EP0725802A1 - Compositions ionomeres a faible turbidite de copolymeres d'alpha-olefines, d'esters d'acide carboxylique et d'eventuels comonomeres, et procedes de production et d'acidification de ces ionomeres - Google Patents

Compositions ionomeres a faible turbidite de copolymeres d'alpha-olefines, d'esters d'acide carboxylique et d'eventuels comonomeres, et procedes de production et d'acidification de ces ionomeres

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Publication number
EP0725802A1
EP0725802A1 EP95901711A EP95901711A EP0725802A1 EP 0725802 A1 EP0725802 A1 EP 0725802A1 EP 95901711 A EP95901711 A EP 95901711A EP 95901711 A EP95901711 A EP 95901711A EP 0725802 A1 EP0725802 A1 EP 0725802A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
acid
composition
alpha
ionomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95901711A
Other languages
German (de)
English (en)
Inventor
James H. Wang
David Rosendale
Victor P. Kurkov
Leslie P. Theard
Ta Yen Ching
Lewis R. Compton
Mitchell P. Eichelberger
Tor H. G. Palmgren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Phillips Chemical Co LP
Original Assignee
Chevron Chemical Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Chemical Co LLC filed Critical Chevron Chemical Co LLC
Publication of EP0725802A1 publication Critical patent/EP0725802A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
    • 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

Definitions

  • This invention provides new polymeric ionomer compositions which have low haze. Low haze makes the compositions especially suited for use in clear packaging films, in addition to the other applications in which ionomers are utilized. This invention also provides a method for making these new polymeric compositions and for modifying the acidity of the compositions.
  • compositions comprise ionomers which can be represented as the polymerization product of alpha-olefins having from two to eight carbon atoms, esters of alpha, beta- ethylenically-unsaturated carboxylic acids, metal salts of acrylic and methacrylic acid, and optional alpha, beta- ethylenically-unsaturated comonomers which impart some desired polymer property or properties, such as acidity and/or solvent resistivity.
  • ionomer compositions can easily be formed into films.
  • Ionomers which can be formed into films and methods of making ionomers are known in the art. Although these previously-known ionomers have similar chemical constituents to the ionomer compositions of this invention, the known ionomers have significantly different properties from the compositions of this invention. In addition, the known processes for making ionomers are also quite different from the method of making compositions of the present invention.
  • the copoly er is homogeneously or heterogeneously dispersed in the alcohol solution.
  • the saponified product can be further acidified to provide a composition having acid groups.
  • Japanese patent number Sho 53-134591 to Harada et al. discloses a film made by the process of Sho 49-31556 which is said to be useful for stretch-wrap applications.
  • Their ionomer comprises a copolymer having 90-98 mole percent ethylene, 9.7 to 2.0 mole percent of an alkyl ester of an unsaturated carboxylic acid, 0 to 2.5 mole percent of unsaturated carboxylic acid, and 0.3 to 2.5 mole percent of a metal salt of an unsaturated carboxylic acid. It is stated that their film has very good mechanical, thermal, and optical properties, but the film is limited to having less than 9.7 mole percent ester because blocking occurs between film layers.
  • copolymer is limited to a maximum of 2.5 mole percent metal salt of an unsaturated carboxylic acid due to the viscosity of the copolymer being too high to allow processing of the copolymer.
  • All copolymers in the films of the examples contain an unsaturated carboxylic acid component, which, the patent states, are used to adjust the modulus of elasticity and transparency of the film.
  • U.S. patent number 4,042,766 to Tatsukami et al. dated Aug. 16, 1977 and which is incorporated by reference in its entirety, provides a method for preparing ionically cross- linked copolymers comprising melt-blending a copolymer comprising 1) ethylene and 2) at least one alkyl acrylate or methacrylate where the alkyl is selected from the group consisting of isopropyl or tert-butyl, with 3) at least one metal compound selected from the group consisting of acetates, formates, and oxides of zinc, magnesium, calcium, and sodium, and maintaining the molten blend at a temperature of about 200 to 320°C.
  • the patent states that high mixing efficiency is desirable in the reaction equipment to assure uniform dispersion of the metal compound into the ester copolymer and to assure quick evaporation of the low molecular-weight byproducts, such as by melt- blending the components.
  • adequate mixing was provided by a 20 mm-diameter single-screw extruder having a retention time of about one minute, as illustrated in Example 1 of that patent.
  • the ionomer is then acidified by either 1) adding acid and replacing some of the basic metal with hydrogen; 2) melt-blending a polymer having acid groups with an ionomer; or 3) exchanging a non-alkali metal ion with the alkali metal ion on the ionomer which has been dispersed in a solvent.
  • U.S. patent number 5,189,113 to Muehlenbernd et al. discloses a process for making ionically cross-linked copolymers of ethylene and alpha, beta- ethylenically-unsaturated carboxylic acids or alpha, beta- ethylenically-unsaturated comonomers donating carboxyl groups, such as anhydrides.
  • This process requires reacting the copolymer with a solid metal compound in a mixing zone of a twin-screw extruder and subsequently pumping in water.
  • the advantages for this process are said to be that no discoloration of the ionomer occurs because no corrosion of the twin-screw extruder occurs, and no specks of unreacted solid metal compound are found in the ionomer film.
  • the invention comprises a copolymer of alpha-olefins having from two to eight carbon atoms, esters of alpha, beta-ethylenically-unsaturated carboxylic acids having from four to twenty-two carbon atoms, and metal salts of acrylic or methacrylic acid, wherein this copolymer has a haze of no more than ten percent as measured by ASTM method D 1003.
  • the invention comprises a copolymer of ethylene, methyl acrylate, and sodium salt of acrylic acid, wherein the haze of the copolymer is no more than five percent.
  • the invention comprises a method of reducing the water solubility of an ionomer composition formed into a shape such as strands, pellets, or film, which method comprises contacting a surface of the shape with an acid.
  • the present invention is based on our finding that films of the composition as described herein have very low haze, particularly when the films are made after saponifying a copolymer as described above under conditions which include intensive mixing, a greater extent of saponification, and higher reaction temperatures. Film haze is no more than ten percent, and many films have a haze of no more than five or even two percent. Furthermore, in a preferred embodiment, the composition has improved properties such as improved tensile strength, hot tack strength, and/or heat seal strength over ionomers of similar composition.
  • compositions of this invention have no acidity, regardless of the extent of saponification.
  • FIG. 1 A JEOL JSM-820 scanning electron microscope was used to generate the micrographs.
  • the micrographs of Figures 1 and 2 show the fracture surface of films which were made by the blown film process of the examples.
  • Figure 3 shows the hot-tack of ionomer of this invention from Example 24 as a function of temperature.
  • the ordinate is temperature in °C
  • the abscissa is hot-tack, measured in Newtons/inch.
  • Line 1 is 35% hydrolyzed ionomer
  • line 2 is 42% hydrolyzed ionomer
  • line 3 is 50% hydrolyzed ionomer.
  • Figure 4 shows the heat seal strength of the ionomer/polyethylene film of Example 26 as a function of temperature.
  • the ordinate is temperature in °F and the abscissa is the heat seal strength in lb/inch.
  • compositions of this invention can be represented as the copolymerization product which contains the following comonomers:
  • esters of alpha,beta-ethylenically-unsaturated carboxylic acids (b) esters of alpha,beta-ethylenically-unsaturated carboxylic acids. (c) metal salts of acrylic or methacrylic acid, and
  • compositions have no more than ten percent haze, preferably no more than seven percent haze, and more preferably, no more than five percent haze.
  • the most preferred compositions have no more than two percent haze. Additionally, these compositions have very good hot tack strength, heat seal strength, and mechanical properties such as tensile strength. Acid functionality can also be introduced into these ionomers.
  • compositions of this invention include ethylene- methyl acrylate-sodium acrylate ionomer, ethylene-methyl methacrylate-sodium methacrylate ionomer, ethylene-ethyl acrylate-sodium acrylate ionomer, ethylene-propylene-methyl acrylate-sodium acrylate ionomer, ethylene-propylene-methyl methacrylate-sodium methacrylate ionomer, ethylene-methyl acrylate-lithium acrylate ionomer, ethylene-methyl acrylate- potassium acrylate ionomer, ethylene-methyl acrylate- cobalt(II) or (III) acrylate ionomer, ethylene-methyl acrylate-zinc acrylate ionomer, ethylene-methyl acrylate- titanium(II) , (III) , or (IV) acrylate ionomer, ethylene- methyl aerylate-magnesium
  • Monomer (a) comprises alpha-olefins having from 2 to 8 carbon atoms.
  • monomer (a) comprises alpha- olefins having from 2 to 3 carbon atoms, and more preferably, monomer (a) consists essentially of ethylene.
  • Monomer (c) is a metal salt of acrylic or methacrylic acid.
  • the metal ion is selected from Group IA, Group IIA, and transition metal ions.
  • the metal ions may also be aluminum, gallium, germanium, and tin. Other examples include lithium, sodium, potassium, rubidium, cesium, calcium, magnesium, zinc, titanium, iron, cobalt, nickel, and copper.
  • the metal ion is a Group IA or Group IIA metal ion, and more preferably, the metal ion is a Group IA metal ion. Most preferred is sodium.
  • Monomer (c) is about 25 to 99 mole percent of the total amount of (b) and (c) present in a composition.
  • monomer (c) is about 35 to 80, and more preferably, is about 40 to 60, mole percent of the total amount of (b) and (c) present in a composition.
  • a composition of this invention contains from about 1 to 20 mole percent of monomers (b) and (c) in total.
  • a composition contains about 3.5 to 12.5 mole percent, and more preferably, about 5.5 to 10 mole percent of monomers (b) and (c) .
  • Most preferred is a composition containing about 7.5 to 10 mole percent of monomers (b) and (c).
  • Monomer (d) is an alpha, beta-ethylenically-unsaturated comonomer which imparts certain desired polymer properties.
  • the amount and type of monomer (d) is determined by the particular properties that are desired in the final composition.
  • monomer (d) may be acrylic or methacrylic acid which is present in an amount that provides the desired acid functionality to the composition.
  • Other examples of monomer (d) include maleic anhydride and maleic acids to impart acidity, acrylonitrile to impart solvent resistance, and styrene to increase the rigidity of the composition.
  • the compositions contain 0 to 10 mole percent of monomer (d) .
  • Preferred compositions contain 0 to 5 mole percent of monomer (d) .
  • Monomer (d) can also be added by grafting a group such as acrylic acid or maleic anhydride to a composition of the present invention or to one of the composition's precursors.
  • compositions can comprise grafted (ethylene, ( eth) acrylate, metal salt of (meth)acrylic acid) copolymers.
  • Maleic anhydride-grafted (ethylene, methyl acrylate, sodium acrylate) copolymer is one such composition.
  • the ionomer compositions of this invention have a number of surprising features which distinguish them from other ionomers having similar chemical constituents.
  • the ionomers of this invention are quite clear. Haze is typically no more than 5 percent.
  • the 60° gloss is typically at least 100, and in many instances, is at least 120.
  • tensile strength of the composition is improved over ionomers of similar composition by 100-300 percent. Hot-tack strength and heat seal strength can also be improved over ionomers of similar composition. Combinations of these improved features are present in some preferred compositions of this invention.
  • the haze, gloss, and tensile strength of ionomer of this invention are substantially different from the haze, gloss, and tensile strength of ionomer made by the process of U.S. Pat. N* 5,218,057.
  • Ethylene-methyl acrylate copolymer having about 20 weight percent (about 7.5 mole percent) methyl acrylate and having about 65% of the methyl acrylate saponified with aqueous sodium hydroxide according to the process of U.S. Pat. 5 5,218,057 had a haze of 15% and 60° gloss of 66.
  • Tensile strength of an ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate which had about 60% of the methyl acrylate groups saponified with aqueous sodium hydroxide according to the process of U.S. Pat. N 5 5,218,057 was 1582 psi in the machine direction.
  • a composition of the present invention made by saponifying an ethylene-methyl acrylate copolymer having about 20 weight percent methyl acrylate with aqueous sodium hydroxide to convert about 65% of the methyl acrylate groups had a haze of 2%, gloss of 133, and tensile strength in the machine direction of 4010 psi.
  • the ionomers of this invention also can be formed into very thin film.
  • the blow-up ratio can be as high as 2:1 to about 2.5:1.
  • a film of ionomer of this invention can have a thickness of less than about 1 mil. Film having a thickness of about 0.5 mil has been made, and film having a thickness of about 0.2 - 0.3 mil can be made on conventional processing equipment.
  • the morphology of prior art ionomers can also differ substantially from the morphology of ionomers of this invention.
  • the morphology of prior art ionomers can also differ substantially from the morphology of ionomers of this invention.
  • Prior-art ionomers can contain highly localized and large clusters of ionic material dispersed throughout the ionomer. Scanning-electron micrographs have shown that these clusters can range in size from about 0.05 micron to greater than 1 micron in size.
  • Figure 2 is a scanning-electron micrograph for the ionomer of Comparative Example G.
  • This ionomer consists essentially of ethylene, 5.7 mole percent methyl acrylate, and 1.8 mole percent of the sodium salt of acrylic acid.
  • the spherical or oblong ionic clusters evident in this micrograph range in size from about 0.1 micron to about 0.5 micron.
  • the clusters were determined to be ionic by energy-dispersive X-ray spectroscopy, which showed a higher sodium content within the clusters when compared to the surrounding continuous phase.
  • Figure 1 is a scanning-electron micrograph for ionomer composition of this invention, which consists essentially of ethylene, 3.7 mole percent methyl acrylate, and 3.7 mole percent of the sodium salt of acrylic acid.
  • This ionomer composition is substantially free of ionic clusters of the size seen in Figure 2, since essentially no ionic clusters are observed in this micrograph.
  • An ionomer composition which is substantially free of ionic clusters contains essentially no ionic clusters about 0.05 micron in size or larger when a freeze-fractured cross-section of 3-mil thick blown film which is made by the method of Example 1 is viewed with a scanning electron microscope at a magnification factor of 8,000.
  • An ionomer composition which is substantially free of ionic clusters will also have a haze of no more than ten percent.
  • the ionomer composition of Figure 1 corresponds to the composition of Example 12, which had a haze of 3%.
  • the large flecks of debris in Figure 1 are believed to be foreign matter. The flecks are not regions having high sodium content.
  • Additives well-known in the art may be included in the ionomer, such as anti-block and slip additives and anti- oxidants.
  • the composition of this invention also contains a polymeric acid having a molecular weight of less than about 10,000, such as ethylene acrylic acid. Ionomer compositions containing these low molecular weight acids are disclosed in copending U.S. Ser. No. 08/188,848, filed Jan. 31, 1994, which is incorporated by reference in its entirety herein.
  • compositions of this invention comprises saponifying a copolymer having ester groups with a Group IA metal-containing solution.
  • a method for making compositions of this invention comprises saponifying a copolymer having ester groups with a Group IA metal-containing solution.
  • This method minimizes the production of localized ionomer regions or domains, which appear as the spherical and oblong ionic clusters of Figure 2.
  • This method also permits a greater extent of saponification of the copolymer without obtaining a saponified product that has so high of a viscosity that it cannot be formed into a film on conventional equipment.
  • reaction components results from selection of reactants with the appropriate physical and chemical characteristics and selection of the proper processing conditions. Particular processing conditions are discussed below for a reactive extruder. However, the general principles disclosed therein apply to processes which are equivalent to saponifying a copolymer with a Group IA metal-containing solution in a reactive extruder.
  • copolymer to be saponified comprise copolymers of ethylene, esters of alpha, beta-ethylenically-unsaturated carboxylic acids, and optional alpha, beta-ethylenically- unsaturated comonomers which impart desirable polymer properties. Typically, these copolymers contain from about 1 to 20 mole percent of esters of alpha, beta-ethylenically- unsaturated carboxylic acids in total.
  • the copolymers contain about 2 to 20 mole percent, more preferably 3.5 to 12.5 mole percent, and even more preferably, about 5.5 to 12.5 mole percent of esters of alpha, beta-ethylenically-unsaturated carboxylic acids in total. Most preferred are those copolymers containing about 6.5 to 10 mole percent of esters of alpha, beta- ethylenically-unsaturated carboxylic acids.
  • the preferred esters are alkyl acrylates.
  • the alkyl group contains from one to eight carbon atoms, and more preferably contains from one to four carbon atoms. Methyl is a preferred alkyl group.
  • copolymers which are saponified include ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene-methyl acrylate copolymer, ethylene- propylene-methyl methacrylate copolymer, ethylene-methyl acrylate-acrylic acid copolymer, ethylene-methyl methacrylate-methacrylic acid copolymer, maleic anhydride- grafted-ethylene-methyl acrylate copolymer, ethylene-methyl acrylate- aleic anhydride copolymer, acrylic acid-grafted- ethylene-methyl acrylate copolymer, and ethylene-methyl aerylate-butyl acrylate copolymer.
  • the copolymers are ethylene-methyl acrylate copolymer, ethylene- methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, maleic anhydride-grafted-ethylene-methyl acrylate copolymer, and ethylene-methyl acrylate-butyl acrylate copolymer. Most preferred is ethylene-methyl acrylate copolymer.
  • the melt index of copolymers to be saponified should be between about 100 and 2000, preferably between about 200 and 800, and more preferably between about 300 and 600 grams/10 minutes. Copolymers having higher melt-index values are preferred when it is desired to have a saponified composition with a higher melt index.
  • One process for making these copolymers comprises polymerizing ethylene, alkyl acrylate and/or alkyl methacrylate, and the optional comonomer in autoclaves using free-radical initiation catalysts. This process is described in U.S. Patent N* 3,350,372, which is incorporated by reference in its entirety. The copolymers of the examples were made by this method, unless specified otherwise.
  • the ethylene-alkyl acrylate copolymer is made by the process described in copending U.S. Ser. No. 07/947,870, filed Sep. 21, 1992 (published as WO 93/06137), which is incorporated by reference in its entirety herein.
  • Copolymer made by this process has a substantially higher melt-point temperature than the copolymer made by the process of U.S. Patent No. 3,350,372.
  • the ionomer of this invention has high melt point temperature and high clarity when made with this copolymer.
  • Another process for producing copolymers useful in making the ionomer compositions of this invention comprises free-radical polymerization of ethylene and alkyl acrylate and/or alkyl methacrylate as described above.
  • the Group IA metal-containing solution comprises a Group IA metal in a solvent, which solvent does not prevent saponification of an ester by the Group IA metal.
  • the solvent is preferably one which evaporates readily under devolatilization conditions typically encountered in reactive extruders.
  • Solvents can be organic or inorganic, and common solvents include water, alcohols, and polyethylene glycols, with water being preferred.
  • the overall concentration of metals in the Group IA metal-containing solution is low enough that the solution is capable of being mixed uniformly and intensively with melted copolymer in a reaction section of a reactive extruder.
  • a sufficient quantity of solvent is present when the Group IA metal-containing solution contains little or no excess solvent beyond that required to solubilize essentially all of the Group IA metal and other metals present.
  • 50% aqueous caustic solution is preferred over 35% aqueous caustic solution.
  • the Group IA metal-containing solution may optionally contain other metal oxides, hydroxides, and/or salts which supply cations for monomer (c) .
  • the metal ions can be alkaline earth or transition-element metals. Specific examples of these metals include calcium, magnesium, zinc, titanium, cobalt, nickel, and copper.
  • Typical anions include hydroxide, halide, acetate, propionate, decanoate, and stearate ions, with acetate ions being preferred anions.
  • the hydroxide form is also preferred.
  • metal ions may optionally be incorporated into the ionomer composition of this invention by other methods.
  • One method is to first saponify a copolymer by the method of this invention, then totally or partially replace the ion of this ionomer composition with other metal ions under ion-exchange conditions, or to react the ionomer composition with an aqueous metal hydroxide.
  • an ion-exchange solution comprising an aqueous solution of zinc oxide or zinc acetate may be mixed with a sodium ionomer composition of this invention in a section of a reactive extruder to replace at least a portion of the sodium ions with zinc ions.
  • metal ions which may be exchanged include the alkaline metals, alkaline earth metals such a magnesium, transition metals such as titanium, cobalt, copper, and zinc, and other metal ions such as aluminum, gallium, germanium, and tin.
  • the anion of a salt used to ion-exchange the ionomer is preferably one which is easily washed out of the ionomer and separated from it during filtration.
  • the anion is preferably one which forms an easily-evolved compound or one which evolves or whose products of decomposition evolve at devolatilization conditions in a reactive extruder.
  • Typical anions include chloride, acetate, propionate, decanoate, and stearate ions. Acetate ions are preferred.
  • a reactive extruder which is useful in producing compositions of this invention comprises an extruder having a copolymer feed section, one or more reaction sections, a subsequent devolatilization section, and an extrusion section. Typically, these sections are separately jacketed to allow for heating or cooling within each section. These sections can also be vented with one or more vent ports per section to allow the escape of volatile components, such as the solvent for the Group IA metal solution and byproducts of the saponification reaction, such as alcohols.
  • the reactive extruder will also have optional means for introducing reactants into any reaction sections as well as means for mixing components in the reaction section(s) and means for conveying the components through the extruder. Typically, the means for mixing and conveying components to be reacted are screws.
  • Reactive extruders can have a single screw or multiple screws. Each screw typically has a central shaft with a key-way or spline upon which mixing elements are secured.
  • the reactive extruder may have either co-rotating or counter-rotating screws.
  • copolymer to be reacted is fed to the screw through a loss-in-weight feeder, and the solid copolymer is melted in a feed section of the reactive extruder.
  • all reactants i.e. copolymer and Group IA metal-containing solution
  • copolymer pellets are introduced into a feed section of a reactive extruder, where the pellets are heated and worked by the screw to form molten or fluid copolymer.
  • the screw elements also convey the molten copolymer from this feed section to a first reaction section, where the molten copolymer and Group IA metal-containing solution are mixed intensively.
  • Intensive mixing can be supplied by incorporating one or more reverse-flow elements along with neutral or reverse- flow kneading blocks on the screw in a reaction zone.
  • the copolymer to be saponified and the Group IA metal-containing solution should be mixed as uniformly and as quickly as possible to provide a fairly uniform reaction of metal- containing solution with the molten copolymer. Mixing should be of sufficient intensity that saponification of only localized areas is prevented.
  • the left-handed elements in the reaction section provide momentary retardation of polymer flow in addition to a shear zone due to impeded and/or reversed flow of the reaction mass, while the neutral kneading blocks imparted intensive mixing and promoted additional shear.
  • Most of the compositions of this invention were produced at a screw speed of about 400 to 550 rp . High screw speeds help to assure intensive mixing.
  • the first number is the pitch, given in distance (mm) traveled in one revolution.
  • the second number is the length of the element (mm) .
  • the PKR element is a wedge-shaped adapter which provides a taper from the 1/2 inch shaft to the first element of the screw.
  • 3. KB indicates a kneading block.
  • the first number is the angle formed by the paddles on the kneading block when compared to the line through the screw shaft, in degrees.
  • the second number is how many paddles are on one element.
  • the third number is the length of the element (mm) .
  • "LH" indicates a left-handed element.
  • Reaction temperature, feed-rate of reactants, and extent of saponification are also important processing parameters when making compositions of this invention.
  • Reaction temperature Compositions of this invention are typically produced where the barrel temperature in the reaction section(s) of the extruder is between about 200 and 350°C, although some clear ionomers were prepared at a temperature between about 150 and 200°C. Any reaction temperatures discussed herein refer to the barrel temperatures of the extruder. The actual temperature of the melted polymer is believed to be lower than the measured barrel temperature because of heat- transfer limitations.
  • the reaction temperature is between 225 and 350°C, and, more preferably, the temperature is between about 275 and 350°C.
  • the upper limit of the temperature range is determined by the temperature at which the copolymer or composition degrades.
  • the lower limit of the temperature range is the temperature at which 1) the copolymer to be reacted is in a molten or fluid state; 2) essentially all of the Group IA metal in the Group IA metal-containing solution is consumed by the saponification reaction within the reaction section; and 3) the composition being extruded remains visually clear.
  • higher reaction temperatures as specified in the more preferable range above provide low-haze ionomers more consistently than lower reaction temperatures.
  • the Group IA metal-containing solution is fed in an amount that is effective to achieve the desired extent of saponification of the copolymer being fed to the reactive extruder. Typically, essentially all of the Group IA metal in solution reacts with the copolymer.
  • the Group IA metal- containing solution may be fed to a reaction section batch- wise or continuously, or it may be fed intermittently so that the solution is mixed intimately and rapidly with the molten copolymer. A continuous feed is preferred.
  • the Group IA metal-containing solution may also be split between multiple reaction sections and be fed continuously and/or intermittently to any reaction section.
  • the copolymer to be saponified is fed to the reactive extruder at a rate high enough that the molten polymer forms a molten polymer seal between consecutive segments of a reaction section and between a reaction section and a devolatilization section.
  • This seal can be formed by having a reverse-flow screw element at the desired seal location.
  • the feed-rate should also be low enough that the reaction mass comprising the copolymer to be saponified and the Group IA metal-containing solution does not move through the reaction section so quickly that the reaction mass is not mixed intensively.
  • the feed-rate should also be low enough that the extruded polymer is visually clear, corresponding to no more than ten percent haze.
  • the copolymer to be saponified may be fed to the extruder batch-wise, intermittently or continuously. A continuous feed is preferred to provide a commercially-attractive process which is easily and effectively controlled.
  • the average residence time for reactants in a Werner & Pfleiderer ZSK-40 twin-screw extruder which has a feed section, one reaction section, devolatilization section, and pumping section is about 30 to about 40 seconds at a continuous feed-rate of approximately 100 lb./hr. of polymer to be saponified and at a screw speed of about 500 rpm.
  • the average residence time in the reaction section of this reactive extruder at these conditions is typically about 5 to about 15 seconds.
  • (c) % saponified The extent of saponification is defined as the percent of moles of esters of alpha, beta-ethylenically-unsaturated ' carboxylic acids converted to metal salts of acrylic and methacrylic acid.
  • Compositions of this invention have been produced where the extent of saponification of the ester groups in the copolymer has been between about 25 and 99%.
  • Ionomer which has an extent of saponification below about 25% above are typically cloudy and have poorer gloss, melt strength, and/or tensile strength than compositions of this invention.
  • a greater extent of saponification generally produces low-haze ionomers more consistently than a low extent of saponification, particularly when the reaction temperature is between about 150 and 225°C.
  • Acidification of a polymer is a useful method for modifying polymer properties.
  • ionomers of this invention have essentially no acidity. These ionomers can be represented as copolymers comprising comonomers of alpha-olefins, esters of alpha, beta- ethylenically-unsaturated carboxylic acids, and metal salts of alpha, beta-ethylenically-unsaturated carboxylic acids. The properties of these non-acidic ionomers can be modified by adding acid groups.
  • some of the ionomers of this invention are highly water-dispersible. This can be an advantage for applications where repulpable compositions are desired, such as repulpable paper coatings and adhesives.
  • water dispersibility is a problem where the ionomer composition is cooled in a water-bath after saponification, which is a common commercial method of cooling polymers. Much of the ionomer to be cooled can end up dispersed in the cooling water, turning the water a milky white color.
  • cooling means may be used for handling highly water- dispersible ionomers, such as hot-face cutting or utilizing an air-cooled conveyor or a conveyor which has a water- chilled surface to cool the polymer strands or pellets.
  • these methods are more expensive and less efficient than passing hot polymer in the form of strands, pellets, or film through a water bath, and these methods require the installation of new equipment in many existing commercial ionomer production facilities.
  • ionomer may discolor when using these cooling means, since the ionomer rapidly oxidizes when it is maintained at elevated temperatures for the extended periods of time inherent in these other cooling means.
  • Cooling ionomer in an aqueous acid bath In a preferred embodiment, highly water-dispersible ionomer of this invention may be cooled in an acid bath to prevent dispersion of much of the ionomer.
  • Highly water-dispersible ionomer typically has a high sodium acrylate content which makes the ionomer water-soluble. It is believed that ion exchange occurs predominantly on the surface of the polymer when passing hot ionomer strands through the acid bath, replacing metal ions on the surface of the polymer with hydrogen ions from the acid. It is believed that this makes the surface of the strands or pellets acidic and substantially reduces their water solubility.
  • any inorganic or water-soluble organic acid can be used in the acid bath.
  • a dilute aqueous solution of a non- oxidizing acid is preferred to reduce processing cost and to improve the washing efficiency when rinsing any excess acid off of the polymer.
  • the following list is illustrative of the types of acids which may be used: sulfuric acid, formic acid, propionic acid, oxalic acid, and the like.
  • Preferred acids are hydrochloric acid, phosphoric acid, and acetic acid.
  • Example 16 illustrates this method for cooling ionomer using an aqueous acid solution.
  • compositions of this invention have carboxylic acid groups, in which case the compositions can be represented as copolymers comprising comonomers of alpha- olefins, esters of alpha, beta-ethylenically-unsaturated carboxylic acids, metal salts of alpha, beta-ethylenically- unsaturated carboxylic acids, and alpha, beta-ethylenically- unsaturated carboxylic acids.
  • Acid groups can plasticize the composition and increase its melt index. This permits tailoring of polymer properties such as polymer flow viscosity, tear strength, polymer reactivity with food, and odor or taste for a particular application.
  • Acidification of a composition comprising a copolymer of alpha-olefins, esters of alpha, beta-ethylenically- unsaturated carboxylic acids, and metal salts of alpha, beta-ethylenically-unsaturated carboxylic acids can occur in a reaction section of a reactive extruder.
  • acidification occurs in a second reaction section when using reactive extrusion, and preferably after the composition comprising the reaction product of a copolymer of alpha- olefins and esters of alpha, beta-ethylenically-unsaturated carboxylic acids has been saponified with a Group IA metal- containing solution in a first reaction section.
  • Other equipment may be used in place of a reactive extruder for acidification of a saponified composition. For example, a Brabender Plasticorder, a resin kettle, or an autoclave may be used.
  • a non-oxidizing acid can be used at a temperature and in a concentration which does not cause significant degradation of the copolymer or composition.
  • the amount of acid required is the amount which provides the desired weight percent of acid groups per combined weight of acid and copolymer to be acidified.
  • these acids include phosphoric acid, hydrochloric acid, benzoic acid, lactic acid, and stearic acid.
  • Polymeric non-oxidizing acids can also be used, such as ethylene-acrylic acid copolymer, exemplified by Dow Chemical Company's Primacor Grade 3330.
  • the non-oxidizing acids may have only one or two monomer units, such as benzoic acid or acetic acid, or they may comprise polymeric acids having multiple monomer units and having a molecular weight well in excess of one million, such as Primacor Grade 3330. Phosphoric acid, lactic acid, and polymer acids are preferred. Typical temperatures for acidification are between about 190 and 300°C, and preferably are between about 230 and 300°C. The acid concentration is preferably between 10 and 95%.
  • any byproducts of acidification can remain in the composition.
  • any byproducts of acidification and/or any excess acid can be removed from the ionomer by washing with water or other solvent and filtering the composition.
  • polymer acidified using phosphoric acid can be washed with water in an autoclave.
  • the byproduct salt in the aqueous phase can subsequently be separated from the polymer by filtration.
  • Acidification of hazy non-acidic ionomer to improve clarity Acid can also be used to improve the clarity of an ionomer which has high haze and little or no acid functionality present before acidification. This provides an easy and inexpensive means for rendering these opaque polymers less hazy or even clear.
  • the adhesion of the acidified polymer improves as well.
  • the melt index of the ionomer also increases.
  • the ionomer to be acidified has a haze greater than 10% but otherwise has the same chemical analysis of components as described in the preceding section for adding acid functions to a clear but non-acidic ionomer composition of this invention. Acidification is also preferably performed as described in the preceding section. Uniform mixing of the acid and ionomer, as supplied by a reactive extruder, for example, provides a consistent and clearer acidified ionomer. In the examples, the haze of the ionomer to be acidified exceeded 90% and could be reduced in half and even by 75%.
  • the previous section also specifies the types of acids useful for acidifying hazy ionomers.
  • the amount of acid required for acidification is that amount which provides an ionomer film having at most half of the haze that was present in the non-acidified ionomer.
  • the amount of acid used also should not exceed that amount which is necessary to provide the greatest reduction in haze for the particular ionomer and acid used.
  • Tables 22 and 23 show, haze begins to increase again once the amount of acid is increased beyond the amount necessary to provide minimum haze for the particular ionomer and acid. Therefore, excess acid beyond the amount required to reduce the haze to its minimum value is to be avoided.
  • the acidified ionomer When the acidified ionomer is analyzed, as little as 0.05 mole of acidic monomer need be present in the ionomer per mole of the saponified monomer that was originally present in the ionomer prior to acidification.
  • ethylene-methyl acrylate-sodium acrylate ionomer having greater than 10% haze is made from ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate which is 25% hydrolyzed using aqueous sodium hydroxide
  • the ionomer has approximately 5.4 weight percent sodium acrylate, or about 1.9 mole percent sodium acrylate. Acidification of at least 5% of the sodium acrylate groups decreases the haze of this ionomer.
  • the amount of acidic monomer in the acidified ionomer is greater than 0.07 mole per mole of hydrolyzed monomer present in the non-acidified ionomer, and preferably the amount of acidified ionomer is greater than 0.1 mole per mole.
  • Examples 20-23 illustrate this method of making clearer ionomers from hazy ionomers.
  • D. Uses of the compositions Ionomer compositions of this invention can be formed into single or multi-layer films using conventional equipment. For example, cast, extruded, or blown film can be made.
  • An ionomer composition of this invention can be coextruded with or laminated to other polymers such as nylon (unoriented and oriented) , polyester (unoriented and oriented) , polystyrene, vinyl acetate, polyacrylonitrile, polyvinylidene dichloride, and polyolefins such as polypropylene (unoriented and oriented) , polyethylene (low density, high density, and linear low density) , ethylene- methyl (meth) acrylate copolymers, ethylene-ethyl (meth) acrylate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene-vinyl alcohol copolymers, ethylene vinyl acetate copolymers, and other polymers and their derivatives capable of being coextruded.
  • polymers such as nylon (unoriented and oriented) , polyester (unoriented and oriented) , polystyrene, vinyl acetate, polyacrylonitrile, polyvinylidene dich
  • Typical uses for ionomer compositions of this invention include their use in single-layer or multi-layer films, where they can be used as tie layers or used for imparting flexibility, strength, hot tack, and/or heat seal capabilities.
  • Such uses include stretch films, bundling (shrink) wrap, food and drug packaging, and skin packaging for protecting the contents of a package.
  • Single-layer ionomer film or multi-layer film in which the ionomer is on one face of the film can be used as a surface protection layer for products such as glass, polycarbonate or poly(methyl methacrylate) products, which can be used in windshields for vehicles or windows.
  • the ionomer layer protects products from scratches and/or nicks because of the iono er's abrasion resistance.
  • the ionomer's adhesion to such substrates is excellent, yet it can be peeled readily from the surface.
  • the transparency of the ionomer of this invention allows visual inspection of the surface of the wrapped product, permitting a customer to inspect a product for flaws prior to receipt and unwrapping of the product.
  • the ionomer of this invention can also serve as its own tie layer due to its good adhesion to other layers. This eliminates the need for separate tie layers in a multi-layer film, reducing the thickness of the multi-layer film and reducing the overall cost of making the multi-layer film.
  • Ionomer compositions of this invention may also be used in thermally extruded and thermally formed products such as automotive interior parts and skin packaging.
  • the ionomer compositions may be used alone or in combination with other polymers in blow-molded or injection molded articles, particular where such articles need to be grease- and oil- resistant such as bottles for fragrances or detergents, and the compositions may also be used in articles such as food trays formed by vacuum thermo-forming.
  • the ionomer compositions of this invention may be used in making articles such as golf ball covers; coated fabrics; orthopedic, prosthetic and medical devices; recreational equipment; and footwear components.
  • the ionomer compositions of this invention are especially useful in applications where the ionomer properties discussed above, as well as the excellent abrasion resistance, transparency, and/or directional tear properties of the ionomer, are useful.
  • EXAMPLE 1 An ethylene-methyl acrylate copolymer (manufactured by Chevron by the method disclosed in U.S. Patent No. 3,350,372) containing 20% by weight methyl acrylate (7.5 mole %) and having a melt index of 400 g/10 min. (190°C) was fed to a Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. The extruder had a ratio of length to diameter of about 44.
  • the screw configuration for Examples 1-13 and Comparative Example A is given in Table 1 column A.
  • Aqueous sodium hydroxide (50% NaOH by weight in all examples, except where noted otherwise) was fed to Zone 3 of the extruder at 9.3 lbs./hr. The screw speed was 550 rpm.
  • Water from the sodium hydroxide solution and the reaction by-product methanol were removed by a two-stage devolatilization.
  • the evolved water and methanol from the first devolatilization stage were condensed at atmospheric pressure.
  • the second devolatilization stage was connected to a vacuum system in all examples.
  • the second devolatilization stage had 28.4 in. Hg vacuum during this run.
  • the product had a melt flow rate of 0.33 g/10 min. (230°C) .
  • the product had a hydrolysis of 53% (i.e., 53% of the methyl acrylate in the ethylene-methyl acrylate copolymer was converted to sodium acrylate) .
  • the polymer was made into blown film on a Victor blown film line at the following processing conditions:
  • the blown film had a thickness of 3.5 mils.
  • the haze of the film was 2%, and the 60° gloss was 122.
  • the 1% secant moduli of the film were 12,740 and 10,080 psi respectively for the machine direction (MD) and the transverse direction (TD).
  • Melt index of feed resin was measured by the method of ASTM D 1239, using a temperature of 190°C and a 2.16 kg weight.
  • the melt flow rate of a composition of this invention was determined by the method of ASTM D 1239 but using a temperature of 230°C rather than 190°C and using a 2.16 kg weight.
  • the hydrolysis of the product is defined as the moles of metal salt of the alpha, beta-ethylenically-unsaturated carboxylic acid present in the product, expressed as a percentage of the moles of the ester of alpha, beta-ethylenically-unsaturated carboxylic acid present prior to saponifying the copolymer.
  • the terms "hydrolysis”, “extent of hydrolysis”, “percent hydrolysis”, “percent saponified”, and “extent of saponification” are used interchangeably.
  • the extent of hydrolysis is determined by dissolving 10 g. of ionomer in 250 ml. of tetrahydrofuran (THF) in a 500 ml. round-bottom flask, to which 1 ml. of glacial acetic acid is added. The flask is fitted with a refluxing condenser, and the contents are boiled for about 20 min. The mixture is poured into 1 liter of cold distilled water (about 15-20°C) , and then filtered. The precipitate is subsequently washed with about 3 liters of distilled water.
  • THF tetrahydrofuran
  • EXAMPLE 2 The ethylene-methyl acrylate copolymer of Example 1 was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 of the extruder at a rate of 11.2 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 28.4 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.20 g/10 min. (230°C) .
  • the hydrolysis of the product was 65%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 2%, and the 60° gloss was 133.
  • the film had a tensile strength of 4010 and 3180 psi respectively for MD and TD.
  • the 1% secant moduli of the film were 14720 and 13110 psi respectively for MD and TD.
  • the vacuum on the second devolatilization zone was 28.5 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.1 g/10 min. (230°C) .
  • the hydrolysis of the product was 70%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 2%, and the 60° gloss was 134.
  • the film had a tensile strength of 4470 and 2420 psi respectively for MD and TD.
  • EXAMPLE 4 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 570 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 13.0 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 25.5 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.87 g/10 min. (230°C) .
  • the hydrolysis of the product was 69%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 2%, and the 60° gloss (ASTM D 2457) was 135.
  • the film had a tensile strength of 2870 and 1760 psi respectively for MD and TD.
  • EXAMPLE 5 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 440 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 13.0 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 28.4 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.81 g/10 min. (230°C) .
  • the hydrolysis of the product was 72%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 2%, and the 60° gloss was 135.
  • the film had a tensile strength of 2600 and 1850 psi respectively for MD and TD.
  • EXAMPLE 6 An ethylene-methyl acrylate copolymer containing 23% by weight methyl acrylate and having a melt index of 500 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 10.7 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 26.7 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.54 g/10 min. (230°C) .
  • the hydrolysis of the product was 51%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 2%, and the 60° gloss was 124.
  • the film had a tensile strength of 2270 and 1470 psi respectively for MD and TD.
  • EXAMPLE 7 An ethylene-methyl acrylate copolymer containing 23% by weight methyl acrylate and having a melt index of 500 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 12.8 lbs./hr. The screw speed was 500 rpm. The following temperatures were measured during the process:
  • the vacuum on the second devolatilization zone was 26.6 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.45 g/10 min. (230°C) .
  • the hydrolysis of the product was 61%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 3%, and the 60° gloss was 132.
  • the film had a tensile strength of 2730 and 1960 psi respectively for MD and TD.
  • EXAMPLE 8 An ethylene-methyl acrylate copolymer containing 23% by weight methyl acrylate and having a melt index of 500 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 9.6 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 26.2 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.60 g/10 min. (230°C) .
  • the hydrolysis of the product was 46%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 2%, and the 60° gloss was 120.
  • the film had a tensile strength of 1950 and 1240 psi respectively for MD and TD. ⁇
  • EXAMPLE 9 An ethylene-methyl acrylate copolymer containing 22% by weight methyl acrylate and having a melt index of 470 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 14.3 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 28.4 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.23 g/10 min. (230°C) .
  • the hydrolysis of the product was 70%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 1%, and the 60° gloss was 134.
  • the film had a tensile strength of 3000 and 2170 psi respectively for MD and TD.
  • EXAMPLE 10 An ethylene-methyl acrylate copolymer containing 23% by weight methyl acrylate and having a melt index of 500 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 8.6 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 25.8 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 1.25 g/10 min. (230°C) .
  • the hydrolysis of the product was 41%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 4%, and the 60° gloss was 104.
  • the film had a tensile strength of 1910 and 970 psi respectively for MD and TD.
  • EXAMPLE 11 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 100 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 4.7 lbs./hr. The screw speed was 500 rpm.
  • the vacuum on the second devolatilization zone was 28.4 in. Hg.
  • the reaction product was extruded, cooled on a Sandvik belt and pelletized in the same way as Example 1.
  • the product had a melt flow rate of 0.67 g/10 min. (230°C) .
  • the hydrolysis of the product was 26%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 3%, and the 60° gloss was 115.
  • the film had a tensile strength of 1150 and 1080 psi respectively for MD and TD.
  • EXAMPLE 12 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 400 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 9.3 lbs./hr. The screw speed was 500 rpm.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 3%, and the 60° gloss was 128.
  • EXAMPLE 13 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 150 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 7.4 lbs./hr. The screw speed was 450 rpm. The following temperatures were measured during the process:
  • the vacuum on the second devolatilization zone was 28.5 in. Hg.
  • the reaction product was extruded, cooled in a water bath, and pelletized. The pellets were dried in a vacuum over at 65°C and 29.5 in. Hg for 48 hours.
  • the product had a melt flow rate of 0.22 g/10 min. (230°C) .
  • the hydrolysis of the product was 42%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 4%, and the 60° gloss was 122.
  • EXAMPLE 14 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 400 g/10 min. (190°C) was fed to a Werner & Pfleiderer ZSK-58mm twin screw extruder at a rate of 425 lbs./hr. The screw was configured to provide substantially the same mixing as provided in the ZSK-40mm extruder in Examples 1- 13. Aqueous sodium hydroxide was fed to the reaction zone on the extruder at a rate of 56 lbs./hr.
  • the screw speed of the extruder was at 500 rpm.
  • the temperatures in the reaction zones were 226°C to 338°C.
  • the product was 71% hydrolyzed.
  • the product had similar optical properties to the product of Example 3.
  • EXAMPLE 15 An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 400 g/10 min. (190°C) was fed to a Werner & Pfleiderer ZSK-70mm twin screw extruder at a rate of 450 lbs./hr.
  • the screw was configured to provide substantially the same mixing as provided in the ZSK-40mm extruder in Examples 1- 13.
  • Aqueous sodium hydroxide was fed to the reaction zone on the extruder at a rate of 50 lbs./hr.
  • the screw speed of the extruder was at 580 rpm.
  • the temperatures in the reaction zones were 330°C to 350°C.
  • the product was 61% hydrolyzed.
  • the product had similar optical properties to the product of Example 3.
  • COMPARATIVE EXAMPLE A An ethylene-methyl acrylate copolymer containing 20% by weight methyl acrylate and having a melt index of 20 g/10 min. (190°C) was fed to the Werner & Pfleiderer corrosion-resistant ZSK-40mm twin screw extruder at a rate of 100 lbs./hr. Aqueous sodium hydroxide was fed to Zone 3 on the extruder at a rate of 4.6 lbs./hr. The screw speed was 400 rpm.
  • the vacuum on the second devolatilization zone was 27.9 in. Hg.
  • the reaction product was extruded, cooled in a water bath, and pelletized. The pellets were dried in a vacuum over at 65°C and 29.5 in. Hg for 48 hours.
  • the product had a melt flow rate of 3.2 g/10 min. (190°C)
  • the hydrolysis of the product was 15%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 81%, and the 60° gloss was 35.
  • COMPARATIVE EXAMPLE B An ethylene-methyl acrylate copolymer containing 20% methyl acrylate by weight and having a melt index of 400 g/10 min. was fed to a Werner & Pfleiderer ZSK-30 corrosion-resistant extruder at 13.2 lbs/hr. 1.73 lbs/hr. of 35% sodium hydroxide solution was fed to zone 3 of the extruder.
  • the extruder had the configuration of elements shown in Table 1 column B.
  • COMPARATIVE EXAMPLE C An ethylene-methyl acrylate copolymer containing 20% methyl acrylate by weight and having a melt index of 400 g/10 min. was fed to a Werner & Pfleiderer ZSK-30 corrosion-resistant extruder at 13.2 lbs/hr. 2.29 lbs/hr. of 35% sodium hydroxide solution was fed to zone 3 of the extruder.
  • the extruder had the configuration of elements shown in Table 1 column B.
  • COMPARATIVE EXAMPLE D Ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate and a 400 melt index (190°C) was saponified with a 35% by weight aqueous solution of sodium hydroxide per the method of Comparative Example B. The product was 60% saponified and had a melt index (190°C) of 0.06. The tensile strength in the machine direction was 1582 psi.
  • COMPARATIVE EXAMPLE E Ethylene-methyl acrylate copolymer having 25 weight percent methyl acrylate and a 457 melt index (190°C) was saponified with a 35% by weight aqueous solution of sodium hydroxide per the method of Comparative Example B. The product was 44% saponified and had a melt index (190°C) of 0.04. The tensile strength in the machine direction was 985 psi.
  • EXAMPLE 16 ACID BATH COOLING OF IONOMER 26.4 lbs./hr.
  • Example 1 ethylene-methyl acrylate copolymer of Example 1 were fed to a Werner & Pfleiderer corrosion resistant ZSK-30 twin-screw extruder having the configuration of elements given in Table 1 column C. 50% aqueous sodium hydroxide was fed into zone 3 at 2.5 lb./hr. The screw speed was 500 rpm.
  • EXAMPLE 17 This example shows a copolymer of ethylene, methyl acrylate, sodium acrylate, and acrylic acid.
  • ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate and 153 melt index (190°C) was saponified in a Werner- Pfleiderer ZSK-30 twin-screw reactive extruder using 50% aqueous sodium hydroxide and substantially the same reaction conditions as Example 16. The extent of saponification was 42%.
  • the pelletized ionomer was clear and glossy and had a melt flow rate (230°C) of 0.17 g/10 min.
  • the ionomer pellets were fed to the extruder at a rate of 12 kg/hr. 85.6% aqueous phosphoric acid was fed to Zone 3 of the extruder at a rate of 0.14 kg/hr., and the product was extruded, cooled in a water bath, and pelletized.
  • EXAMPLE 18 Ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate and 400 melt index (190°C) was saponified in a ZSK-30 extruder having the configuration of elements given in Table 1 column C with 50% aqueous sodium hydroxide at a reaction temperature of about 148°C. The screw speed was 500 rpm. The copolymer was fed to the extruder at a rate of 12 kg/hr. , and the product was about 54% saponified. The product was visually clear.
  • COMPARATIVE EXAMPLE F Ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate and 400 melt index (190°C) was saponified with 50% aqueous sodium hydroxide in a ZSK-30 extruder having the configuration of screw elements given in Table 1 column B at a reaction temperature of about 149°C. The screw speed was 500 rpm. The copolymer was fed to the extruder at a rate of 16 kg/hr., and the product was about 52% saponified. The product was visually cloudy.
  • the extruder temperatures were substantially the same as those given in Table 19. Volatile components were removed in a two port devolatilization section, and the second port had a vacuum of 28 in. Hg.
  • the following table summarizes the feed rate of potassium hydroxide, the melt flow rate (230°C) , and the extent of saponification of the methyl acrylate groups.
  • COMPARATIVE EXAMPLE G An ethylene-methyl acrylate copolymer containing 20% methyl acrylate by weight and having a melt index of 20 g/10 min. (190°C) was f ed to a Werner & Pfleiderer ZSK-40 corrosion- resistant extruder at 100 lbs/hr. 4.7 lbs/hr. of 50% sodium hydroxide solution was fed to zone 3 of the extruder. The screw speed was 275 rpm.
  • the vacuum on the second devolatilization zone was 27.0 in. Hg.
  • the reaction product was extruded, cooled in a water bath, and pelletized. The pellets were dried in a vacuum over at 65°C and 29.5 in. Hg for 48 hours.
  • the product had a melt index of 1.6 g/10 min. (190°C) .
  • the hydrolysis of the product was 24%.
  • the polymer was made into blown film on a Victor blown film line using the processing conditions similar to those in Example 1.
  • the haze of the blown film was 97%, and the 60° gloss was 43.
  • EXAMPLE 20 Ethylene-methyl acrylate copolymer having 20% by weight methyl acrylate and a melt index of 20 g/10 min. (190°C) was 25% hydrolyzed by the method of Comparative Example A, and this sodium ionomer was ground to 60 mesh-sized powder. 10 grams of the ground ionomer were put into a 500 ml single- neck round-bottom flask, and 250 ml of stabilized THF and a magnetic stirrer were added. The above mixture was heated to reflux and stirred for about 10 minutes to ensure that the ionomer dissolved. After dissolution, 1.6 ml of 2 N aqueous hydrochloric acid was added to the flask. The reaction continued for 2 hours, then the solution was precipitated in 1 liter of cold water, filtered, and dried under vacuum.
  • the reaction produced 9.7 grams of white polymer precipitate having a melt index of 0.9 g/10 min. (190°C) .
  • Fourier- transform infrared (FT-IR) analysis showed that the carboxylic acid group was present (1708 cm “1 , absorbance 1.5259) as well as sodium acrylate (1558 cm “1 , absorbance 1.0294). This indicated that 60% of the sodium acrylate groups present in the ionomer prior to acidification was converted to acid groups, thus giving a stoichiometric reaction of this acid with sodium acrylate.
  • FT-IR Fourier- transform infrared
  • the acidified ionomer was a tetrapolymer of ethylene, methyl acrylate, sodium acrylate, and acrylic acid having about 5.7 mole percent methyl acrylate, 0.8 mole percent sodium acrylate, and 1.1 mole percent acrylic acid.
  • the melt index of the acidified ionomer was 6.3 g/10 min. (190°C) .
  • the acidified ionomer had excellent adhesion to a polar substrate such as unprimed aluminum foil. Both non- acidified ionomer and acidified ionomer were separately pressed between two pieces of unprimed aluminum foil in a hydraulic press having two heated plates. The pellets and foil were heated without pressure for about 5 minutes at 350°C, then the pressure was increased to 20,000 psi and maintained for an additional 5 minutes at 350°C. The acidified ionomer sealed the aluminum foil and could not be separated from it without tearing the foil. The non- acidified ionomer was easily peeled from the foil.
  • Separate films of acidified ionomer and non-acidified ionomer were each made by placing 0.2 g of the ionomer between two pieces of Mylar film. The ionomer was heated and pressed as above. The Mylar was separated from the ionomer with a small amount of acetone. The acidified ionomer film was clear, having no observable haze and having an observable high gloss. The non-acidified ionomer film was opaque, dull, and frosty.
  • Example 20 was repeated, except that 0.2556 g of glacial acetic acid was substituted in place of the hydrochloric acid.
  • the reaction produced 9.8 grams of acidified ionomer as a white precipitate.
  • FT-IR analysis indicated that 80% of the sodium acrylate present in the ionomer prior to acidification were converted to acid groups.
  • the acidified ionomer was a tetrapolymer of ethylene, methyl acrylate, sodium acrylate, and acrylic acid, having about 5.7 mole percent methyl acrylate, 0.4 mole percent sodium acrylate, and 1.5 mole percent acrylic acid in the acidified ionomer.
  • the acidified ionomer had a melt index of 11.7 g/10 min. (190°C) .
  • the acidified ionomer produced a clear film with no observable haze and observably high gloss.
  • the non- acidified ionomer produced opaque, dull, and frosty film.
  • the acidified ionomer also exhibited excellent adhesion to aluminum foil, particularly when compared to the non- acidified ionomer.
  • EXAMPLE 22 An ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate and a melt index of 153 g/10 min. (190°C) was 35% hydrolyzed by the method of Comparative Example A. The melt index of this ionomer was 9.7 g/10 min. (190°C) , and the haze of a cast film was 98%, the 60° gloss was 6, and the tear strength (g/mil) in the machine direction was 33 and in the transverse direction was 41.
  • EXAMPLE 23 The non-acidified ionomer of Example 22 was fed continuously to the extruder at a rate of 8 kg/hr. and was acidified using 21.5% phosphoric acid, as detailed below. The properties of a cast film of the acidified copolymer made on the Randcastle mini-extruder are listed in Table 23. Table 23
  • EXAMPLE 24 An ethylene-methyl acrylate copolymer having 20 weight percent methyl acrylate was saponified substantially by the method of Example 1. The percent hydrolysis and properties of the polymer are listed in the following Table 24.
  • Melt point temperature was measured using a differential scanning calorimeter I and standard methods well-known in the art. o
  • Elongation at break was measured using ASTM D-882.
  • EXAMPLE 25 Samples of ethylene methyl acrylate copolymer having the methyl acrylate contents in following Table 25 were saponified to various degrees of hydrolysis using substantially the method of Example 1.
  • Table 25 summarizes the melt point temperatures of these ionomers.
  • EXAMPLE 26 Ionomer was made substantially by the method of Example 1. This ionomer was cast coextruded individually with three polymers on a Randcastle Mini-Extruder to form three 2-layer films, where each layer was 2 mil thick. Adhesion strength of the 2-layer films was analyzed using TAPPI Uniform Method 541, "Adhesion to Non-Porous Flexible Substrates", which is incorporated by reference in its entirety herein.
  • Ionomer/propylene film (Fina 3275) had an adhesion of 770 g/inch; ionomer/high density polyethylene (Chevron HiD® 9650) could not be separated; and ionomer/nylon (Allied Chemical's Capron 8350) had an adhesion of 80 g/inch.
  • EXAMPLE 27 Ethylene-methyl acrylate-butyl acrylate copolymer containing 10 weight percent methyl acrylate and 10 weight percent butyl acrylate is about 50% hydrolyzed substantially by the method of Example 1. This yields an ethylene-methyl acrylate-butyl acrylate-sodium acrylate copolymer. It is expected that the methyl acrylate reacts at a faster rate than the butyl acrylate, so more methyl acrylate is converted to the sodium salt than butyl acrylate. This product is useful in applications where a higher melt-point temperature is desired, such as films or bags which contact hot food or liquids.

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Abstract

L'invention concerne des compositions ionomères présentant des propriétés optiques améliorées. Ces compositions comprennent des ionomères pouvant être représentés comme le produit de polymérisation d'alpha-oléfines comportant deux à huit atomes de carbone, d'esters d'acides carboxyliques à insaturation éthylénique alpha et bêta, des sels métalliques d'acide acrylique et méthacrylique, et d'éventuels comonomères à insaturation éthylénique alpha et bêta conférant certaines propriétés polymères requises telles que l'acidité et/ou la résistance aux solvants. L'invention porte également sur des procédés de fabrication de ces compositions ionomères dans une extrudeuse réactive et leur traitement à l'acide de manière à conférer une acidité à ces compositions ou seulement à leur surface.
EP95901711A 1993-10-27 1994-10-27 Compositions ionomeres a faible turbidite de copolymeres d'alpha-olefines, d'esters d'acide carboxylique et d'eventuels comonomeres, et procedes de production et d'acidification de ces ionomeres Withdrawn EP0725802A1 (fr)

Applications Claiming Priority (5)

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US14379993A 1993-10-27 1993-10-27
US14417393A 1993-10-27 1993-10-27
US143799 1993-10-27
US144173 1993-10-27
PCT/US1994/012366 WO1995011929A1 (fr) 1993-10-27 1994-10-27 Compositions ionomeres a faible turbidite de copolymeres d'alpha-olefines, d'esters d'acide carboxylique et d'eventuels comonomeres, et procedes de production et d'acidification de ces ionomeres

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EP (1) EP0725802A1 (fr)
JP (1) JPH09504330A (fr)
AU (1) AU1084495A (fr)
FI (1) FI961757A (fr)
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WO (1) WO1995011929A1 (fr)

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AU3716595A (en) * 1994-09-09 1996-03-27 Chevron Chemical Company Water dispersible ethylene ionomers
US6107405A (en) * 1996-10-18 2000-08-22 Kimberly Clark Corporation Method of making grafted polyolefin compositions
US6297326B1 (en) 1996-10-18 2001-10-02 Kimberly-Clark Corporation Grafted polyolefin compositions
US5916969A (en) * 1996-11-22 1999-06-29 Kimberly-Clark Corporation Article and composition of matter made from polyolefins and PEO blend and method of making the same
US5700872A (en) * 1996-12-31 1997-12-23 Kimberly Clark Worlwide, Inc. Process for making blends of polyolefin and poly(ethylene oxide)
US6153700A (en) * 1996-12-31 2000-11-28 Kimberly-Clark Worldwide, Inc. Water-degradable flushable film of polyolefin and poly(ethylene oxide) and personal care article therewith
US6111014A (en) 1996-12-31 2000-08-29 Kimberly-Clark Worldwide, Inc. Film of monomer-grafted polyolefin and poly(ethylene oxide)
US6100330A (en) 1996-12-31 2000-08-08 Kimberly-Clark Worldwide, Inc. Water-degradable film of monomer grafted to polyolefin and poly(ethylene oxide)
US5912076A (en) * 1996-12-31 1999-06-15 Kimberly-Clark Worldwide, Inc. Blends of polyethylene and peo having inverse phase morphology and method of making the blends
US6063866A (en) * 1996-12-31 2000-05-16 Kimberly-Clark Worldwide, Inc. Blends of polyolefin and poly(ethylene oxide) and process for making the blends
US6117947A (en) * 1997-12-31 2000-09-12 Kimberly-Clark Worldwide, Inc. Method of modifying poly(ethylene oxide)
US20040076846A1 (en) 2001-03-29 2004-04-22 Domine Joseph D Ionomer laminates and articles formed from ionomer laminates
US20040161623A1 (en) 2001-03-29 2004-08-19 Domine Joseph D Ionomer laminates and articles formed from ionomer laminates
US20070054139A1 (en) 2003-05-27 2007-03-08 Domine Joseph D Ionomer laminates, composite articles, and processes for making the same
WO2004106057A1 (fr) 2003-05-27 2004-12-09 Exxonmobil Chemical Patents Inc. Couches de support et substrats pour articles façonnes a partir de stratifies d'ionomere
US7479327B2 (en) 2003-05-27 2009-01-20 Exxonmobil Chemical Patents Inc. Tie-layer materials for use with ionomer-based films and sheets as skins on other materials
WO2005105438A1 (fr) * 2004-04-14 2005-11-10 Mayco Plastics, Inc. Article presentant une enveloppe exterieure a film multicouche comprenant au moins une couche contenant une couche pigmentee et procede de fabrication
US8404773B2 (en) 2008-03-17 2013-03-26 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles
US20090297747A1 (en) * 2008-05-30 2009-12-03 E.I. Du Pont De Nemours And Company Molded articles comprising ionomer compositions
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AU1084495A (en) 1995-05-22
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FI961757A (fi) 1996-04-24
NO961658D0 (no) 1996-04-25
NO961658L (no) 1996-06-26

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