WO1998025979A1 - Materiau maillant et procede de realisation correspondant - Google Patents

Materiau maillant et procede de realisation correspondant Download PDF

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Publication number
WO1998025979A1
WO1998025979A1 PCT/US1997/022544 US9722544W WO9825979A1 WO 1998025979 A1 WO1998025979 A1 WO 1998025979A1 US 9722544 W US9722544 W US 9722544W WO 9825979 A1 WO9825979 A1 WO 9825979A1
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WO
WIPO (PCT)
Prior art keywords
weight percent
polyolefin
acrylic acid
water
grafted
Prior art date
Application number
PCT/US1997/022544
Other languages
English (en)
Inventor
James Hongxue Wang
David Michael Schertz
Pavneet Singh Mumick
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 CA002272697A priority Critical patent/CA2272697A1/fr
Priority to EP97954546A priority patent/EP0948550A1/fr
Priority to AU58971/98A priority patent/AU732005B2/en
Publication of WO1998025979A1 publication Critical patent/WO1998025979A1/fr

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Classifications

    • 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
    • C08L51/06—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
    • 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

Definitions

  • the present invention relates to method of making a modified polyolefin and a water-responsive article made from a compositional thermoplastic blend of hydrophilic and hydrophobic polymers. More particularly, the present invention relates to a polyolefin having acrylic acid grafted thereto and a water-responsive article comprising the grafted polyolefin and % poly(ethylene oxide).
  • Personal care products such as diapers, sanitary napkins, adult incontinence garments, and the like are generally constructed from a number of different components and materials. Such articles usually have some portion, usually the 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 from exuding from the absorbent which may then soil the user or 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 is often 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.
  • Polyolefins have also been modified using acryiate esters such as methyl acrylate, 2-butyl acryiate, 2-ethylhexyl acryiate, decyl acryiate, octadecyl acryiate and corresponding esters of methacrylate.
  • acryiate esters such as methyl acrylate, 2-butyl acryiate, 2-ethylhexyl acryiate, decyl acryiate, octadecyl acryiate and corresponding esters of methacrylate.
  • One aspect of the present invention is a method of making a modified polyolefin having from about 0.5 weight percent to about 30 weight percent of acrylic acid grafted thereto, wherein the percent grafted acrylic acid is based on the total weight of the polyolefin and the weight of the acrylic acid.
  • the method includes the steps of adding an amount of polyolefin with predetermined amounts of a free radical initiator and acrylic acid to a reaction vessel and mixing the constituents under melt grafting conditions to form the modified or grafted polyolefin.
  • modified polyolefin and "grafted polyolefin” are used interchangeably.
  • the modified polyolefin may then be formed into an article of choice using methods well known in the art or solidified and pelletized for later thermoforming operations.
  • compositional blend having at least about 15 weight percent of the modified polyolefin and about 85 weight percent of poly(ethylene oxide).
  • Another aspect of the present invention is a water-responsive article, such as a film, having at least 15 weight percent of the modified polyolefin and about 85 weight percent of poly(ethylene oxide) wherein the article is mesh-forming when subjected to water immersion. It is an object of the invention to provide a method of making a modified polyolefin. Specifically, it is an object of the invention to provide a method for grafting acrylic acid onto a polyolefin.
  • Another object of the invention is to provide a water-responsive article having at least 15 weight percent of the modified polyolefin and about 85 weight percent of poly(ethylene oxide).
  • water-responsive includes an article that is water- dispersible and/or mesh-forming when tested in accordance with the water- responsive test described below.
  • 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 20 mesh.
  • Mesh-forming describes a 5 mil film that, under the water-responsive test, remains in tact but loses rigidity and forms an open pore structure having an average pore size of less than about 500 microns.
  • One aspect of the invention provides a method for grafting acrylic acid onto a polyolefin.
  • the method includes the steps of blending an amount of the polyolefin with a free radical initiator and acrylic acid (collectively reactants) in a reaction vessel and mixing the reactants under melt grafting conditions to graft from about 0.5 weight percent to about 30 weight percent acrylic acid onto the polyolefin.
  • the saturated ethylene polymers useful in the practice of this invention are homopolymers or copolymers of ethylene and polypropylene and are essentially linear in structure.
  • the term "saturated" refers to polymers which are fully saturated, but also includes polymers containing up to about 5% unsaturation.
  • the homopolymers of ethylene include those prepared under either low pressure, i.e., linear low density or 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).
  • the high density polyethylenes useful as a base resin in the present invention have a density ranging from about 0.94 g/cc to about 0.97 g/cc.
  • the polyethylenes can have a melt index, as measured at 2.16 kg and 190°C, ranging from about 0.01 decigrams per minute (dg/min) to 100 dg/min.
  • the polyethylene has a melt index of 0.01 dg/min to about 50 dg/min and more desirably of 0.05 dg/min to about 25 dg/min.
  • mixtures of polyethylene can be used as the base resin in producing the graft copolymer compositions, and such mixtures can have a melt index greater than 0.005 dg/min to less than about 100 dg/min.
  • the low density polyethylene has a density of less than 0.94 g/cc and are usually in the range of 0.91 g/cc to about 0.93 g/cc.
  • the low density polyethylene has a melt index ranging from about 0.05 dg/min to about 100 dg/min and desirably from 0.05 dg/min to about 20 dg/min.
  • Ultra low density polyethylene can be used in accordance with the present invention. Generally, 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 of about 0.90 g/cc, a melting point of about 168°C to about 171°C for isotactic polypropylene and a tensile strength of 5000 psi.
  • Polypropylene can also have other tacticities including syndiotactic and atactic.
  • the above polyolefins can also 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, isotactic-atactic stereoblock copolymer.
  • Copolymers of ethylene which can be useful in the present invention may include copolymers of ethylene with one or more additional polymerizable, unsaturated monomers.
  • copolymers include, but are not limited to, copolymers of ethylene and alpha olefins (such as propylene, butene, hexene or octene) including linear low density polyethylene, copolymers of ethylene and vinyl esters of linear or branched carboxylic acids having 1-24 carbon atoms such as ethylene-vinyl acetate copolymers, and copolymers of ethylene and acrylic or methacrylic esters of linear, branched or cyclic alkanols having 1-28 carbon atoms. Examples of these latter copolymers include ethylene-alkyl (meth)acrylate copolymers, such as ethylene-methyl acryiate copolymers.
  • the mixture of polyolefin and acrylic acid are subjected to mechanical deformation in the presence of the free radical initiator in a suitable mixing device, which preferably, is an extruder.
  • the extruder can have more than one port for the addition of the polyolefin polymer. Desirably, there is at least one injection port on the extruder that is at a position where polyolefin is melted or at least partially melted for addition of acrylic acid and/or the initiator.
  • the extruder may also have a section with a reduced pressure zone for venting off any unreacted acrylic acid and/or volatiles formed during the process.
  • Free radical initiators useful in the practice of this invention include acyl peroxides such as benzoyl peroxide; dialkyl; diaryl; or aralkyl peroxides such as di-t- butyl peroxide; dicumyl peroxide; cumyl butyl peroxide; 1,1-di-t-butyl peroxy-3,5,5- trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and bis(a-t-butyl peroxyisopropylbenzene); peroxyesters such as t-butyl peroxypivalate; t-butyl peroctoate; t-butyl perbenzoate; 2,5- dimethylhexyl-2,5-di(perbenzoate); t-butyl di(perphthalate); dialky
  • graft copolymers can be added to further enhance the properties of the resulting material.
  • polyethylene glycol can be added to improve the melt viscosity.
  • Additives of other types normally used in polymer blends can also be incorporated to provide specific properties as needed. For example, anti-static agents, pigments, colorants and the like. Additionally, processing characteristics can be improved by incorporating lubricants or slip agents into the blends. All of these additives are generally used in relatively small amounts, usually less than 3 weight percent. The feed rates of the constituents to the extruder are important.
  • the acrylic acid and initiator can be metered continuously into the extruder or in several portions over a period of time to promote homogeneous grafting of the acrylic acid throughout the mass of the melted polyolefin polymer.
  • the free radical initiator should be fed to the melt at a rate relative to the feed rate of the acrylic acid, that is, the ratio of initiator feed (weight basis) to acrylic acid feed (weight basis) is greater than about 0.025, preferably, the free radical initiator relative feed rate is from about 0.025 to about 0.1 , more preferably, from about 0.025 to about 0.075 and most preferably, from about 0.0375 to about 0.06.
  • the acrylic acid monomer can be fed to the melt at a rate relative to the feed rate of the polyolefin, that is, the ratio of acrylic acid monomer (weight basis) to polyolefin (weight basis) is from 0.02 to about 0.3 preferably the monomer relative feed rate is from about 0.05 to about 0.25 and more preferably, the relative feed rate is from about 0.1 to about 0.2.
  • the grafted acrylic acid content of the final modified polyolefin polymer can be from about 0.5 weight percent to about 15 weight percent based on the total amount of acrylic acid and polyolefin resin fed.
  • the polyolefin i.e. polyethylene or polypropylene, has grafted thereto from about 0.75 weight percent to about 10 weight percent.
  • Another aspect of the invention is a water-responsive thermoplastic article made from a compositional blend of the modified polyolefin and poly(ethylene oxide).
  • Suitable poly(ethylene oxide) resins can have a molecular weight ranging from about 100,000 to about 8,000,000.
  • Poly(ethylene oxide) is available from Union Carbide Corporation under the trade name of POLYOX ® .
  • poly(ethylene oxide) is a dry free flowing white powder having a crystalline melting point in the order of about 65°C, above which the poly(ethylene oxide) resin becomes thermoplastic and can be formed by molding, extrusion and other methods known in the art.
  • the blend has from about 15 weight percent to about 50 weight percent of the modified polyolefin and from about 85 weight percent to about 50 weight percent poly(ethylene oxide).
  • the blend has from about 20 weight percent to about 50 weight percent of the modified polyolefin and from about 80 weight percent to about 50 weight percent poly(ethylene oxide) and more preferably, from about 30 weight percent to about 50 weight percent of the modified polyolefin and from about 70 weight percent to about 50 weight percent poly(ethylene oxide).
  • the article can be made by blending under melt conditions the above described portions of the above described modified polyolefin and poly(ethylene oxide) and forming the article from the melt blend. Unexpectedly, the article formed from the blend is mesh-forming when immersed in water.
  • a five mil thick film made from the blend will form a mesh having an average pore size, as determined by the equivalent hydraulic diameter, of less than about 500 microns. Desirably, the mesh will have an average pore size of a few micron to 200 microns and more preferably from about 40 microns to about 200 microns.
  • Water-responsive articles that can be produced from the blends include thermoplastic tampon tubes, garbage bags, thermoplastic films and personal care barrier films.
  • the porous mesh itself may be used as a porous membrane for filtration.
  • the wall thickness or caliper of the article, e.g., the tampon applicator or film is 5 mils or less.
  • a typical blend formulation including a lubricant would be in the order of about 75 weight percent of poly(ethylene oxide), about 20 weight percent of a polyolefin and 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.
  • the blends may contain other 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 CARBOWAX* .
  • the polyolefin and poly(ethylene oxide) blend of the invention can be prepared by mixing the desired weight ratio of the constituents into a blend using any standard equipment commonly used for blending and preferably, melt blending thermoplastic resins.
  • a batch or continuous blender may be used to blend the polyolefin and poly(ethylene oxide) using heat and high shear.
  • the blend can be solidified and pelletized or extruded into a film using techniques known in the art.
  • the water-responsive blend of the present invention is capable of being thermoformed using conventional techniques known in the art.
  • the water-responsiveness of the five (5) mil films prepared from the melt blends was determined by testing a section of the film measuring about 0.25 of an inch by about 0.5 of an inch. Using a pair of tweezers to hold the section of film, it was immersed into a scintillation vial filled with 20 milliliters of water and held for 2 minutes. After 2 minutes, if the section of film begin to disperse, the contents of the scintillation vial were emptied through a "20 mesh" U.S.A. Standard Testing Sieve (ASTME-11 Specification, No. 20). In the examples 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 20 mesh after 2 minutes.
  • Mesh-forming the film will lose rigidity and form a porous structure having an average pores size less than about 500 microns.
  • EXAMPLE 1 A low density polyethylene polymer having a melt index of 1.9 dg/min (available from Dow Chemical Company, Midland, Ml) was grafted with acrylic acid (available from Aldrich Chemical Company, Milwaukee, WI) by reactive extrusion. This was a continuous process in which the grafting reaction was conducted in a 30 millimeter twin-screw extruder (Werner & Pfleiderer, ZSK-30). The extruder had a total processing length of 880 millimeters, nine barrel sections and five heating zones. Barrel no. 1 was cooled by water.
  • the heating elements for barrels 2 and 3 were coupled as Zone 1 , barrels 4 and 5 were coupled as Zone 2, barrels 6 & 7 were coupled as Zone 3, barrel 9 was Zone 4 and the die was Zone 5.
  • the polyethylene resin feed rate was 22 Ib/hr, the acrylic acid monomer feed rate was 2.2 Ib/hr and the respective feed rate of the free radical initiator was 0.11 Ib/hr.
  • the feed to the extruder comprised adding the low density polyethylene to the extruder at the feed throat.
  • the reaction products were purified.
  • 5 grams of the modified polyolefin product obtained from Example 1 above was added to a round- bottom flask containing 150 milliliters of xylenes. The flask was fitted with a condenser for refluxing and stirred by a magnetic stirrer. The contents were heated to 140°C to 150°C in an oil bath and refluxed for three (3) hours. The modified polyolefin was completely dissolved in the solution.
  • the hot xylenes solution was added, stirring continuously, to a beaker containing 800 milliliters of acetone at room temperature.
  • the purified precipitate was collected by vacuum filtration and washed with 100 milliliters of acetone.
  • the purified precipitate was dried in a vacuum oven at 50°C and 25-30 inches of Hg until all solvent had been removed.
  • the amount of acrylic acid grafted onto the polyethylene was determined by dissolving 0.5 grams of the purified precipitate in 50 milliliters of hot xylenes. The samples were titrated, while hot, with 0.0080 N potassium hydroxide in methanol solution. The volume of potassium hydroxide consumed was then converted into weight percent of grafted acrylic acid using the formula:
  • % grafted acrylic acid [(ml KOH) x 0.008 x 72.06]/[wt. of sample (g) x 10].
  • the amount of acrylic acid grafted onto the polyethylene was determined by titration to be 0.95 weight percent.
  • COMPARATIVE EXAMPLE A A blend containing 4.2 grams of the modified low density polyethylene of Example 1 and 37.8 grams of poly(ethylene oxide) having a molecular weight of 200,000 g/mol (POLYOX ® WSR N-80 available from Union Carbide Co ⁇ .) was prepared using a Haake Rheomix 600 twin-roller mixer, (available from Haake, 53 West Century Rd. Paramus, NJ, 07652) 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. The film began to form fine pores instantaneously. The pores were transient and unstable. After 9 seconds, the film began to disperse.
  • POLYOX ® WSR N-80 available from Union Carbide Co ⁇ .
  • a blend containing 5.5 grams of the modified low density polyethylene of Example 1 and 36.5 grams of polyethylene oxide) (POLYOX ® WSR N-80) was prepared using the Haake Rheomix 600 twin-roller mixer. Each zone of the Haake mixer was preheated to 180°C. The material was mixed for 20 minutes at a screw speed of 150 ⁇ m. After 20 minutes, the melt was removed from the mixer and cooled in air.
  • Example B The film was determined to be water-dispersible. The film began to form fine pores instantaneously. The pores were transient and unstable. After 22 seconds, the film began to disperse.
  • COMPARITIVE EXAMPLE C This example shows the effects of aging on the stability of the mesh.
  • the composition of Example B was stored at ambient conditions for 1 year. A compression molded film was prepared. When a piece of the film was submerged in water the film was determined to be mesh-forming.
  • EXAMPLE 2 A blend containing 21 grams of the modified low density polyethylene of Example 1 and 21 grams of poly(ethylene oxide) (POLYOX ® WSR N-80) was prepared using the Haake Rheomix 600 twin-roller mixer. 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.
  • POLYOX ® WSR N-80 poly(ethylene oxide)
  • the film was determined to be mesh-forming. After 90 seconds of water immersion a stable mesh was formed. The average pore size of the mesh was determined by equivalent hydraulic diameter to be 55.8 ⁇ 36.8 microns. The average open area of the mesh was determined by image analysis of a photograph to be 3.2 ⁇ 1.2 %.
  • a blend containing 12.6 grams of the modified low density polyethylene of Example 1 and 29.4 grams of poly(ethylene oxide) (POLYOX ® WSR N-80) was prepared using the Haake Rheomix 600 twin-roller mixer. Each zone of the Haake mixer was preheated to 180°C. The material was mixed for 20 minutes at a screw speed of 150 ⁇ m. After 20 minutes, the melt was removed from the mixer and cooled in air.
  • POLYOX ® WSR N-80 poly(ethylene oxide)
  • the film was determined to be mesh-forming. After 60 seconds of water immersion a stable mesh was formed. The average pore size of the mesh was determined to be 68.7 ⁇ 70.6 microns and the average open area in the mesh was determined by image analysis of a photograph to be 3.9 ⁇ 3.3 %.
  • EXAMPLE 4 A blend containing 9.5 grams of the modified low density polyethylene of Example 1 and 32.5 grams of polyethylene oxide) (POLYOX* WSR N-80) was prepared using the Haake Rheomix 600 twin-roller mixer. Each zone of the Haake mixer was preheated to 180°C. The material was mixed for 20 minutes at a screw speed of 150 ⁇ m. After 20 minutes, the melt was removed from the mixer and cooled in air.
  • the film was determined to be mesh-forming. After 30 seconds of water immersion a stable mesh was formed. The average pore size of the mesh was determined to be 68.7 ⁇ 70.6 microns and the average open area in the mesh was determined by image analysis of a photograph to be 3.9 ⁇ 3.3 %.
  • EXAMPLE 5 A blend containing 8.4 grams of the modified low density polyethylene of Example 1 and 33.6 grams of poly(ethylene oxide) (POLYOX ® WSR N-80) was prepared using the Haake Rheomix 600 twin-roller mixer. 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 mesh-forming. After 30 seconds of water immersion a stable mesh was formed. The average pore size of the mesh was determined to be 42.6 ⁇ 24.8 microns and the average open area in the mesh was determined by image analysis of a photograph to be 6.5 ⁇ 4.1 %.
  • POLYOX ® WSR N-80 poly(ethylene oxide)
  • a blend containing 6.7 grams of the modified low density polyethylene of Example 1 and 35.3 grams of polyethylene oxide) (POLYOX ® WSR N-80) was prepared using the Haake Rheomix 600 twin-roller mixer. Each zone of the Haake mixer was preheated to 180 ⁇ C. The material was mixed for 20 minutes at a screw speed of 150 ⁇ m. After 20 minutes, the melt was removed from the mixer and cooled in air.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Glass Compositions (AREA)
  • Filtering Materials (AREA)

Abstract

Cette invention a trait à une méthode consistant à greffer un acide acrylique fondu sur une polyoléfine afin de former une polyoléfine modifiée. L'invention a trait aussi non seulement à un article qui réagit à l'eau mais également à une méthode visant à former cet article à partir d'un mélange fait pour 15 % et 50 % de son poids de polyoléfine modifiée, et pour 85 % et 50 % de son poids de poly(éthylène oxyde).
PCT/US1997/022544 1996-12-09 1997-12-03 Materiau maillant et procede de realisation correspondant WO1998025979A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002272697A CA2272697A1 (fr) 1996-12-09 1997-12-03 Materiau maillant et procede de realisation correspondant
EP97954546A EP0948550A1 (fr) 1996-12-09 1997-12-03 Materiau maillant et procede de realisation correspondant
AU58971/98A AU732005B2 (en) 1996-12-09 1997-12-03 Mesh-forming material and method of making the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76192496A 1996-12-09 1996-12-09
US08/761,924 1996-12-09

Publications (1)

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WO1998025979A1 true WO1998025979A1 (fr) 1998-06-18

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KR (1) KR20000069359A (fr)
AU (1) AU732005B2 (fr)
CA (1) CA2272697A1 (fr)
WO (1) WO1998025979A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003078487A1 (fr) * 2002-03-20 2003-09-25 Polimeri Europa S.P.A. Procede pour la fonctionnalisation des polyolefines
US10293289B2 (en) 2013-02-14 2019-05-21 Nanopareil, Llc Hybrid felts of electrospun nanofibers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830888A (en) * 1972-04-03 1974-08-20 Exxon Research Engineering Co Compositions comprising a blend of a vinyl resin and grafted olefin polymer
US3953655A (en) * 1972-04-03 1976-04-27 Exxon Research And Engineering Company Polymers with improved properties and process therefor
WO1996020831A1 (fr) * 1994-12-30 1996-07-11 Kimberly-Clark Worldwide, Inc. Film evacuable dans l'eau
EP0725090A2 (fr) * 1995-01-10 1996-08-07 PCD-Polymere Gesellschaft m.b.H. Procédé de préparation de polymères greffés de polypropylène à haute viscosité

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830888A (en) * 1972-04-03 1974-08-20 Exxon Research Engineering Co Compositions comprising a blend of a vinyl resin and grafted olefin polymer
US3953655A (en) * 1972-04-03 1976-04-27 Exxon Research And Engineering Company Polymers with improved properties and process therefor
WO1996020831A1 (fr) * 1994-12-30 1996-07-11 Kimberly-Clark Worldwide, Inc. Film evacuable dans l'eau
EP0725090A2 (fr) * 1995-01-10 1996-08-07 PCD-Polymere Gesellschaft m.b.H. Procédé de préparation de polymères greffés de polypropylène à haute viscosité

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003078487A1 (fr) * 2002-03-20 2003-09-25 Polimeri Europa S.P.A. Procede pour la fonctionnalisation des polyolefines
US10293289B2 (en) 2013-02-14 2019-05-21 Nanopareil, Llc Hybrid felts of electrospun nanofibers
USRE49773E1 (en) 2013-02-14 2024-01-02 Nanopareil, Llc Hybrid felts of electrospun nanofibers

Also Published As

Publication number Publication date
AU732005B2 (en) 2001-04-12
CA2272697A1 (fr) 1998-06-18
EP0948550A1 (fr) 1999-10-13
KR20000069359A (ko) 2000-11-25
AU5897198A (en) 1998-07-03

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