacrylic acid copolymers and their ionomers.
  • Ionomers are copolymers produced by partially or fully neutralizing the carboxylic acid groups of precursor or parent polymers that are acid copolymers comprising copolymerized residues of ⁇ -olefins and ⁇ , ⁇ -ethylenically unsaturated carboxylic acids.
  • a variety of articles made from ionomers by injection molding processes have been used in our daily life.
  • golf balls with ionomer-containing covers have been produced by injection molding. See, e.g.; U.S. Pat. Nos. 4,714,253; 5,439,227; 5,452,898; 5,553,852; 5,752,889; 5,782,703; 5,782,707; 5,803,833; 5,807,192; 6,179,732; 6,699,027; 7,005,098; 7,128,864; 7,201,672; and U.S. Patent Appln. Publn. Nos. 2006/0043632; 2006/0273485; and 2007/0282069.
  • Ionomers have also been used to produce injection molded hollow articles, such as containers. See, e.g., U.S. Pat. Nos. 4,857,258; 4,937,035; 4,944,906; 5,094,921; 5,788,890; 6,207,761; and 6,866,158, U.S. Patent Publication Nos. 20020180083; 20020175136; and 20050129888, European Patent Nos. EP1816147 and EP0855155, and PCT Patent Publn. Nos. WO2004062881; WO2008010597; and WO2003045186.
  • ionomers for packaging films, injection molded articles, and other end-uses is well known in the art.
  • Some films are designed to be breathable, to allow oxygen and/or moisture to pass through, to exhibit elastic properties, or to protect the materials they surround. See, for example, U.S. Pat. Nos. 7,438,940 and 7,635,509; and U.S. Patent Appln. Publn. Nos. 2006/0094824 and US2010/0272898.
  • Ionomeric materials can also be used to fabricate blown films and thermoformed articles. See, for example, U.S. Patent Appln. Publn. Nos. 2011/0028622 and 2009/0099313 and U.S. Pat. No. 8,110,138.
  • an ethylene acid copolymer comprising copolymerized units of ethylene, about 10 to about 30 wt % of copolymerized units of a first ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 10 carbon atoms; and about 5 to about 15 wt % of copolymerized units of a derivative of a second ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 10 carbon atoms.
  • the weight percentages of the copolymerized units are based on the total weight of the ethylene acid copolymer.
  • at least a portion of the carboxylic acid groups of the copolymerized ⁇ , ⁇ -unsaturated carboxylic acid units are neutralized to form carboxylate salts.
  • packaging films injection-molded articles such as containers, golf balls and components of golf balls, and other structures comprising the ethylene acid copolymers and ionomers described herein.
  • a finite amount refers to an amount that is greater than zero.
  • the terms “comprises,” “comprising,” “includes,” “including,” “containing,” “characterized by,” “has,” “having” or any other variation thereof, refer to a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • compositions, a process, a structure, or a portion of a composition, a process, or a structure is described herein using an open-ended term such as “comprising,” unless otherwise stated the description also includes an embodiment that “consists essentially of” or “consists” of the elements of the composition, the process, the structure, or the portion of the composition, the process, or the structure.
  • ranges set forth herein include their endpoints unless expressly stated otherwise.
  • an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed.
  • the scope of the invention is not limited to the specific values recited when defining a range.
  • copolymer refers to polymers comprising copolymerized units resulting from copolymerization of two or more comonomers.
  • a copolymer may be described herein with reference to its constituent comonomers or to the amounts of its constituent comonomers, for example “a copolymer comprising ethylene and 15 weight % of acrylic acid”, or a similar description.
  • dipolymer refers to polymers consisting essentially of two monomers
  • terpolymer refers to polymers consisting essentially of three monomers
  • (meth)acrylic refers to acrylic or methacrylic, for example, “acrylic acid or methacrylic acid”, or “alkyl acrylate or alkyl methacrylate”.
  • ionomer refers to a polymer that comprises ionic groups that are carboxylate salts, for example, ammonium carboxylates, alkali metal carboxylates, alkaline earth carboxylates, transition metal carboxylates and/or combinations of such carboxylates.
  • carboxylate salts for example, ammonium carboxylates, alkali metal carboxylates, alkaline earth carboxylates, transition metal carboxylates and/or combinations of such carboxylates.
  • Such polymers are generally produced by partially or fully neutralizing the carboxylic acid groups of precursor or parent polymers that are acid copolymers, as defined herein, for example by reaction with a base.
  • an alkali metal ionomer as used herein is a zinc/sodium mixed ionomer (or zinc/sodium neutralized mixed ionomer), for example a copolymer of ethylene and methacrylic acid wherein all or a portion of the carboxylic acid groups of the copolymerized methacrylic acid units are in the form of zinc carboxylates and sodium carboxylates.
  • an ethylene acid copolymer that comprises copolymerized units of ethylene, about 10 to about 30 wt % of copolymerized units of a first ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 10, preferably 3 to 8, carbon atoms; and about 5 to about 15 wt % of copolymerized units of a derivative of a second ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 10, preferably 3 to 8, carbon atoms.
  • the amount of copolymerized acid(s) is about 15 to about 25 wt %, or about 20 to 24 wt %, or about 22 wt %.
  • the amount of copolymerized acid derivative(s) is about 8 to about 12 wt %, or about 10 wt %. In some preferred ethylene acid copolymers, the sum of the weight percentages of the copolymerized acid and acid derivative is about 20 to about 45 wt %. The weight percentages of the copolymerized units are based on the total weight of the ethylene acid copolymer, and the sum of the weight percentages of the copolymerized units is 100 wt %.
  • at least a portion of the carboxylic acid groups of the copolymerized units of the ⁇ , ⁇ -unsaturated carboxylic acid units are neutralized to form carboxylate salts.
  • Suitable first ⁇ , ⁇ -ethylenically unsaturated acid comonomers include, without limitation, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and mixtures of two or more thereof.
  • the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, and mixtures of two or more thereof.
  • the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is methacrylic acid.
  • the ethylene acid copolymer further comprises copolymerized units of one or more additional comonomer(s), such as a second ⁇ , ⁇ -ethylenically unsaturated carboxylic acid having 3 to 10, or preferably 3 to 8 carbons, or derivatives thereof.
  • additional comonomer(s) such as a second ⁇ , ⁇ -ethylenically unsaturated carboxylic acid having 3 to 10, or preferably 3 to 8 carbons, or derivatives thereof.
  • Suitable acid derivatives include acid anhydrides, amides, and esters. Esters are preferred, and alkyl esters are more preferred.
  • the suitable additional comonomers are selected from methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, glycidyl methacrylate, vinyl acetate, and mixtures of two or more thereof.
  • the first ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is the same as the second ⁇ , ⁇ -ethylenically unsaturated carboxylic acid; in yet another preferred ethylene copolymer, however, the first and the second ⁇ , ⁇ -ethylenically unsaturated carboxylic acids are different.
  • suitable ethylene acid copolymers may be synthesized as described in U.S. Pat. Nos. 3,404,134; 5,028,674; 6,500,888; 6,518,365; 8,334,033, or 8,399,096, for example.
  • a method described in U.S. Pat. No. 8,399,096 is used, and a sufficiently high level and complementary amount of the derivative of the second ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is present in the reaction mixture.
  • the ethylene acid copolymers are partially neutralized by reaction with one or more bases.
  • An example of a suitable procedure for neutralizing the ethylene acid copolymers is described in U.S. Pat. Nos. 3,404,134 and 6,518,365. After neutralization, about 1% to about 90%, or about 10% to about 60%, or about 20% to about 55%, or about 20 to about 30% of the hydrogen atoms of carboxylic acid groups present in the ethylene acid copolymer are replaced by other cations. Stated alternatively, about 1% to about 90%, or about 10% to about 60%, or about 20% to about 55%, or about 20 to about 30% of the total content of the carboxylic acid groups present in the ethylene acid copolymer are neutralized.
  • the acid groups are neutralized to a level of about 1% to about 90%, or about 10% to about 60%, or about 20% to about 55%, or about 20 to about 30%, based on the total content of carboxylic acid groups present in the ethylene acid copolymers as calculated or measured for the non-neutralized ethylene acid copolymers.
  • the neutralization level can be tailored for the specific end-use.
  • the ionomers comprise cations as counterions to the carboxylate anions.
  • Suitable cations include any positively charged species that is stable under the conditions in which the ionomer composition is synthesized, processed and used. Suitable cations may be used in combinations of two or more.
  • the cations are metal cations, which may be monovalent, divalent, trivalent, or multivalent. Useful monovalent metal cations include but are not limited to cations of sodium, potassium, lithium, silver, mercury, copper, and the like.
  • Useful divalent metal cations include but are not limited to cations of beryllium, magnesium, calcium, strontium, barium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel, zinc, and the like.
  • Useful trivalent metal cations include but are not limited to cations of aluminum, scandium, iron, yttrium, and the like.
  • Useful multivalent metal cations include but are not limited to cations of titanium, zirconium, hafnium, vanadium, tantalum, tungsten, chromium, cerium, iron, and the like.
  • the metal cations used are monovalent or divalent metal cations.
  • Preferred metal cations are sodium, lithium, magnesium, zinc, potassium, and combinations of two or more of these metal cations.
  • the cations are sodium cations, zinc cations and combinations of sodium and zinc cations.
  • the resulting neutralized ionomer has a melt index, as determined in accordance with ASTM method D1238-89 at 190° C. and 2.16 kg, that is lower than that of the corresponding ethylene acid copolymer.
  • the ionomer's melt index depends on a number of factors, including the melt index of the ethylene acid copolymer, the amount of copolymerized acid, the neutralization level, the identity of the cation and its valency.
  • the desired value of the ionomer's melt index may be determined by its intended end use.
  • the ionomer has a melt index of about 1000 g/10 min or less, about 750 g/10 min or less, about 500 g/10 min or less, about 250 g/10 min or less, about 100 g/10 min or less, about 50 g/10 min or less, about 25 g/10 min or less, or about of 20 g/10 min or less, or about 10 g/10 min or less, or about 5 g/10 min or less, or about 0.7 to about 7.5 g/10 min, as determined in accordance with ASTM method D1238-89 at 190° C. and 2.16 kg.
  • the ethylene acid copolymers and ionomers described herein may be formulated into compositions that further comprise additives known within the art.
  • the additives include, but are not limited to, processing aids, flow enhancing additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, anti-blocking agents such as silica, thermal stabilizers, UV absorbers, UV stabilizers, dispersants, surfactants, chelating agents, coupling agents, reinforcement additives, such as glass fiber, fillers and the like.
  • suitable additives suitable levels of the additives in the ethylene acid copolymers and ionomers, and methods of incorporating the additives into the ethylene acid copolymers and ionomers may be found in reference texts such as, for example, the Kirk Othmer Encyclopedia, the Modern Plastics Encyclopedia, McGraw-Hill (New York, 1995) or the Wiley Encyclopedia of Packaging Technology, 2d edition, A. L. Brody and K. S. Marsh, Eds., Wiley-Interscience (Hoboken, 1997).
  • Four types of additives are of note for use in the ionomeric polymers, specifically thermal stabilizers, UV absorbers, hindered amine light stabilizers (HALS), and silane coupling agents. Further information about these four types of additives, such as preferred examples and suitable levels in ionomeric polymers, may be found in the reference texts cited above and in U.S. Pat. No. 7,641,965, for example.
  • the ethylene acid copolymers or ionomers are cross-linked.
  • Several methods of decreasing the melt flow of ethylene acid copolymers and their ionomers are known and are described in U.S. Patent Appln. Publn. No. 2009/0126859, by Cadwallader et al., for example.
  • Organic peroxides in particular, have been used as cross-linking agents for ethylene acid copolymers and their ionomers.
  • the copolymer composition includes a hydroxyl-containing crosslinking agent and one or more silane adjuvants.
  • hydroxyl-containing crosslinking agent refers to any molecule that is miscible with the ethylene copolymer and that has two or more hydroxyl groups.
  • suitable hydroxyl-containing crosslinking agents include, without limitation, diols such as 1,4-butanediol, 1,3-propanediol and 1,6-hexanediol. 1,4-Butanediol is particularly preferred.
  • the hydroxyl-containing crosslinking agent is included in the acid copolymer composition in an amount of up to about 5 wt %, preferably about 2 wt % or less or about 1.5 wt % or less, more preferably about 1 wt % or less, 0.5 wt % or less, or 0.25 wt % or less, or 0.1 wt %, based on total weight of the acid copolymer composition.
  • Those of skill in the art are able to determine an appropriate level of cross-linking based on the physical properties that are desired in the cross-linked composition. For example, higher levels of cross-linking are correlated with a higher flex modulus, better high temperature adhesion, lower melt indices, and better heat resistance. The level of cross-linking must be adjusted, however, so that the desired end use performance is obtained. Those of skill in the art are also aware that the time required to obtain a desired level of cross-linking depends directly on the concentration of carboxylic acid groups and hydroxyl-containing groups.
  • cross-linking reactions can require heat, but the reaction may also be carried out using catalysis, or by using a combination of heat and catalysis.
  • esterification reactions are known to be catalyzed by acid catalysts and by base catalysts.
  • the hydroxyl-containing crosslinking agent can be added to the ionomer in any convenient manner.
  • One particularly useful way is to add the agent to the ionomer flake, pellets or granules in the pre-mix chamber of an extruder.
  • Another way to introduce this agent is through an injection port.
  • the cross-linking agent is incorporated into the polymer composition and may react so that the cross-linking occurs in the ionomer as it is extruded. Alternatively, the cross-linking reaction can take place during melt mixing or extrusion of the melt.
  • the cross-linkable polymer composition may optionally comprise one or more adjuvants.
  • suitable adjuvants include silanes. When silanes are used, they can be added in amounts of between 0.025 wt % and 0.1 wt %, 0.25 wt %, 0.5 wt %, 0.75 wt % or 1.0 wt %, based on the total weight of the polymer composition.
  • Non-limiting examples of preferred silanes include N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and combinations thereof.
  • the adjuvant can be added at the same time and in the same manner as the hydroxyl-containing crosslinking agent, or by any other known method.
  • Catalysts may also be included, such as the creation of either acidic or basic conditions to catalyze the cross-linking reaction.
  • a specific catalyst such as dibutyl tin oxide or similar compound, may be employed.
  • the present invention also includes a product of cross-linking the ethylene acid copolymer or ionomer composition, so that at least a portion of the carboxylic acid groups of one or more ethylene acid copolymer (or ionomer) molecules are reacted with at least two hydroxyl groups of the hydroxyl-containing crosslinking agent, thereby forming cross-links between or within the ethylene acid copolymer (or ionomer) molecules.
  • At least a portion of the carboxylic acid groups of two or more ethylene acid copolymer (or ionomer) molecules are reacted with at least two hydroxyl groups of the hydroxyl-containing crosslinking agent, thereby forming cross-links between the ethylene acid copolymer (or ionomer) molecules.
  • the resulting cross-linked polymer composition may have a MFR of 25 g/10 min or less, or about of 20 g/10 min or less, or about 10 g/10 min or less, or about 5 g/10 min or less, or about 0.7 to about 5 g/10 min or to about 7.5 g/10 min, as determined in accordance with ASTM method D1238-89 at 190° C. and 2.16 kg.
  • the ethylene acid copolymers and ionomers described herein are surprisingly well-suited for use with the polyhydroxyl crosslinking agents and silane adjuvants.
  • the creep resistance of the copolymers and ionomers described herein exhibits favorable effects when cross-linked, when compared with conventional ethylene acid copolymers and ionomers that are cross-linked using the same system.
  • the cross-linked acid copolymers and ionomers described herein exhibit greater elongation with integrity when compared to sheets or films of previously known acid copolymers and ionomers that are cross-linked using the same system.
  • the term “elongation with integrity”, as used herein, refers to the ability of a film to stretch by 10% or greater without incurring any defects that would impair performance. Non-limiting examples of such defects include breaking, stretching and necking down to a thin fiber-like construction, and material unable to support its own weight.
  • articles comprising the ethylene acid copolymers and ionomers described herein and articles comprising the products of cross-linking the ethylene acid copolymers and ionomers described herein. More specifically, the polymers and compositions described herein are suitable for use in various objects including packaging films or sheets and injection molded or thermoformed articles. Accordingly, provided herein are sheets and films comprising or made from the polymer composition. Further provided are sheets and films comprising or made from a product of crosslinking the polymer composition.
  • the difference between a film and a sheet is the thickness; however, there is no set industry standard as to when a film becomes a sheet.
  • the term “film” refers to a structure having a thickness of about 20 mils (0.50 mm) or less
  • the term “sheet” refers to a structure having a thickness of greater than about 20 mils (0.50 mm).
  • the polymer compositions when used as packaging films, they can be of any useful thickness.
  • these polymer compositions can have a thickness between about 0.4 mil and about 20 mils (about 10 to about 500 micrometers), and preferably between about 0.9 and about 6 mils (about 25 to about 150 micrometers).
  • the packaging films can comprise more than one layer.
  • Sheets comprising the polymer compositions may be formed by any suitable method, including without limitation dipcoating, solution casting, compression molding, injection molding, lamination, melt extrusion casting, blown film, extrusion coating, tandem extrusion coating, or by a combination of two or more of these methods.
  • the sheets are formed by an extrusion method, such as melt extrusion casting, melt coextrusion casting, melt extrusion coating, or tandem melt extrusion coating processes.
  • the article is a film or sheet, which may be prepared by any convention process, such as, dipcoating, solution casting, lamination, melt extrusion, blown film, extrusion coating, tandem extrusion coating, or by any other procedures that are known to those of skill in the art.
  • the films or sheets are formed by melt extrusion, melt coextrusion, melt extrusion coating, blown film process, or tandem melt extrusion coating process.
  • the article comprising the polymer composition described herein is a molded article, which may be prepared by any conventional molding process, such as, compression molding, injection molding, extrusion molding, blow molding, injection blow molding, injection stretch blow molding, extrusion blow molding and the like. Articles may also be formed by combinations of two or more of these processes, such as for example when a core formed by compression molding is overmolded by injection molding.
  • the article comprising the polymer composition disclosed herein is an injection molded article having a minimum thickness (i.e, the thickness at the smallest dimension of the article) of at least about 1 mm.
  • the injection molded article may have a thickness of about 1 mm to 100 mm, or 2 mm to 100 mm, or 3 to about 100 mm, or about 3 to about 50 mm, or about 5 to about 35 mm.
  • the article is an injection molded article in the form of a multi-layer structure (such as an over-molded article), wherein at least one layer of the multi-layer structure comprises or consists essentially of the ionomer composition disclosed above and that layer has a minimum thickness of at least about 1 mm.
  • the at least one layer of the multi-layer article has a thickness of about 1 to about 100 mm, or 2 mm to 100 mm, or 3 to about 100 mm, or about 3 to about 50 mm, or about 5 to about 35 mm.
  • the article is an injection molded article in the form of a sheet, a container (e.g., a bottle or a bowl), a cap or stopper (e.g., for a container), a sealant for a container (a bottle cap liner), a tray, a medical device or instrument (e.g., an automated or portable defibrillator unit), a handle, a knob, a push button, a decorative article, a panel, a console box, or a footwear component (e.g., a heel counter, a toe puff, or a sole).
  • a container e.g., a bottle or a bowl
  • a cap or stopper e.g., for a container
  • a sealant for a container a bottle cap liner
  • a tray e.g., a medical device or instrument (e.g., an automated or portable defibrillator unit), a handle, a knob, a push button, a decorative article, a
  • the article is an injection molded intermediate article for use in further shaping processes.
  • the article may be a pre-form or a parison suitable for use in a blow molding process to form a container (e.g., a cosmetic container).
  • the injection molded intermediate article may be in the form of a multi-layer structure such as the one described above, and it may therefore produce a container having a multi-layer wall structure.
  • the article is an injection molded article in the form of a golf ball or a sub-part of a golf ball, for example a core or a mantle of a golf ball.
  • Injection molding is a well-known molding process.
  • the article disclosed herein is in the form of an injection molded article, it may be produced by any suitable injection molding process.
  • Suitable injection molding processes include, for example, co-injection molding and over-molding (also referred to as two-shot or multi-shot molding processes).
  • the polymer composition may be used as the substrate material, the over-mold material or both.
  • the polymer composition disclosed herein may be over-molded on a glass or metal container.
  • the polymer compositions may be over-molded on any other articles (such as house items, medical devices or instruments, electronic devices, automobile parts, architectural structures, sporting goods, and etc.) to form a soft touch and/or protective overcoating.
  • the over-mold material comprises the polymer composition described herein
  • the melt index of the polymer composition is preferably from 0.75 up to about 25 g/10 min, as determined in accordance with ASTM D1238 at 190° C. and 2.16 kg.
  • the polymer composition may notably comprise an ionomer having zinc cations.
  • the precursor acid copolymer preferably has a melt index of about 10 to about 100 g/10 min, or about 10 to 70 g/10 min, as determined in accordance with ASTM D1238 at 190° C. and 2.16 kg.
  • the zinc ionomer preferably has a melt index of from about 0.1 to about 2.0 g/10 min, as determined in accordance with ASTM D1238 at 190° C. and 2.16 kg.
  • the polymer composition may be molded at a melt temperature of about 120° C. to about 250° C., or about 130° C. to about 210° C. In general, slow to moderate fill rates with pressures of about 30 to about 210 MPa or of about 69 to about 110 MPa may be used.
  • the mold temperatures may be in the range of about 5° C. to about 50° C. Based on the polymer composition and the process type that is to be used, one skilled in the art would be able to determine the proper molding conditions required to produce a particular type of article.
  • injection molding conditions may include temperatures, pressures and cycle times as indicated in Table A.
  • compositions described herein may be used with any type of ball construction. It may be used in the core, cover, or one or more intermediate layers of a golf ball. Suitable golf ball constructions, including one-piece golf balls, two-piece golf balls, three-piece golf balls and multi-piece golf balls, are described in U.S. Pat. Nos. 8,044,136 and 8,202,925, both issued to de Garavilla, and in the references cited therein.
  • Acid copolymer resins and their ionomers were obtained from DuPont under the trademarks Nucrel®, Surlyn® or SentryGlas®. Alternatively, the polymers were synthesized by the methods described in U.S. Pat. No. 8,399,096.
  • the first ⁇ , ⁇ -ethylenically unsaturated carboxylic acid was acrylic acid or methacrylic acid.
  • a sufficiently high level and complementary amount of the derivative of the second ⁇ , ⁇ -ethylenically unsaturated carboxylic acid here, i-butyl acrylate or n-butyl acrylate
  • the compositions of the synthesized polymers which are set forth in Table 1, were determined by nuclear magnetic resonance (NMR) spectroscopy, by titration, or by mass balance methods.
  • the counterions of the ionomers were sodium cations.
  • the acid copolymers and ionomers are also formed into sheets, which in turn are used as interlayers in glass laminates. Again, the methods are set forth in U.S. Pat. No. 8,399,096.
  • Comparative Example CE2 the haze level of a glass laminates comprising a prior art ionomer interlayer sheet is strongly dependent on the cooling rate under which the laminate is obtained. In general, slower cooling rates increase the laminates' haze. As illustrated by Table 1, however, glass laminates comprising interlayer sheets made from the acid copolymers and ionomers described herein (Examples 1, 2 and 3) tend to have lower haze than those comprising prior art acid copolymer and ionomer interlayer sheets (Comparative Examples CE1 and CE2). Moreover, the haze levels of laminates of Examples 2 and 3 were affected to a significantly lesser extent than Comparative Examples CE2 by the cooling rate under which the laminates were obtained.

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KR102274719B1 (ko) 2021-07-14
US20170369610A1 (en) 2017-12-28
KR20180086541A (ko) 2018-08-01
WO2015199750A1 (en) 2015-12-30

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