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WO1997011989A1 - Polymeres sulfones et procede de sulfonation de polymeres - Google Patents

Polymeres sulfones et procede de sulfonation de polymeres Download PDF

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Publication number
WO1997011989A1
WO1997011989A1 PCT/US1996/013938 US9613938W WO9711989A1 WO 1997011989 A1 WO1997011989 A1 WO 1997011989A1 US 9613938 W US9613938 W US 9613938W WO 9711989 A1 WO9711989 A1 WO 9711989A1
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WO
WIPO (PCT)
Prior art keywords
oxygen
polymer
product
sulfur dioxide
exposing
Prior art date
Application number
PCT/US1996/013938
Other languages
English (en)
Inventor
David L. Myers
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
Priority claimed from US08/679,607 external-priority patent/US5798078A/en
Application filed by Kimberly-Clark Worldwide, Inc. filed Critical Kimberly-Clark Worldwide, Inc.
Priority to EP96930634A priority Critical patent/EP0852598A1/fr
Priority to AU69608/96A priority patent/AU717573B2/en
Priority to BR9610713A priority patent/BR9610713A/pt
Priority to CA002230110A priority patent/CA2230110C/fr
Publication of WO1997011989A1 publication Critical patent/WO1997011989A1/fr
Priority to MXPA/A/1998/002333A priority patent/MXPA98002333A/xx

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/14—Chemical modification with acids, their salts or anhydrides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C08B5/14—Cellulose sulfate
    • 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
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/36—Sulfonation; Sulfation
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts

Definitions

  • the present invention is directed to surface modified polymers. More particularly, the present invention is directed to sulfonated polymers. Still more particularly, the present invention is directed to gas phase sulfonation of polymers.
  • thermoplastic polymers for example thermoplastic polymers
  • thermoplastic polymers for example polyolefin polymers
  • polyolefin fibers may be employed in a variety of commercial applications.
  • absorbent products, disposable absorbent products and disposable nonwoven absorbent products the inherent hydrophobic nature of such polymers is a disadvantage.
  • hydrophobic nature of these polymers requires alteration.
  • One method of altering the hydrophobic nature of such polymers, for example shaped polymers, is sulfonation.
  • shaped polymer or “shaped polymers” means any solid form of a polymer, in contrast to a polymer in gaseous or liquid phase, or in solution.
  • shaped polymers can be in particulate form, such as powder or granules or chips, a molded article, an extruded shape, fiber ⁇ , woven or nonwoven fabrics, films, foams or the like.
  • sulfonation means methods of forming a compound containing sulfonic acid, the -S0 2 ⁇ ' group.
  • Such methods include, for example, converting organic compounds to sulfonic acids or sulfonates containing the structural group C-SO-,-0 " or in some cases , N-S0-.-0 .
  • conventional sulfonation methods require the use and/or storage of materials which pose both health and safety concerns. Examples of such materials include, for example, sulfur trioxide, concentrated sulfuric acid, oleum, and chlorosulfuric acid.
  • undesirable surface discoloration may occur.
  • fibers formed from un-dyed polymers such as polyolefin fibers and desirably, polypropylene fibers
  • the surface color of such fibers changes such that the fibers appear generally yellow, brown or black in color.
  • such polymers may have applications as absoroenr articles.
  • the discoloring of polymer fibers is generally not desirable, particularly when such polymer fibers are incorporated into personal absorbent articles, such as diapers, feminine pads, or adult incontinence articles. Therefore, there is a need for improved methods of sulfonation which avoid the disadvantages of conventional sulfonation processes.
  • Such an improved sulfonation method and the products thereof are provided by the present invention and will become more apparent upon further review of this specification.
  • the present invention provides methods of sulfonating a polymer which avoid storing large quantities of sulfur trioxide, concentrated sulfuric acid, oleum, or chlorosulfuric acid.
  • the methods of the present invention also avoid the undesirable discoloring and, particularly, the undesirable brown coloring, inherent in many conventional sulfonating processes.
  • the method of sulfonating a polymer includes exposing sulfur dioxide and a source of oxygen to free radical producing energy to produce a product and contacting the polymer with the product of preceding step.
  • the steps of exposing sulfur dioxide and the source of oxygen to free radical producing energy and contacting the polymer with this product are performed in a reduced pressure environment.
  • the source of the free radical producing energy may be ultra-violet light, gamma radiation, electron beam, noble gas radio frequency (rf) plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas or a combination thereof.
  • the method of sulfonating a polymer includes contacting the polymer with sulfur dioxide and a source of oxygen and exposing the contacted polymer to free radical producing energy.
  • the polymer may be contacted with a mixture of sulfur dioxide and the source of oxygen or the polymer may be separately contacted with sulfur dioxide and the source of oxygen.
  • the polymer may first be contacted with sulfur dioxide and then contacted with the source of oxygen.
  • the contacting and exposing steps occur in a reduced pressure, i.e., generally, less than 1 atmosphere, environment.
  • the source of the free radical producing energy may also be ultra-violet light, gamma radiation, electron beam, noble gas rf plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas or a combination thereof.
  • Another embodiment of the present invention provides a method of imparting hydrophilic character to a shaped polymer. This method includes exposing sulfur dioxide and a source of oxygen to free radical producing energy and contacting the polymer with the product of the preceding step. Desirably, the contacting and exposing steps occur in a reduced pressure environment.
  • the source of the free radical producing energy may be ultra-violet light, gamma radiation, electron beam, noble gas rf plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas or a combination thereof.
  • Another method of imparting hydrophilic character to a shaped polymer includes contacting the polymer with sulfur dioxide and a source of oxygen and exposing the contacted polymer to radical producing energy. Desirably, the contacting and exposing steps occur in a reduced pressure environment.
  • the source of the free radical producing energy may also be ultra- violet light, gamma radiation, electron beam, noble ga ⁇ rf plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas or a combination thereof.
  • FIG. 1 is a schematic illustration of a reaction chamber.
  • oxygen donating gas or "source of oxygen” means di-oxygen or a gas which is capable of contributing an oxygen atom or an oxygen radical.
  • free radical producing energy means any energy which results in homolytic or heterolytic cleavage of at least two covalently bonded atoms.
  • hydrophilic or “hydrophilic character" when associated with a material, such as, for example, a polymer or shaped polymer, means that the water (deionized, distilled water) contact angle of a droplet of water positioned on the surface of such material is less than 90° .
  • hydrophobic when associated with a material, such as, for example, a polymer, means that the water (deionized, distilled water) contact angle of a droplet of water positioned on the surface of such material is greater than 90°.
  • polymer may mean both synthetic or natural polymers. Examples of natural polymeric materials include, cotton, silk, wool, and cellulose, by way of illustration only. Synthetic polymers, in turn, can be either thermosetting or thermoplastic materials, with thermoplastic materials being more common.
  • thermosetting polymers include, by way of illustration only, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate, and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds; amino resins, such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyandiamide- formaldehyde resins, melamine-formaldehyde resins, sulfonamide- formaldehyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins, such as
  • thermoplastic polymers include, by way of illustration only, end-capped polyacetals, such as poly(oxy- methylene) or polyformaldehyde, poly(trichloroacetaldehyde) , poly(n-valeraldehyde) , poly(acetaldehyde) , poly(propionalde- hyde) , and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid) , poly(methacrylic acid) , poly(ethyl acrylate) , poly(methyl methacrylate) , and the like; fluoro ⁇ carbon polymers, such as poly(tetrafluoroethylene) , per- fluorinated ethylene-propylene copolymers, ethylene-tetra- fluoroethylene copolymers, poly(chlorotrifluoroethylene) , ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride) , poly(vinyl fluor
  • polyaryl ethers such as poly(oxy-2 , 6-d ⁇ methyl-l, 4-phenylene) or poly ( p.-phenylene oxide) , and the like
  • polyaryl sulfones such as P oly(oxy-l,4-phenylenesulfonyl-l,4-phenyleneoxy-l,4- phenylene-isopropylidene-l,4-phenylene) , poly(sulfonyl-1,4- phenyleneoxy-l,4-pheny!enesulfonyl-4,4'-biphenylene) , and the like
  • polycarbonates such as poly(bisphenol A) or poly ( carbonyldioxy-l,4-phenylene ⁇ sopropylidene-l,4-phenylene) , and the like
  • polyesters such as poly(ethylene terephthalate) , poly ( tet
  • shaped polymer or “shaped polymers” means any solid form of a polvmer, in contrast to a polymer in gaseous or liquid phase, or in solution.
  • shaped polymers can be in particulate form, such as powder or granules or chips, a molded article, an extruded shape, fibers, woven or nonwoven fabrics, films, foams or the like.
  • sulfonation means methods of converting organic compounds to sulfonic acids or sulfonates containing the struc t ural group C-S0 2 -0 or in some cases, N- S0 2 - 0 .
  • Sulfonation of a shaped polymer is useful, for example, in altering the surface properties of such shaped polymer. The properties of such surface may be altered, for example, such that the altered surface becomes hydrophobic, is more receptive to the placement of an adhesive thereon, and/or becomes printable.
  • nonwoven fabric refers to a fabric that has a structure of individual fibers or filaments which are interlaid, but not in an identifiable repeating manner.
  • spunbond fibers refers to fibers which are formed by extruding molten thermoplastic material as filaments from a plurality of fine, usually circular capillaries of a spinnerette with the diameter of the extruded filaments then being rapidly reduced as by, for example, in U.S. Patent no. 4,340,563 to Appel et. al., and U.S. Patent no. 3,692,618 to Dorschner et. al. , U.S. Patent no. 3,802,817 to Matsuki et. al., U.S. Patent nos. 3,338,992 and 3,341,394 to Kinney, U.S. Patent nos. ,502,763 and 3,909,009 to Levy, and U.S. Patent no. 3,542,615 to Dobo et. al. which are all herein incorporated by reference.
  • meltblown fibers means fiber ⁇ formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into a high velocity, usually heated gas (e.g. air) stream which attenuates the filaments of molten thermoplastic material to reduce their diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a fabric of randomly disbursed meltblown fibers. Meltblowing is described, for example, in U.S. Patent no. 3,849,241 to Buntin, U.S. Patent no. 4,307,143 to Meitner et. al., and U.S.
  • Patent 4,663,220 to Wisneski et. al. which are all herein incorporated by reference.
  • the sulfonating methods of the present invention avoid the requirement of having or storing quantities of materials, such as, for example, sulfur trioxide, concentrated sulfuric acid, oleum and chlorosulfuric acid, which are traditionally required to initiate conventional sulfonation processes.
  • the methods of the present invention also avoid the inherent brown coloring produced by many conventional sulfonation processes.
  • the method of sulfonating a polymer includes exposing sulfur dioxide and a source of oxygen to free radical producing energy and contacting the polymer with the product of preceding step.
  • the steps of exposing sulfur dioxide and the source of oxygen to free radical producing energy and contacting the polymer with this product are performed in a reduced pressure environment.
  • the source of the free radical producing energy may be ultra-violet light, gamma radiation, electron beam, noble gas radio frequency (rf) plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas, described in greater detail below, or a combination thereof.
  • the method of sulfonating a polymer includes contacting the polymer with sulfur dioxide and a source of oxygen and exposing the contacted polymer to free radical producing energy.
  • the polymer may be contacted with a mixture of sulfur dioxide and the source of oxygen or the polymer may be separately contacted with sulfur dioxide and the source of oxygen.
  • the polymer may fir ⁇ t be contacted with sulfur dioxide and then contacted with the source of oxygen.
  • the contacting and exposing steps occur in a reduced pressure environment.
  • the source of the free radical producing energy may also be ultra-violet light, gamma radiation, electron beam, noble gas rf plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas, or a combination thereof.
  • Another embodiment- of the present invention provides a method of imparting hydrophilic character to a shaped polymer.
  • Thi ⁇ method includes exposing sulfur dioxide and a source of oxygen to free radical producing energy and contacting the polymer with the product of preceding step. Desirably, the contacting and exposing steps occur in a reduced pressure environment.
  • the source of the free radical producing energy may be ultra ⁇ violet light, gamma radiation, electron beam, noble gas rf plasma or corona discharge.
  • the source cf oxygen may include oxygen, an oxygen donating gas, or a combination thereof.
  • Another method of imparting hydrophilic character to a shaped polymer includes contacting the polymer with sulfur dioxide and a source of oxygen and exposing the contacted polymer to radical producing energy. Desirably, the contacting and exposing steps occur in a reduced pressure environment.
  • the source of the free radical producing energy may also be ultra ⁇ violet light, gamma radiation, electron beam, noble gas rf plasma or corona discharge.
  • the source of oxygen may include oxygen, an oxygen donating gas, or a combination thereof.
  • the concentrations of sulfur dioxide and oxygen are not critical, provided that such concentrations are sufficient to impart the desired degree of sulfonation and/or hydrophilic character to the polymer.
  • the concentration of sulfur dioxide and oxygen are sufficient when either the amount of ⁇ 0 2 present exceeds the amount of oxygen (0 2 ) , or when the concentrations of SO- and 0 2 are stoichiometric. In either case, it is desirable to avoid the presence of excess quantities of oxygen, i.e. , quantities of oxygen greater than stoichiometric quantities, in the reaction atmosphere during the sulfonation reaction.
  • reaction atmosphere may be anhydrous or the reaction atmosphere may be substantially or relatively water-free.
  • small amounts of residual water may be removed by the formation of S0 during the reaction.
  • the ⁇ 0 3 reacts with the water to produce sulfuric acid.
  • the presence of residual water may not effect the outcome of the sulfonation reaction.
  • the relative ratios of S0 2 to 0 2 for carrying out the methods of the present invention may be expressed as mole ratios.
  • the minimal mole ratio of ⁇ 0 2 to o. for the sulfonation methods of the present invention is 2:1 (i.e. exactly stoichiometric). Desirably, the mole ratios may be expressed in whole numbers.
  • the range of mole ratios of SO. to 0 2 may range from 2:1 to 5:1.
  • an oxygen donating gas may be used in place of all or part of the 0 2 requirement in the S0 2 and 0 2 blend.
  • nitrous oxide an example of an oxygen donating gas
  • Other oxygen donating gases may include, for example, nitrogen dioxide and the halogen dioxides like chlorine dioxide.
  • one or more oxygen donating gases with or witiiout 0 2 may be employed provided, the overall stoichiometries of S0 2 to the other oxygen and/or oxygen donating gases conform to the S0 2 to 0 2 mole ratios expressed above.
  • Inert gases may also be employed in the sulfonation methods of the present invention.
  • an inert gas may be blended with S0 2 and 0 2 and/or oxygen donating gas(es) .
  • an inert gas may be used to flush less desirable gases, such as air, from the reaction atmosphere and/or article, such as a porous or fibrous web, prior to initiating the sulfonation reaction.
  • the pressure of the reaction atmosphere may either be below one atmosphere (reduced pressure) , or at or above one atmosphere.
  • inert gases examples include nitrogen, argon, helium, and krypton.
  • argon is capable of excluding oxygen due to its atomic weight and density.
  • the use of argon gas may provide a continuous sulfonation process.
  • the article such as a fibrous web, is purged with an argon gas stream to remove the air entrained therein.
  • the essentially air-free web may then pass into a UV chamber having a blend of S0 2 , 0 ⁇ (or other source of oxygen) , and Ar for irradiation, and sulfonation.
  • S0 2 , 0 ⁇ or other source of oxygen
  • Ar for irradiation, and sulfonation.
  • the quantities of SO, and O- are best expressed as mole fractions.
  • the mole fraction range of total gas present as sulfur dioxide is from about 0.83 to about 0.2.
  • the mole fraction of total gas present as sulfur dioxide may be about 0.83 and desirably about 0.8, and more desirably about 0.75, and mo ⁇ t de ⁇ irably 0.67.
  • the corre ⁇ ponding mole fraction range of oxygen is about 0.17 to about 0.33.
  • the mole fraction of oxygen may be about 0.17, and desirably 0.2, and more desirably 0.25, and most desirably 0.33.
  • the mole fraction of that gas would be determined by the stoichiometry of the reaction leading to the formation of the S0 3 .
  • Polymers and desirably, shaped polymers, and more desirably, fabrics formed from polymer fibers are useful in the practice of the present invention.
  • Such polymer fabrics may be either woven or nonwoven.
  • Nonwoven fabrics can be made from a variety of processes including, but not limited to, air laying processes, wet laid processes, hydroentangling processes, spunbonding, meltblowing, staple fiber carding and bonding, and solution spinning.
  • the fibers themselves can be made from a variety of polymer materials, including, but not limited to, polyesters, polyolefins, nylons and copolymers of these materials.
  • the fibers may be relatively short, staple length fibers, typically less than 3 inches, or longer more continuous fibers such as are typically produced by a spunbonding process.
  • shaped polymers other than wovens or nonwovens may be used. Examples of such other shaped polymers include, films, foam/film laminates and combinations hereof, with and without woven or nonwovens.
  • these fabrics may be formed from a single layer or multiple layers.
  • the layers are generally positioned in a juxtaposed or surface-to- ⁇ urface relation ⁇ hip and all or a portion of the layers may be bound to adjacent layer ⁇ .
  • nonwoven fabrics formed from such fibers are the polypropylene nonwoven fabrics produced by the Assignee of record, Kimberly-Clark Corporation
  • the quartz reactor 10 shown in FIG. 1 was used for the sulfonation of the samples described in Examples 1-5.
  • the quartz reactor 10 is formed from optical grade fused quartz a product of Technical Glass Products, Inc. , Ohio.
  • the quartz reactor 10 includes a reactor housing 12 having separable top and bottom portions, 14 and 15 respectively, for selectively placing and removing samples into the interior of the reaction housing 12.
  • the top portion 14 further includes a vacuum port
  • a pressure sensor 32 such as a capacitance manometer model no. CM100, manufactured by Leybold Inficon, Inc., NY., by valve 34.
  • Wetting Tension Test Kit Model ⁇ TT ll-l from Pillar Technologies, Inc., Hartland, WI.
  • the surface tension for wetting was taken as the surface ten ⁇ ion of the fluid which spontaneously absorbed into the fibrous nonwoven substrates.
  • the Wetting Tension Kit conforms to ASTM Standard D2578-67.
  • Contact Angle Contact angle measurements were made using a Rame-Hart Model 100-06 NRL Contact Angle Goniometer. The contact angle is taken as the line tangent to the edge of a fluid droplet in contact with the substrate surface. The contact angle values were derived by averaging the observations taken from a minimum of three droplets. Eacli droplet produced a pair of observations.
  • Example 1 Sulfonation of Polypropylene Meltblown A sample of 0.5 ounces per square yard (osy) polypropylene meltblown (PP MB) material was placed in the quartz reactor 10 shown in FIG. 1. With the sample positioned in the bottom portion 16, the reactor housing 12 was evacuated via the vacuum port 18 to less than 1x10 3 Torr total pressure. After 5 min the reactor housing 12 wa ⁇ back-filled via ga ⁇ port 24 with an inert ga ⁇ (N 2 or Ar) to a pre ⁇ sure of 760 Torr. The reactor housing 12 was then re-evacuated. The cycles of back filling and evacuating were repeated three times and concluded with a final evacuation of the reactor housing 12 to a pressure of less than 1x10 3 Torr total pressure.
  • osy polypropylene meltblown
  • the final evacuation was followed by introduction into the reactor housing 12 via gas port 24 of a sulfur dioxide (SO-) and oxygen (0-.) gas mixture to a total pressure of 200 Torr.
  • SO- sulfur dioxide
  • oxygen (0-.) gas mixture was 2:1.
  • the reactor was then placed in an annular ultraviolet light reactor (Rayonet Photochemical Reactor, The Southern New England Ultraviolet Company) equipped with 16 low pressure mercury lamps. Each lamp had a principle emission wavelength of 254 nm.
  • the combined output of all 16 lamps, measured at the center of the reactor chamber, was 6 milliwatts per centimeter squared (mW/cm 2 ) .
  • the UV irradiation time (Reaction Time) for individual PP MB samples was varied from 5 min to 15 min.
  • the reactor was purged with inert ga ⁇ (N 2 or Ar) , via ga ⁇ port 24, to remove re ⁇ idual S0 2 or SO... 5 Minute Reaction Time.
  • the PP MB material was white in color and was wettable to an aqueous test solution with a ⁇ urface ten ⁇ ion of 56 dyne/cm.
  • Surface analysis of the sulfonated meltblown PP using ESCA revealed the following surface atomic composition: 88.3 atom% carbon, 9.2 atom% oxygen, and 2.5 atom, sulfur.
  • the PP MB material was white in color and was wettable to an aqueous test solution with a surface tension of 72 dyne/cm (i.e. equivalent to water) .
  • Surface analysis of this sulfonated meltblown using ESCA revealed the following surface atomic composition: 88.5 atom% carbon, 9.2 atom% oxygen, and 2.3 atom% ⁇ ulfur.
  • the PP MB material wa ⁇ very faint brown in color and was wettable to an aqueou ⁇ test solution with a surface tension of 72 dyne/cm (i.e. equivalent to water) .
  • Surface analysi ⁇ of thi ⁇ sulfonated meltblown using ESCA revealed the following surface atomic composition: 84.9 atom% carbon, 12.1 atom* oxygen, and 3.0 atom% sulfur.
  • Each of the reaction times yielded materials with significantly altered surface properties in comparison with the control meltblown polypropylene.
  • the ESCA data acquired from each sample provides evidence for the incorporation of sulfur on the surface of each material.
  • the sulfur is present as ⁇ ulfonic acid. This indicates that a carbon to sulfur bond formed in the sulfonation process leading the formation of R- SO 3 H groups.
  • Example 2 Sulfonation of Polyethylene Meltblown
  • PE MB polyethylene meltblown
  • the PE MB material was white in appearance after sulfonation.
  • the material was wettable to an aqueous test solution with a surface tension of 72 dyne/cm (i.e. equivalent to water) .
  • a control non-sulfonated PE MB was wettable to only a 36 dyne/cm test solution.
  • Surface analysis of the PE MB using ESCA indicated the following surface compo ⁇ ition: 95.4 atom% carbon, 3.5 atom% oxygen, and 1.1 atom% ⁇ ulfur.
  • the appearance of sulfur on the surface indicates its incorporation into the surface of the material.
  • the sulfur is present as sulfonic acid.
  • the experimental procedure used to sulfonate cellulose was the same as outlined in Example 1.
  • the cellulose substrate was a Whatman Type 1 Filter Paper.
  • a sample of the cellulose was irradiated in the S0 2 /0 2 atmosphere for 10 min.
  • the cellulose substrate was white following sulfonation. A comparison of surface tension for wetting failed to reveal any difference in the cellulose substrate before and after sulfonation.
  • the sulfonated cellulose had a slight sulfur- like odor. This odor was effectively removed by washing in deionized water and drying at 80°C.
  • the ESCA analysis of the cellulose samples clearly shows the incorporation of sulfur in the cellulo ⁇ e surface.
  • the sulfur appears to be present as sulfonic acid ⁇ .
  • the presence of fluorine may be attributed to either a fluorochemical additive in the Whatman Filter paper, or to fluorochemicals present in the high vacuum grease used to seal the quartz reactor tube (see Figure 1) .
  • PET fibers The experimental procedure used to sulfonate polyethylene terephthalate (PET) fibers was the same as outlined in Example 1.
  • the PET fibers were irradiated for 10 min in the S0 2 /0 2 atmosphere described in Example 1.
  • the sulfonated PET fibers were white in color.
  • the sulfonated PET fibers were wettable to an aqueous solution with a surface tension of 72 dyne/cm (i.e. equivalent to water).
  • non-sulfonated control PET fibers were wettable to an aqueous solution with surface tension of 56 dyne/cm and the contact angle of water was observed to be greater than 90°.
  • a contact angle for water on the sulfonated fibers could not be measured due to spontaneous absorption of the water droplet. Water washing of the sulfonated PET fibers and drying at 80°c did not alter their wettability.
  • the surface composition (ESCA) of the PET fiber ⁇ is summarized in Table 2.
  • the ESCA analysi ⁇ clearly shows the incorporation of sulfur into the PET fiber surfaces.
  • the sulfur is pre ⁇ ent as sulfonic acids.
  • the fluorine present on the sulfonated and water washed sulfonated fibers is due to the high vacuum grease used in sealing the quartz tube reactor.
  • PS film sulfonate polystyrene (PS) film was the same a ⁇ outlined in Example 1.
  • PS film wa ⁇ irradiated for 10 min in the S0 2 /0 2 atmo ⁇ phere.
  • the water contact angle on the sulfonated PS film was effectively 0°, and the water droplet spread spontaneously to a film.
  • the water contact angle on the non-sulfonated PS film was 92°.
  • a water wash of the sulfonated PS film did not alter its water wettability.
  • the surface composition (ESCA) of the sulfonated PS film is summarized in Table 3.
  • control PS film should have a surface composition of around 100 atom% carbon.
  • the silicon, chlorine, and oxygen observed on the control are present due to handling of the film sample.
  • the large increase in atomic percent composition of oxygen and sulfur in the sulfonated PS film is a clear evidence that sulfonation has drastically altered the PS surface.
  • the ⁇ ulfur is pre ⁇ ent as ⁇ ulfonic acid groups. Again, the fluorine is due to surface contamination by the high vacuum grease used in the quartz tube reactor.

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Abstract

Procédés de sulfonation d'un polymère, dont l'un consiste à exposer du dioxyde de soufre et de l'oxygène à de l'énergie produisant des radicaux libres et à mettre en contact ledit polymère avec le produit de l'étape précédente. De préférence, lesdites étapes sont menées dans un environnement à pression réduite. Un autre procédé de sulfonation d'un polymère consiste à mettre en contact ledit polymère avec du dioxyde de soufre et de l'oxygène et à exposer le polymère ainsi obtenu à de l'énergie produisant des radicaux libres. Le polymère peut être mis en contact avec un mélange de dioxyde de soufre et d'oxygène, ou bien il peut être mis en contact séparément avec du dioxyde de soufre et de l'oxygène. Lorsque ledit polymère est mis en contact séparément avec le dioxyde de soufre et l'oxygène, il peut être d'abord mis en contact avec le dioxyde de soufre et ensuite avec l'oxygène. La source d'énergie produisant des radicaux libres peut être de la lumière ultraviolette, un faisceau d'électrons, un plasma à radiofréquence (RF) à gaz rare, une décharge lumineuse ou un rayonnement gamma.
PCT/US1996/013938 1995-09-28 1996-08-29 Polymeres sulfones et procede de sulfonation de polymeres WO1997011989A1 (fr)

Priority Applications (5)

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EP96930634A EP0852598A1 (fr) 1995-09-28 1996-08-29 Polymeres sulfones et procede de sulfonation de polymeres
AU69608/96A AU717573B2 (en) 1995-09-28 1996-08-29 Sulfonated polymers and method of sulfonating polymers
BR9610713A BR9610713A (pt) 1995-09-28 1996-08-29 Polímeros sulfonados e método para sulfonação de polímeros
CA002230110A CA2230110C (fr) 1995-09-28 1996-08-29 Polymeres sulfones et procede de sulfonation de polymeres
MXPA/A/1998/002333A MXPA98002333A (en) 1995-09-28 1998-03-25 Sulphonated polymers and sulphonate polime method

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US08/679,607 US5798078A (en) 1996-07-11 1996-07-11 Sulfonated polymers and method of sulfonating polymers

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Cited By (4)

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WO1999016964A1 (fr) * 1997-09-30 1999-04-08 Scapa Group Plc Traitement de tissus industriels
WO2000049069A1 (fr) * 1999-02-16 2000-08-24 Mikael Paronen Membrane polymere et procede de production correspondant
EP1072635A1 (fr) * 1999-07-22 2001-01-31 Wolfgang Dr. Kern Procédé pour modifier des surfaces polymères
US6664340B1 (en) 1999-04-23 2003-12-16 Danisco Finland Oy Sulphonated polymer resin and preparation thereof

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
KR20160101078A (ko) * 2013-12-16 2016-08-24 바스프 에스이 세탁 세제에 사용하기 위한 및 항 그레잉제로서 사용하기 위한 개질된 다당류

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US3464952A (en) * 1967-01-23 1969-09-02 Grace W R & Co Polyethylene stabilized by treatment with sulfur dioxide in the presence of free radicals
GB1414671A (en) * 1972-01-14 1975-11-19 Nunc As Method of improving the surface properties of articles made from a plastics material
JPS515868B2 (fr) * 1972-08-03 1976-02-23
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999016964A1 (fr) * 1997-09-30 1999-04-08 Scapa Group Plc Traitement de tissus industriels
WO2000049069A1 (fr) * 1999-02-16 2000-08-24 Mikael Paronen Membrane polymere et procede de production correspondant
US6630518B1 (en) 1999-02-16 2003-10-07 Mikael Paronen Polymer membrane and a process for the production thereof
US6902849B2 (en) 1999-02-16 2005-06-07 Mikael Paronen Polymer membrane and a process for the production thereof
US6664340B1 (en) 1999-04-23 2003-12-16 Danisco Finland Oy Sulphonated polymer resin and preparation thereof
EP1072635A1 (fr) * 1999-07-22 2001-01-31 Wolfgang Dr. Kern Procédé pour modifier des surfaces polymères
AT408227B (de) * 1999-07-22 2001-09-25 Wolfgang Dr Kern Verfahren zur modifizierung von polymeroberflächen

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MX9802333A (es) 1998-08-30
KR19990063820A (ko) 1999-07-26

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