WO2001000731A1 - Compositions comprenant un melange d'oxyde de poly(ethylene) et une polyolefine greffee ainsi que procede de fabrication correspondant - Google Patents

Compositions comprenant un melange d'oxyde de poly(ethylene) et une polyolefine greffee ainsi que procede de fabrication correspondant Download PDF

Info

Publication number
WO2001000731A1
WO2001000731A1 PCT/US2000/017787 US0017787W WO0100731A1 WO 2001000731 A1 WO2001000731 A1 WO 2001000731A1 US 0017787 W US0017787 W US 0017787W WO 0100731 A1 WO0100731 A1 WO 0100731A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
acrylate
poly
grafted
polyolefin
Prior art date
Application number
PCT/US2000/017787
Other languages
English (en)
Inventor
James Hongxue Wang
David Michael Schertz
Original Assignee
Kimberly-Clark Worldwide, Inc.
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 Kimberly-Clark Worldwide, Inc. filed Critical Kimberly-Clark Worldwide, Inc.
Priority to AU58970/00A priority Critical patent/AU5897000A/en
Publication of WO2001000731A1 publication Critical patent/WO2001000731A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

Definitions

  • the present invention relates to water-responsive compositions comp ⁇ sing a thermoplastic blend of hydrophilic and hydrophobic polymers. More particularly, the pre sent invention relates to water-responsive articles made from a composition comprising a blend of poly(ethylene oxide) and a grafted polyolefin and includes articles comprising such compositions and methods of making such compositions.
  • Personal care products such as diapers, sanitary napkins, adult incontinence garments, and the like are generally constructed from a number of different components an d materials.
  • Such articles usually have some portion, usually th e backing layer, constructed of a liquid repellent film material.
  • the liquid repellent film commonly used includes plastic materials such as a polyethylene film or copolymers of ethylene and other polar and nonpolar monomers.
  • the purpose of the liquid repellent layer is to minimize or prevent absorbed liquid that may, during use, exude from the absorbent and soil the user o r adjacent clothing.
  • the liquid repellent film also has the advantage of allowing greater utilization of the absorbent capacity of the product.
  • the packaging in which the disposable article is distributed is also made from a water-resistant material.
  • Water resistivity is necessary to prevent the degradation of the packaging from environmental conditions and to protect the disposable articles therein.
  • this packaging may be safely stored with other refuse for commercial disposal, and especially in the case of individual packaging of the products, it would be more convenient to dispose of the packaging in the toilet with the discarded disposable article.
  • packaging is composed of a water-resistant material, the aforementioned problems persist.
  • hydrophilic materials can be made, to a degree, hydrophobic.
  • the material has to b e treated with a hydrophobic material to impart the desired water- resistant properties to the material.
  • the problem with this method is that the material used to impart water repellency t o the hydrophilic material may further interfere with disintegration of the article when flushed, negating any advantage of using a hydrophilic material.
  • a hydrophobic material can be made, to a degree, hydrophilic. This typically has been achieved by modifying a water resistant material, such as polyethylene, with a hydrophilic monomer such as (meth)acrylic acids, (meth)acrylate esters, hydroxyalkyl (meth)acrylate, polyethylene glycol, and glycidal methacrylate thereby making a hydrophobic material more hydrophilic.
  • a hydrophilic monomer such as (meth)acrylic acids, (meth)acrylate esters, hydroxyalkyl (meth)acrylate, polyethylene glycol, and glycidal methacrylate thereby making a hydrophobic material more hydrophilic.
  • One consideration when modifying the hydrophobic property of the barrier film by blending a hydrophobic polymer with a hydrophilic polymer, is the compatibility of the two polymers. If the two polymers are completely non-compatible, then articles comprising the blend of non-compatible polymers have poor mechanical and aesthetic compatibilities. Generally,
  • the present invention relates to water-responsive articles and compositions comprising a blend of polyolefin an d poly(ethylene oxide).
  • the water responsive composition comprises a blend having from about 1 weight percent to about 55 weight percent of a grafted polyolefin and from about 45 weight percent to about 99 weight percent o f poly (ethylene oxide).
  • the polyolefin can be grafted with fro m about 1 weight percent to about 20 weight percent of a compatibilizing monomer, desirably a polar vinyl monomer, such as poly(ethylene glycol) methacrylate.
  • the blend is water dispersible and comprises from about 1 weight percent to about 35 weight percent of grafted polyolefin, such as polyethylene o r polypropylene, and from about 65 weight percent to about 9 9 weight percent of poly(ethylene oxide).
  • grafted polyolefin such as polyethylene o r polypropylene
  • water responsive includes article materials that are water dispersible, water disintegratable and water weakenable.
  • Water dispersible is used herein to describe a 5 mil (0.005 of an inch) film that, under the water-responsive test described below, dissolves or breaks into pieces smaller than a 20-mesh screen.
  • Water disintegratable describes a 5-mil film that, under the water-responsive test, breaks into multiple pieces after 2 minutes with some of the pieces caught by a 20-mesh screen.
  • Water weakenable describes a 5 mil film that, under the water-response test, remains in tact but loses rigidity and becomes drapable, i.e., will bend without an external force applied to the film when it is held by one corner at a substantially horizontal position.
  • Another aspect of the invention provides for a method o f making the grafted polyolefin and poly(ethylene oxide) blend compositions.
  • the method includes blending under melt conditions specified amounts of either a modified or a n unmodified polyolefin with an ethylene oxide polymer.
  • the blend will have from about 1 weight percent to about 55 weight percent of the modified polyolefin with from about 45 weight percent to about 99 weight percent of poly(ethylene oxide).
  • It is an object of the invention to provide a water- responsive composition comprising a polyolefin an d poly(ethylene oxide).
  • Another object of the invention is to provide water- responsive, thermoplastic compositions that will be attractive, economical and capable of being flushed without the adverse effects presently attributed to such products.
  • Figure 1 is a scanning electron photomicrograph of a film made from a blend of 70 weight of percent poly(ethylene oxide) and 30 weight percent of ungrafted polyethylene.
  • Figure 2 is a scanning electron photomicrograph, at the same magnification as Figure 1, of a film made of a blend of 7 0 weight percent poly(ethylene oxide) and 30 weight percent of a grafted polyethylene.
  • the present invention resides in the discovery that water- responsive, thermoplastic articles can be made from a compositional blend comprising a polyolefin and poly(ethylene oxide).
  • the water responsiveness of the compositions and articles therefrom can b e varied by modifying the polyolefin or polyolefins, for example by grafting the polyolefin or mixture of polyolefins.
  • the water responsiveness of the compositions and articles therefrom c an also be varied by varying the ratio of polyolefin(s) or modified polyolefin(s) in the blend relative to amount of poly(ethylene oxide) present in the blend.
  • the polyolefin component of the compositions of the present invention may comprise a mixture of polyolefins.
  • the polyolefins are thermoplastic to facilitate processing.
  • Saturated ethylene polymers are useful as a polyolefin component in the compositions of present invention .
  • the term "saturated” refers to polymers, which are fully saturated, but also includes polymers containing up t o about 5% unsaturation.
  • Suggested polyolefins include, but are not limited to, homopolymers and copolymers of ethylene and polypropylene that are essentially linear in structure.
  • Suggested homopolymers of ethylene include, but are not limited to, those prepared under either low pressure, i.e., linear low density o r high density polyethylene, or high pressure, i.e., branched or low density polyethylene.
  • High-density polyethylenes are typically characterized by a density that is about equal to or greater than 0.94 grams per cubic centimeter (g/cc).
  • High-density polyethylenes useful as the polyolefin resin in the pre sent invention have a density ranging from about 0.94 g/cc to about 0.97 g/cc.
  • the polyolefins can have a melt index, a s measured at 2.16 kg and 190°C, ranging from about 0.01 decigrams per minute (dg/min) to 100 dg/min. More desirably, the polyolefins have a melt index of 0.01 dg/min to about 5 0 dg/min and more desirably of 0.05 dg/min to 25 dg/min.
  • Low- density polyethylene has a density of less than 0.94 g/cc and is usually in the range of 0.91 g/cc to about 0.93 g/cc.
  • Low-density polyethylene has a melt index ranging from about 0.05 dg/min t o about 100 dg/min and desirably from 0.05 dg/min to about 2 0 dg/min.
  • Ultra low-density polyethylene can also be used as th e polyolefin in accordance with the present invention.
  • ultra low-density polyethylene has a density of less than 0.90g/cc.
  • polypropylene has a semi-crystalline structure having a molecular weight of about 40,000 or more, a density o f about 0.90 g/cc, a melting point of about 168°C to about 171 °C for isotactic polypropylene and a tensile strength of about 5000 psi.
  • Polypropylene can also have other tacticities including syndiotactic and atactic. Mixtures of polyethylenes an d polypropylenes and other known polyolefins can be used as the polyolefin component of the compositions of the pre sent invention.
  • the above polyolefins can be manufactured by using the well-known multiple-site, Ziegler-Natta catalysts or the more recent single-site, metallocene catalysts.
  • the metallocene- catalyzed polyolefins have better-controlled polymer microstructures than polyolefins manufactured using Ziegler- Natta catalysts, including narrower molecular weight distribution, well-controlled chemical composition distribution, comonomer sequence length distribution, and stereoregularity.
  • Metallocene catalysts are known to polymerize propylene into atactic, isotactic, syndiotactic, and isotactic-atactic stereoblock copolymers .
  • Suggested copolymers of ethylene that are useful as a polyolefin in the present invention may include copolymers o f ethylene with one or more additional polymerizable, unsaturated monomers.
  • copolymers include, but are n o t limited to, copolymers of ethylene and -olefins (such a s propylene, butene, hexene or octene) including linear low density polyethylene; copolymers of ethylene and vinyl esters of linear o r branched carboxylic acids having 1 to 24 carbon atoms such a s ethylene-vinyl acetate copolymers; and copolymers of ethylene and acrylic or methacrylic esters of linear, branched or cyclic alkanols having 1 to 28 carbon atoms. Examples of these latter copolymers include ethylene-alkyl (meth)acrylate copolymers, such as ethylene-methyl acrylate copolymers.
  • the polyolefin is a graft copolymer.
  • the polyolefin may be grafted prior to or during the combination with the poly (ethylene oxide) component of the compositions of the present invention.
  • the polyolefin is grafted with 0.1 to 20 weight percent of one or more compatabiuzing monomers relative to the weight of polyolefin prior to grafting. More desirably, the compatabiuzing monomer is a polar vinyl monomer, oligomer, macromonomer or polymer.
  • the term "monomer” includes reactive species capable of covalently bonding with the polyolefin and includes monomers, oligomers and polymers or macromers having double bonds capable of covalently bonding with the polyolefin t o provide a grafted polyolefin.
  • the grafted polyolefins have a melt index greater than 0.005 dg/min to less than about 100 dg/min.
  • water-responsiveness for the compositions an d articles comprising the compositions can be varied by modifying the polyolefin and by varying the amount of the polyolefin in the composition.
  • the polyolefin is modified by grafted one or more compatabiuzing monomers with the polyolefin.
  • suitable compatabiuzing monomers include 2 - hydroxyethyl methacrylate and poly(ethylene glycol) ethyl ether methacrylate. Grafting of compatabiuzing monomers is described in greater detail in the commonly assigned U.S.
  • the modified polyolefin constituent of the compositons c an have as little as 0.1 weight percent of a compatibilizing monomer grafted thereto.
  • the modified polyolefin has grafted thereto from about 1 weight percent to about 20 weight percent, based on the weight of polyolefin, of a compatibilizing monomer . More desirably, the modified polyolefin has from about 1 weight percent to about 10 weight percent, based on the weight o f polyolefin, of a compatibilizing monomer is grafted to the polyolefin.
  • polar, vinyl monomers, oligomer, and polymers and mixtures of the above may be useful as a compatabiuzing monomer in the present invention, as long as, the monomers , oligomers and polymers are capable of covalent bonding with th e parent polymer(s), the polyolefins.
  • Ethylenically unsaturated monomers containing a polar functional group, such as hydroxyl, carboxyl, amino, carbonyl, halo, glycidyl, cyano, thiol, sulfonic, sulfonate, etc. are appropriate for this invention and are suggested. Desired ethylenically unsaturated monomers include acrylates and methacrylates.
  • Suggested polar vinyl monomers include, but are not limited to: 2-hydroxyethyl acrylate, 2 - hydroxyethyl methacrylate, poly(ethylene glycol) acrylates, poly(ethylene glycol) methacrylates, poly(ethylene glycol) diacrylates, acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, acrylamide, glycidyl methacrylate, 2-bromoethyl acrylate, 2-bromoethyl methacrylate, carboxyethyl acrylate, sodium acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-chloroacrylonitrile, 4-chlorophenyl acrylate, 2 - cyanoethyl acrylate, glycidyl acrylate, 4-nitrophenyl acrylate, pentabromophenyl acrylate, poly(propylene glycol) acrylates, poly(propylene glycol) methacryl
  • Suggested derivatives include, but are not limited to, poly(ethylene glycol) ethyl ether acrylates, poly(ethylene glycol) alkyl ether acrylates, poly (ethylene glycol) alkyl ether methacrylates, an d poly(ethylene glycol) ethyl ether methacrylates of various molecular weights.
  • Any polar vinyl monomer or a mixture of monomers including a polar vinyl monomer or monomers may be added t o and reacted with the polyolefin separately from and prior to, o r during the blending process with the poly(ethylene oxide).
  • the addition of a polar vinyl monomer and an initiator to the process is desirable.
  • the polymers and the monomer(s) may be added simultaneously.
  • the polymer, the initiator and the monomer(s) may be added together into the hopper of a n extruder, barrel #1. It is more desirable to add the polymers t o the reactive vessel first and to melt the polymers before adding either the initiator or monomer.
  • Examples of such methods include melting the polymers and then injecting a solution comprising initiator and monomer into the molten polymers; an d adding the initiator and then adding the monomer or mixture o f monomers to the molten polymers. It is even more desirable t o add and disperse the monomer(s) in the molten polymers before adding the initiator. Thus, it is desired to add the polymers to th e extruder first and then inject and disperse the monomer(s) in the polymers before adding initiator.
  • Poly(ethylene oxide) resins suitable for the present invention can have an average molecular weight ranging from about 100,000 to about 8,000,000 grams per mol. Desirable, water-soluble poly(ethylene oxide)s are available from Union Carbide Corporation under the tradename of POLYOX® . Typically, poly(ethylene oxide) is a dry, free-flowing, white powder having a crystalline melting point in the order of about 650°C, above which the poly(ethylene oxide) resin becomes thermoplastic and can b e formed by molding, extrusion and other methods known in the art. The poly(ethylene oxide) may also be grafted and can b e grafted before or during mixing with the polyolefin.
  • Suggested monomers and amounts of monomer that can be grafted include the monomers and amounts of monomer as described above for grafting polyolefins. Grafting of poly(ethylene oxide) is described in greater detail in the commonly assigned U.S. Application No. 09/002, 197 entitled “METHOD OF MODIFYING POLY(ETHYLENE OXIDE)" filed December 31 , 1997, the disclosure of which is incorporated herein by reference in it entirety and is made a p art hereof.
  • the water-responsive compositions comprise a blend o f from about 1 weight percent to about 55 weight percent polyolefin and from about 45 weight percent to about 99 weight percent poly(ethylene oxide).
  • the water- responsive compositions are water-dispersible.
  • the water- dispersible compositions comprise a blend of from about 1 weight percent to about 35 weight percent polyolefin and fro m about 65 weight percent to about 99 weight percent poly(ethylene oxide).
  • the water-dispersible compositions comprise from about 1 weight percent to about 2 0 weight percent of polyolefin and from about 80 weight percent t o about 99 weight percent poly(ethylene oxide) and, more desirably, from about 1 weight percent to about 15 weight percent of polyolefin and from about 85 weight percent to about 99 weight percent poly (ethylene oxide).
  • the water-responsive compositions are water disintegratable.
  • the water-disintegratable compositions comprise a blend of from about 35 weight to about 45 weight percent of grafted polyolefin and from about 55 weight percent to about 65 weight percent poly(ethylene oxide).
  • the water-responsive compositions are water weakenable.
  • the water-weakenable compositions comprise a blend of from about 45 weight percent to about 55 weight percent of polyolefin and from about 45 weight percent to about 55 weight percent of poly(ethylene oxide).
  • Articles manufactured from compositions of the pre sent invention may be selectively water responsive.
  • the water responsiveness of articles manufactured form the compositions of the present invention can be selected by blending th e component polymers of the compositions, polyolefin a n d poly(ethylene oxide), with the above ranges.
  • Non-limiting examples of various water-responsive articles that can b e manufactured using the composition of the present invention include thermoplastic tampon tubes, garbage bags, thermoplastic films, fibers and the like.
  • the wall thickness or caliper o f the article, e.g., the tampon or film is 5 mils or less.
  • an article having a caliper greater than 5 mils would still be water-responsive but may take longer than 2 minutes after being subjected to water before becoming affected.
  • caliper and “thickness” may be used interchangeably.
  • a shaped article such as a tube or other configuration having a wall
  • the caliper of the wall would more accurately describe the thickness measurement.
  • Processing characteristics of the compositions can b e enhanced by the incorporation of lubricants, slip agents and various known additives into the compositions. Generally, such additives are incorporated in the compositions in amounts up t o about 5 weight percent.
  • a typical blend formulation including a lubricant would be in the order of about 75 weight percent o f poly(ethylene oxide), about 20 weight percent of a polyolefin an d about 5 weight percent of a lubricant.
  • Lubricants are well known in the art and include TWEEN® 20, TURGITOL® NP13 available from Union Carbide, and various fatty acids such as KENAMIDE® E available from Witco Chemical.
  • compositions may contain o ther components to enhance the properties of the resulting material.
  • polyethylene glycol can be added to lower the melt viscosity of the melted blend to a range suitable for other processes such as meltblown or meltsprayed nonwoven materials .
  • the amount of polyethylene glycol can be from about 0.1 weight percent to about 10 weight percent. Suitable polyethylene glycols are available from Union Carbide under the tradename
  • the water-responsive blends of the pre sent invention are capable of being thermoformed using conventional techniques known in the art but yet do not form a single phase blend morphology.
  • a n article formed in accordance with the invention exhibits two- phase morphology where one polymer forms a continuous phase and the second polymer forms a dispersed or discontinuous phase.
  • Articles made from blends of unmodified polyethylene and poly(ethylene oxide) exhibit water-responsiveness at up t o about 35 weight percent of unmodified polyethylene.
  • articles made from blends of grafted polyethylene and poly(ethylene oxide) exhibit water-responsiveness up t o about 55 weight percent of grafted polyethylene.
  • the polyolefin and poly(ethylene oxide) blends of the invention can be prepared by mixing the desired weight ratio o f the constituents into a blend using any standard equipment commonly used for blending thermoplastic resins.
  • a batch or continuous blender may be used to blend the polyolefin and poly (ethylene oxide) using heat and high shear.
  • n o t preferred, a single screw or twin screw extruder that utilizes various mixing screw sections, kneading sections and the like c an be used.
  • the composition may be solidified and pelletized or extruded into a film using techniques known in the art.
  • the film did not disperse or disintegrate, the film was held immersed in the water for additional 3 minutes to observe any loss in rigidity.
  • the vial was rinsed with 20 milliliter of water from a squeeze bottle and emptied through the sieve.
  • the following terms are used to describe the effect of water on the section of film:
  • Water dispersible the film dissolves or breaks into pieces smaller than a 20-mesh screen after 2 minutes.
  • Water disintegratable the film breaks into multiple pieces after 2 minutes with some of film caught by a 20-mesh screen.
  • Water weakenable the film remains in one piece but weakens an d loses rigidity significantly in 5 minutes.
  • Water stable the film remains in one piece and does not lose any of its rigidity after 5 minutes.
  • a blend containing 21 grams of low density polyethylene having a melt index of 1.9 g/10 minute (available from Dow Chemical) and 21 grams of poly(ethylene oxide), having a molecular weight of 200,000 g/mol (POLYOX WSR N-80 is available from Union Carbide) was prepared using a Haake Rheomix 600 twin-roller mixer (available from Haake, 53 West Century Rd. Paramus, NJ, 07652). Each zone of the Haake mixer was preheated to 180°C. The material was mixed for 20 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air. The film was determined to be water stable.
  • Example 1 The constituents of Example 1 were blended using
  • Figure 1 is a photomicrograph of the fracture surface of a 5-mil film of this composition using scanning electron microscopy. The film was determined to be water dispersible.
  • Example 1 The constituents of Example 1 were blended using 4.2 grams of low-density polyethylene and 37.8 grams of poly(ethylene oxide) in a HAAKE Rheomix mixer for 20 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air. The film was determined to be water dispersible.
  • a blend containing 21 grams of a modified low-density polyethylene and 21 grams of poly(ethylene oxide) was prepared using the Haake Rheomix mixer for 20 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air.
  • the low-density polyethylene was modified by grafting 11.1 weight percent of a compatabiuzing monomer, specifically 2-hydroxyethyl methacrylate, to the polyethylene. The film was determined to be water weakenable.
  • a blend containing 18.9 grams of a modified low-density polyethylene of Example 4 and 23.1 grams of poly (ethylene oxide) was prepared using the Haake Rheomix mixer for 2 0 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air. The film was determined to be water disintegratable. The film lost rigidity a nd curled after 19 seconds and began forming fibers after 69 seconds. The film began to disintegrate after 90 seconds.
  • a blend containing 16.8 grams of a modified low-density polyethylene of Example 4 and 25.2 grams of poly(ethylene oxide) was prepared using the Haake Rheomix mixer for 2 0 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air. The film was determined to be water disintegratable. The film lost rigidity and curled after 11 seconds and began forming fibers after 6 1 seconds. The film began to disintegrate after 90 seconds.
  • a blend containing 14.7 grams of a modified low-density polyethylene of Example 4 and 27.3 grams of poly(ethylene oxide) was prepared using the Haake Rheomix mixer for 2 0 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed 5 from the mixer and cooled in air. The film was determined to be water-disintegratable. The film lost rigidity and curled after 10 seconds and began forming fibers after 3 3 seconds. The film began to disintegrate after 33 seconds.
  • Example 8 A blend containing 12.6 grams of a modified low-density polyethylene of Example 4 and 29.4 grams of poly(ethylene oxide) was prepared using the Haake Rheomix mixer for 20 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air.
  • Fig. 2 is a photomicrograph of the fracture surface of a 5-mil film of this composition using scanning electron microscopy. The film was determined to be water dispersible.
  • a blend containing 4.2 grams of a modified low-density polyethylene of Example 4 and 37.8 grams of poly(ethylene oxide) was prepared using the Haake Rheomix mixer for 2 0 minutes at a screw speed of 150 rpm. After 20 minutes, the melt was removed from the mixer and cooled in air. The film was determined to be water dispersible.
  • This example describes the preparation of poly(ethylene glycol) ethyl ether methacrylate grafted polyethylene.
  • the grafted polyethylene was prepared by a reactive extrusion process on a ZSK-30 twin-screw extruder manufactured by Werner & Pfleiderer Corporation of Ramsey, New Jersey.
  • the extruder has a pair of screws, which contain a number o f conveying, kneading, and left-handed screw elements to provide high intensity distributive and dispersive mixing.
  • the two screws are co-rotating.
  • the nominal screw diameters are 30 mm.
  • the screw lengths are 1328 mm.
  • the extruder has 14 processing barrels, numbered consecutively from 1 to 14 from the feed barrel to the die.
  • the first barrel, barrel #1 received polyethylene and was not heated but cooled by water. The other barrels were heated.
  • PEGEEMA is a derivative of polyethylene glycol methacrylate (PEGMA).
  • the PEGEEMA was injected into barrel #5 and the initiator was injected to barrel #6. Both the monomer and the initiator were inj ected via a pressured nozzle injector, also manufactured by Werner & Pfleiderer.
  • the first heating zone was heated to 170°C; all th e other heating zones were heated to 180°C.
  • the screw speed was set at 300 rpm.
  • a low-density polyethylene having a melt index of 1.9 g/ 1 0 min (available from Dow) was fed to the feed throat at a rate o f 20 lb/hr through a gravimetric feeder manufactured by K-Tron o f Pitman, New Jersey.
  • the PEGEEMA was fed to barrel #5 at a rate of 2 lb/hr, and the initiator, LUPERSOL 101 , was fed to barrel # 6 at a rate of 0.1 lb/hr.
  • the resulting grafted polyethylene was cooled in a 20-foot water bath and subsequently pelletized.
  • Example 1 The same polyethylene, PEGEEMA monomer, initiator, an d equipment as in Example 11 were used, except that the rate o f PEGEEMA was 1 lb/hr and the rate of LUPERSOL 101 was 0.07 lb/hr .
  • Example 12 The same polyethylene, PEGEEMA monomer, initiator, an d equipment as in Example 11 were used, except that the rate o f PEGEEMA was 1 lb/hr and the rate of LUPERSOL 101 was 0.07 lb/hr .
  • Example 12 The same polyethylene, PEGEEMA monomer, initiator, an d equipment as in Example 11 were used, except that the rate o f PEGEEMA was 1 lb/hr and the rate of LUPERSOL 101 was 0.07 lb/hr .
  • This example describes the method for making 2 - hydroxyethyl methacrylate (abbreviated as HEMA) grafted poly(ethylene oxide).
  • HEMA 2 - hydroxyethyl methacrylate
  • POLYOX WSR N-750 having an approximate molecular weight of 300,000 g/mol was fed to the feed throat of the ZSK-30, twin-screw extruder, at a feeding rate of 20 lb/hr .
  • HEMA was fed to the same extruder at barrel #5 at a rate of 0.3 lb/hr and peroxide initiator was fed to the barrel #6 extruder at a rate of 0.03 lb/hr.
  • the resulting grafted polyethylene oxide was cooled on a 15-foot conveyer belt fan-cooled by air.
  • Example 14 A blend containing 4.2 grams of a modified low-density polyethylene of Example 4 and 37.8 grams of poly(ethylene oxide) (PEO) grafted with 1.5 percent by weight of 2-hydroxyethyl methacrylate was prepared using, the Haake Rheomix mixer a t 180°C and at a screw speed of 150 rpm for 20 minutes. After 20 minutes, the melt was removed from the mixer and cooled in air.
  • PEO poly(ethylene oxide)
  • a blend containing 8.4 grams of a modified low density polyethylene of Example 4 and 33.6 grams of PEO grafted with 1.5% by weight of 2-hydroxyethyl methacrylate (HEMA) was prepared using the Haake Rheomix mixer, at 180°C and a screw speed of 150 rpm for 20 minutes. After 20 minutes, the, melt was removed from the mixer and cooled in air. A film was pressed from this blend. The film was determined to be water dispersible.
  • HEMA 2-hydroxyethyl methacrylate

Abstract

L'invention concerne des compositions thermoplastiques réagissant sélectivement à l'eau qui comprennent un mélange d'un oxyde de poly(éthylène) pouvant être greffé ou enlevé ainsi qu'une polyoléfine greffée. De préférence, la polyoléfine est greffée avec un monomère de compatibilisation. Le monomère de compatibilisation peut être n'importe quelle substance réactive capable de se lier par covalence avec la polyoléfine et comprend des monomères, des oligomères et des polymères ou des macromères comportant des liaisons doubles, par exemple, une espèce insaturée α, β-éthyléniquement qui est capable de se lier par covalence avec la polyoléfine pour donner une polyoléfine greffée. De préférence, le monomère est un monomère vinylique polaire tel que le méthacrylate de poly(éthylèneglycol). Les compositions réagissant à l'eau peuvent avoir la capacité d'être dispersées par l'eau, désintégrées par l'eau ou affaiblies par l'eau en fonction des quantités relatives de l'oxyde de poly(éthylène) et de la polyoléfine greffée faisant partie du mélange. On peut modifier cette capacité de réagir avec l'eau en modifiant la polyoléfine et en réduisant la teneur du mélange en polyoléfine d'environ 55 % en poids à environ 1 % en poids.
PCT/US2000/017787 1999-06-29 2000-06-28 Compositions comprenant un melange d'oxyde de poly(ethylene) et une polyolefine greffee ainsi que procede de fabrication correspondant WO2001000731A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58970/00A AU5897000A (en) 1999-06-29 2000-06-28 Compositions comprising a blend of poly(ethylene oxide) and grafted polyolefin and method of making the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34265199A 1999-06-29 1999-06-29
US09/342,651 1999-06-29

Publications (1)

Publication Number Publication Date
WO2001000731A1 true WO2001000731A1 (fr) 2001-01-04

Family

ID=23342703

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/017787 WO2001000731A1 (fr) 1999-06-29 2000-06-28 Compositions comprenant un melange d'oxyde de poly(ethylene) et une polyolefine greffee ainsi que procede de fabrication correspondant

Country Status (2)

Country Link
AU (1) AU5897000A (fr)
WO (1) WO2001000731A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006016179A1 (fr) * 2004-08-12 2006-02-16 The University Of Bristol Matériaux polymériques de pégosité réduite, méthodes de fabrication de ces matériaux et compositions de chewing-gum comprenant de tels matériaux
WO2009068569A1 (fr) * 2007-11-26 2009-06-04 Revolymer Limited Matériau polymère amphiphile

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998022532A1 (fr) * 1996-11-22 1998-05-28 Kimberly-Clark Worldwide, Inc. Melanges de polyolefines et de polyethylene oxyde
WO1998029502A1 (fr) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Pellicule en polyolefine modifiable dans l'eau et jetable dans les toilettes
US5807930A (en) * 1996-12-31 1998-09-15 Kimberly-Clark Worldwide, Inc. Process for making blends of 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998022532A1 (fr) * 1996-11-22 1998-05-28 Kimberly-Clark Worldwide, Inc. Melanges de polyolefines et de polyethylene oxyde
WO1998029502A1 (fr) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Pellicule en polyolefine modifiable dans l'eau et jetable dans les toilettes
US5807930A (en) * 1996-12-31 1998-09-15 Kimberly-Clark Worldwide, Inc. Process for making blends of 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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006016179A1 (fr) * 2004-08-12 2006-02-16 The University Of Bristol Matériaux polymériques de pégosité réduite, méthodes de fabrication de ces matériaux et compositions de chewing-gum comprenant de tels matériaux
AU2005271001B2 (en) * 2004-08-12 2008-07-24 Revolymer Limited Polymeric materials having reduced tack, methods of making the materials and chewing gum compositions containing such materials
US8211980B2 (en) 2004-08-12 2012-07-03 Revolymer Limited Polymeric materials having reduced tack, methods of making the materials and chewing gum compositions containing such materials
WO2009068569A1 (fr) * 2007-11-26 2009-06-04 Revolymer Limited Matériau polymère amphiphile
US9732177B2 (en) 2007-11-26 2017-08-15 Revolymer (U.K.) Limited Amphiphilic copolymeric material

Also Published As

Publication number Publication date
AU5897000A (en) 2001-01-31

Similar Documents

Publication Publication Date Title
EP0951508B1 (fr) Melanges de polyethylene et de poly(ethylene oxyde) dotes d'une morphologie en phase inversee et procede de realisation desdits melanges
US5807930A (en) Process for making blends of polyolefin and poly(ethylene oxide)
US5916969A (en) Article and composition of matter made from polyolefins and PEO blend and method of making the same
US6063866A (en) Blends of polyolefin and poly(ethylene oxide) and process for making the blends
CA2275669A1 (fr) Pellicule en polyolefine modifiable dans l'eau et jetable dans les toilettes
US6362277B1 (en) Personal care article with layer of monomer-grafted polyolefin and unmodified PEO
US6255386B1 (en) Blends of polyolefin and poly(ethylene oxide) and process for making the blends
WO2001000731A1 (fr) Compositions comprenant un melange d'oxyde de poly(ethylene) et une polyolefine greffee ainsi que procede de fabrication correspondant
US6359063B1 (en) Personal care article with layer of monomer-grafted polyolefin and PEO
AU732005B2 (en) Mesh-forming material and method of making the same
MXPA01012354A (es) Mezclas de fase inversa de poli(oxido de etileno) y poliolefina y metodo de extruccion reactiva para hacer mezclas de fase inversa.
MXPA99004435A (en) Polyolefin/polyethylene oxide blends
MXPA00012368A (en) Water-modifiable flushable polyolefin-containing film and article made therefrom
MXPA00012673A (en) Blends of polyolefin and poly(ethylene oxide) and process for making the blends
MXPA00012369A (en) Water-modifiable flushable polyolefin-containing film and article made therefrom
MXPA01003944A (es) Mezclas de poliolefina y de poli(oxido de etileno) y proceso para hacer las mezclas.

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP