CN1202187A - Sulfonated polymers and method of sulfonating polymers - Google Patents

Sulfonated polymers and method of sulfonating polymers Download PDF

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Publication number
CN1202187A
CN1202187A CN96198332A CN96198332A CN1202187A CN 1202187 A CN1202187 A CN 1202187A CN 96198332 A CN96198332 A CN 96198332A CN 96198332 A CN96198332 A CN 96198332A CN 1202187 A CN1202187 A CN 1202187A
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oxygen
polymkeric substance
product
polymer
free radical
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D·L·迈尔斯
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Kimberly Clark Worldwide Inc
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Priority claimed from US08/679,607 external-priority patent/US5798078A/en
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Publication of CN1202187A publication Critical patent/CN1202187A/en
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    • 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
    • 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
    • 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

Abstract

Methods of sulfonating a polymer are provided. One method of sulfonating a polymer includes exposing sulfur dioxide and oxygen to free radical producing energy and contacting the polymer with the product of preceding step. Desirably, the steps of exposing sulfur dioxide and oxygen to free radical producing energy and contacting the polymer with this product are performed in a reduced pressure environment. Another method of sulfonating a polymer includes contacting the polymer with sulfur dioxide and oxygen and exposing the contacted polymer to free radical producing energy. The polymer may be contacted with a mixture of sulfur dioxide and oxygen or the polymer may be separately contacted with sulfur dioxide and oxygen. When the polymer is separately contacted with sulfur dioxide and oxygen, the polymer may first be contacted with sulfur dioxide and then contacted with oxygen. The source of the free radical producing energy may be ultra-violet light, electron beam, noble gas radio frequency (rf) plasma, corona discharge, or gamma radiation.

Description

The method of sulfonating of sulfonated polymer and polymkeric substance
Invention field
The present invention relates to the surface modification polymkeric substance.Specifically, the present invention relates to sulfonated polymer.More particularly, the present invention relates to the gas phase xanthation of polymkeric substance.
Background of invention
As everyone knows, the surface of some polymkeric substance, the surface of thermoplastic polymer for example, for essence not wettable or hydrophobic.Same well-knownly be, thermoplastic polymer, for example polyolefin polymer can be shaped as fiber.This type of polyolein fiber can be applicable to various commercial uses.With regard to some commercial use, for example absorbent article, with promptly abandoning absorbent article and with promptly abandoning the non woven fabric absorbent article, this base polymer institute inherent hydrophobic property is a shortcoming.Just because of this, the hydrophobic polymkeric substance of this class essence is used to need to change its hydrophobic property before the above-mentioned absorbent article.
A kind of this base polymer of change for example has the polymkeric substance of shape, the method for hydrophobic property be sulfonation.Term as used herein " polymkeric substance that shape is arranged " is meant the polymkeric substance of any solid form that is different from gas phase or liquid phase or solution form polymkeric substance.Therefore, the polymkeric substance that shape is arranged can be a particle form, and for example powder or pellet or section, weaved or non woven fabric, film, foam materials etc. moulded parts, extruded profile, fiber.Term as used herein " sulfonation " be meant make contain sulfonic acid or-SO 2O -The method of the compound of group.These class methods comprise, for example organic compound are converted into and contain building stone C-SO 2O contains N-SO under some situation 2The sulfonic acid of O or sulfonate.
Yet the material that jeopardizes health or safety need be used or be stored to the traditional chemical method in many cases.This type of material comprises, for example sulphur trioxide, the vitriol oil, oleum and chlorsulfonic acid.In addition, when to polymer surfaces, when for example the non-surface of knitting fibre web (weds) matrix of polyolefine being handled with traditional method of sulfonating, undesirable surface discolouration will take place in many cases.For example, with the fiber that undyed polymkeric substance is made,, better be polypropylene fibre as polyolein fiber, be generally translucent.After handling through traditional method of sulfonating, the surface color of this fibrid can change, so that fiber presents Huang, color such as brown or black usually.Mention above, this base polymer may be used as such as absorbent article.Therefore, the polymer fiber variable color generally is undesirable in some cases, especially when this type of polymer fiber is added in the individual absorbent article, when for example joining in diaper, sanitary napkin or the adult-incontinence articles.
Therefore, exist needs to the improvement method of sulfonating of eliminating traditional method of sulfonating shortcoming.The present invention just provides such improvement method of sulfonating and products thereof, and it is more clear that this point will become after further having studied this specification sheets carefully.
The invention summary
At the above-mentioned variety of problems that those skilled in the art ran into, the invention provides the polymkeric substance method of sulfonating of avoiding storing a large amount of sulphur trioxides, the vitriol oil, oleum or chlorsulfonic acid.Method of the present invention also can avoid taking place the peculiar undesirable discoloration of many traditional method of sulfonating, especially is with undesirable brown.
In one embodiment of the present invention, the polymkeric substance method of sulfonating comprises: the energy that allows sulfurous gas and oxygen source be exposed to produce free radical allows polymkeric substance contact with the product of previous step to generate a kind of product then.It is desirable for sulfurous gas and oxygen source and be exposed to energy and the polymkeric substance and the contacted step of this product that can produce free radical, all in reduced pressure atmosphere, carry out.The energy source that can produce free radical can be ultraviolet ray, gamma-rays, electron beam, rare gas radio frequency (rf) plasma body or corona discharge.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
In another embodiment, the polymkeric substance method of sulfonating comprises: allow polymkeric substance contact with oxygen source with sulfurous gas, allow the polymkeric substance after contacting be exposed to the energy that can produce free radical then.In this embodiment, can allow polymkeric substance contact, perhaps allow polymkeric substance contact with oxygen source with sulfurous gas respectively with the mixture of sulfurous gas and oxygen source.When polymkeric substance contacts with sulfurous gas and oxygen source respectively, can allow polymkeric substance contact with sulfurous gas earlier, and then contact with oxygen source.It is desirable for this contact and exposing step all in decompression, promptly in usually less than 1 atmospheric environment, carry out.In this embodiment, also ultraviolet ray, gamma-rays, electron beam, rare gas radio-frequency plasma or corona discharge of the energy source that can produce free radical.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
Another embodiment of the present invention provides the polymkeric substance of the giving shape method with water-wet behavior.This method comprises: allow sulfurous gas and oxygen source be exposed to the energy that can produce free radical, allow polymkeric substance contact with the product of previous step then.It is desirable for this contact and exposing step all carries out in reduced pressure atmosphere.In this embodiment, the energy source that can produce free radical can be ultraviolet ray, gamma-rays, electron beam, rare gas radio frequency (rf) plasma body or corona discharge.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
The polymkeric substance of giving shape comprises with the another kind of method of water-wet behavior: allow polymkeric substance contact with oxygen source with sulfurous gas, allow the polymkeric substance after the contact be exposed to the energy that can produce free radical then.It is desirable for this contact and exposing step all carries out in reduced pressure atmosphere.The energy source that can produce free radical is ultraviolet ray, gamma-rays, electron beam, rare gas radio-frequency plasma or corona discharge also.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
The accompanying drawing summary
Fig. 1 is the synoptic diagram of reaction chamber.
Detailed Description Of The Invention
Term as used herein " for carrier of oxygen " or " oxygen source " refer to molecular oxygen (di-oxygen) Perhaps can contribute the gas of oxygen atom or oxygen radical.
Term as used herein " can produce the energy of free radical " and refer to any can causing at least The atom generation homogeneous phase of two covalent bondings or the energy of heterogeneous cracking.
Ought relate to a kind of material herein, for example polymer or when the polymer of shape is arranged institute make With term " hydrophilic " or " water-wet behavior ", refer to be positioned at the water of the water droplet of this material surface (deionized water, distilled water) contact angle is less than 90 °.
Ought relate to a kind of material herein, employed term " hydrophobic " during polymer for example, Refer to be positioned at water (deionized water, the distilled water) contact angle of water droplet of this material surface greater than 90 °.
Term as used herein " polymer " had both referred to synthesize, had also referred to natural polymerization Thing. Only as an example explanation, the example of natural polymeric material comprises cotton, silk, wool and fibre Dimension is plain.
Synthetic polymer can be again a thermosetting material, or thermoplastic material, and comparatively general with thermoplastic material.Only explanation as an example, the example of thermosetting polymer comprises Synolac, for example Tetra hydro Phthalic anhydride-glycerol resin, maleic acid-glycerol resin, hexanodioic acid-glycerol resin and Tetra hydro Phthalic anhydride-pentaerythritol resin; Allyl resin (allylicresins), wherein such as monomers such as Phthalic acid, diallyl ester, diallyl isophthalate, diallyl maleate and chlorine mattress diallyl phthalates as the non-volatile linking agent in the polyester mixing material; Aminoresin, for example aniline-formaldehyde resin, ethylene urea formaldehyde resin, dicyandiamide-formaldehyde resin, melamino-formaldehyde resin, sulphonamide-formaldehyde resin and urea-formaldehyde resin; Resins, epoxy, for example crosslinked Epicholorohydrin-bisphenol a resin; Resol, for example phenol (first) urea formaldehyde comprises phenolic varnish and phenol-formaldehyde A; And thermosetting polyester, silicone and urethane.
Only explanation as an example, the example of thermoplastic polymer comprises end capped polyacetal, for example poly-(oxygen-methylene radical) or polyoxymethylene, poly-(trichoro-aldehyde), poly-(valeraldehyde), poly-(acetaldehyde), poly-(propynal) etc.; Acrylic polymers, for example polyacrylamide, poly-(vinylformic acid), poly-(methacrylic acid), poly-(ethyl propenoate), poly-(methyl methacrylate) etc.; Fluorocarbon polymer, for example poly-(tetrafluoroethylene), perfluoro ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, poly-(trifluorochloroethylene), ethylene-chlorotrifluoro-ethylene copolymer, poly-(vinylidene fluoride), poly-(vinyl fluoride) etc.; Polymeric amide, for example poly-(6-aminocaprolc acid) or poly-(ε-Ji Neixianan), poly-(hexanedioyl-1,6-hexanediamine), poly-(sebacoyl-1,6-hexanediamine), poly-(the amino undecanoic acid of 11-) etc.; Polyaramide, for example poly-(imino--1,3-phenylene imino-isophthaloyl) or poly-(mpd-i) etc.; Poly-para xylylene, for example poly-to xylylene, poly-(chloro-is to xylylene) etc.; Polyarylether, for example poly-(oxygen-2,6-dimethyl-1,4-phenylene) or poly-p-phenylene oxide etc.; Polyaryl sulfone, for example poly-(oxygen-1,4-phenylene alkylsulfonyl-1,4-phenylene oxygen-1,4-phenylene-isopropylidene-1,4-phenylene), poly-(alkylsulfonyl-1,4-phenylene oxygen-1,4-phenylene alkylsulfonyl-4,4 '-biphenylene) etc.; Polycarbonate, for example poly-(dihydroxyphenyl propane) or poly-(carbonylic dioxo-1,4-phenylene isopropylidene-1,4-phenylene) etc.; Polyester, for example poly-(ethylene glycol terephthalate), poly-(terephthalic acid 1,4-butanediol ester), poly-(cyclohexylidene-1,4-dimethylene terephthalate) or poly-(oxygen methylene radical-1,4-cyclohexylidene methylene radical oxygen paraphenylene terephthalamide) etc.; Polyarylene sulfide, for example poly-p-phenylene sulfide or poly-(sulphur-1,4-phenylene) etc.; Polyimide, for example poly-(1,2,4,5-diimides base-1,4-phenylene) etc.; Polyolefine, for example polyethylene, polypropylene, poly-(1-butylene), poly-(2-butylene), poly-(1-amylene), poly-(2-amylene), poly-(3-Methyl-1-pentene), poly-(4-methyl-1-pentene), 1,2-poly--1,3-divinyl, 1,4-poly--1,3-divinyl, polyisoprene, polychlorostyrene are for isoprene, polyacrylonitrile, poly-(vinyl-acetic ester), poly-(vinylidene chloride), polystyrene etc.; The multipolymer of above-mentioned substance, for example acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer etc.
Term as used herein " polymkeric substance that shape is arranged " is meant the polymkeric substance of any solid form that is different from gas phase or liquid phase or solution form polymkeric substance.Therefore, the polymkeric substance that shape is arranged can be a particle form, and for example powder or pellet or section can be moulded parts, extruded profile, fiber, weave or non woven fabric, film, foam materials or the like.
Term as used herein " sulfonation " is meant organic compound is converted into and contains building stone C-SO 2-O contains N-SO under some situation 2The sulfonic acid of-O or the method for sulfonate.The sulfonation reaction that the polymkeric substance of shape is arranged for example can be used for changing the surface properties of this type of tangible shaped polymer.For example, the surface properties of this type of material is hydrophobic through making behind the oversulfonate that surface after the modification becomes, thus more or less freely thereon application of adhesive, and/or become and can print.
Term as used herein " non woven fabric " is meant the cloth that a kind of its structure system is made of many single fibers or long filament, and these single fibers are to intersect to spread to be put, yet but is to put according to a kind of repetitive mode shop that can not recognize.
Term as used herein " spun-bonded fibre " is meant makes a fibrid like this: with molten thermoplastic many tiny from spinning jet, be generally to extrude in the circular pore and be the filament shape, this diameter of extruding silk is attenuated rapidly, for example by the method drawing-down described in the following document: people's such as Appel United States Patent (USP) 4,340,563 and people's such as Dorschner United States Patent (USP) 3,692,618, people's such as Matsuki United States Patent (USP) 3,802,817, the United States Patent (USP) 3,338 of Kinney, 992 and 3,341,394, the United States Patent (USP) 3,502 of Levy, 763 and 3,909,009 and people's such as Dobo United States Patent (USP) 3,542,615, all these all receive the reference of making this paper.
Term as used herein " meltblown fibers " is meant a fibrid of making like this: with molten thermoplastic from many tiny, be generally in the circular mouth mould pore and be expressed at a high speed, be generally in gas (for example air) stream of heating, thereby this air-flow attenuates the filament of molten thermoplastic and makes its reduced with fused silk thread or filament form.Subsequently, this meltblown fibers is carried secretly and is deposited on by this high velocity air and collects on the surface, and the result forms the cloth that is made of the random meltblown fibers that is scattered.Meltblowing method for example can be seen in, people's such as people's such as the United States Patent (USP) 3,849,241 of Buntin, Meitner United States Patent (USP) 4,307,143 and Wisneski United States Patent (USP) 4,663,220, and all these all receive the reference of making this paper.
Method of sulfonating of the present invention can be eliminated must possess or store a large amount of needs such as materials such as sulphur trioxide, the vitriol oil, oleum or chlorsulfonic acids for causing traditional sulfonation process in the past.Method of the present invention also can be eliminated the distinctive color browning phenomenon that many traditional method of sulfonating produce.
In one embodiment of the present invention, the polymkeric substance method of sulfonating comprises: allow sulfurous gas and oxygen source be exposed to the energy that can produce free radical, allow polymkeric substance contact with the product of previous step then.It is desirable for sulfurous gas and oxygen source and be exposed to energy and the polymkeric substance and the contacted step of this product that can produce free radical, all in reduced pressure atmosphere, carry out.The energy source that can produce free radical can be ultraviolet ray, gamma-rays, electron beam, rare gas radio frequency (rf) plasma body or corona discharge.Oxygen source can comprise oxygen, gas or the combination of the two.
In another embodiment, the polymkeric substance method of sulfonating comprises: allow polymkeric substance contact with oxygen source with sulfurous gas, allow the polymkeric substance after contacting be exposed to the energy that can produce free radical then.In this embodiment, can allow polymkeric substance contact, perhaps allow polymkeric substance contact with oxygen source with sulfurous gas respectively with the mixture of sulfurous gas and oxygen source.When polymkeric substance contacts with sulfurous gas and oxygen source respectively, can allow polymkeric substance contact with sulfurous gas earlier, and then contact with oxygen source.It is desirable for this contact and exposing step all in decompression, promptly in usually less than 1 atmospheric environment, carry out.This energy source that can produce free radical is ultraviolet ray, gamma-rays, electron beam, rare gas radio-frequency plasma or corona discharge also.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
Another embodiment of the present invention provides the polymkeric substance of the giving shape method with water-wet behavior.This method comprises: allow sulfurous gas and oxygen source be exposed to the energy that can produce free radical, allow polymkeric substance contact with the product of previous step then.It is desirable for this contact and exposing step all carries out in reduced pressure atmosphere.The energy source that can produce free radical can be ultraviolet ray, gamma-rays, electron beam, rare gas radio-frequency plasma or corona discharge.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
The polymkeric substance of giving shape comprises with the another kind of method of water-wet behavior: allow polymkeric substance contact with oxygen source with sulfurous gas, allow the polymkeric substance after the contact be exposed to the energy that can produce free radical then.It is desirable for this contact and exposing step all carries out in reduced pressure atmosphere.The energy source that can produce free radical is ultraviolet ray, gamma-rays, electron beam, rare gas radio-frequency plasma or corona discharge also.Oxygen source can comprise oxygen, oxygen supply gas or the combination of the two.
In above-mentioned all embodiments, the sulfonation effect is also insensitive to the concentration of sulfurous gas and oxygen, as long as these concentration are enough to give sulfonation degree and/or the water-wet behavior of polymkeric substance to require.Generally speaking, the concentration of sulfurous gas and oxygen is no matter surpass oxygen (O at the content of sulfurous gas 2) under the situation of content or at sulfurous gas and O 2Content meet under the situation of stoichiometric equation, all be enough.Any existence of all wishing to avoid excess of oxygen in the both of these case, promptly oxygen level all must not be above the quantity greater than stoichiometric equation in the reaction atmosphere of sulfonation reaction.
In addition, reaction atmosphere can be anhydrous, and perhaps reaction atmosphere can be substantially or be relatively not moisture.Under latter event, a spot of residual water-content can be by the generation of sulphur trioxide between the reaction period and is removed.Sulphur trioxide and water reaction generate sulfuric acid.The sulfurous gas and the oxygen that have had content to be enough to make the reaction atmosphere dehydration and to make polymeric matrix generation sulfonation reaction in reaction atmosphere, the existence of residual water just can not have influence on the result of sulfonation reaction.
Be used to implement the SO of the inventive method 2With O 2Ratio can recently represent with mole.Be used to implement the SO of method of sulfonating of the present invention 2With O 2Minimum mol ratio be 2: 1 (promptly equaling the ratio of stoichiometric equation just).It is desirable for this mol ratio and can be expressed as integer.And, work as SO 2With O 2Mol ratio be 2: 1 o'clock, sulfonation reaction can successfully be produced substantially non-yellowing or non-discoloring sulfonated polymer.It is desirable for SO 2With O 2Molar ratio range at 2: 1～5: 1.
In addition, can use oxygen supply gas instead SO 2With O 2O in the mixing 2All or part of of requirement.For example nitrous oxide as an example of oxygen supply gas, just can be used for substituting O in the sulfonation process 2All or part of of requirement.Other oxygen supply gases can comprise, the dioxide of nitrogen peroxide and halogen for example is as dioxide peroxide.It is to be further understood that and also can use one or more oxygen supply gas, no matter also whether use oxygen in addition, as long as SO 2Meet the top SO that is explained with total stoichiometric ratio of remaining oxygen and/or oxygen supply gas 2With O 2Mol ratio get final product.
In method of sulfonating of the present invention, can also use rare gas element.In a kind of embodiment of low-pressure vapor phase method of sulfonating, rare gas element can with SO 2And O 2And/or oxygen supply gas mixes.Alternatively, rare gas element can be before sulfonation reaction begins, and is used to rinse out reaction atmosphere and/or wishes the gas that exists such as little in the based article of porous or fibrous reticulum, as air.Under the situation that adopts inert gas purge reaction atmosphere and/or goods, the pressure of reaction atmosphere can be lower than a normal atmosphere (decompression) or be equal to or higher than a normal atmosphere.The example of rare gas element comprises nitrogen, argon gas, helium and krypton gas.In the middle of these rare gas elementes, argon gas is because itself nucleidic mass and density can be got rid of oxygen.
In another embodiment, use argon gas that sulfonation process is carried out continuously.In this case, the cleaning by argon gas stream is able to the air of wherein being carried secretly is driven away such as fibroreticulate goods.Then, not aeriferous substantially fibrous reticulum can be by containing SO 2And O 2The ultraviolet chamber of (or other oxygen sources) and argon gas is so that accept radiation, thus the generation sulfonation.
SO 2And O 2The most handy molar fraction of content represent.The restriction of doing like this to have general suitability and not being subjected to reaction atmosphere volume size.Like this, polymkeric substance respectively with SO 2And O 2Under the situation of contact, all molar fraction scopes with the gas that the sulfurous gas form exists are about 0.83～about 0.2.Specifically, polymkeric substance respectively with SO 2And O 2Under the situation of contact, the molar fraction of the gas that all exist with the sulfurous gas form is about 0.83, wishes for about 0.8, more wishes to wish to be 0.67 most for about 0.75.Correspondingly, the molar fraction scope of oxygen is about 0.17～about 0.33.Specifically, it is about 0.17 that the molar fraction of oxygen can be, and hope is 0.2, more wishes to be 0.25, wishes to be 0.33 most.Using different oxidizing gases to replace under the situation of oxygen, the molar fraction of this gas will be according to causing generating SO 3Chemical equation, come to determine by calculating.
Employed polymkeric substance wishes to have the polymkeric substance of shape when enforcement is of the present invention, more wishes it is the cloth of being made by polymer fiber.This kind polymkeric substance cloth can be woven or non-woven.Non woven fabric can adopt diversified method to make, and includes but not limited to air web method, wet lapping method, hydroentanglement processes, spun-bond process, meltblown, staple card and bonding and solution spinning.The available diversified polymeric material of fiber itself includes but not limited to the multipolymer of polyester, polyolefine, nylon and these materials.Fiber can be short relatively, and the length of staple fibre typically says less than 3 inches, or long, comparatively successive fiber, the typically the sort of fiber of for example producing with spun-bond process.Yet should be pointed out that also can use except that weave or non woven fabric the polymkeric substance that shape is arranged.These type of other have the example of the polymkeric substance of shape to comprise, film, foams/film laminates and their combination cooperate or mismatch to use and weave or non woven fabric all can.
And these clothes can be made up of single or multiple lift.Under the multiwalled situation, these layers are and intersect overlapping or face-to-face relation and place, and all or part of of these layers can be bonded together with adjacent layer.The example of this class non woven fabric of being made by this fibrid is by this registration transferee, the polypropylene non woven fabric that Kimberly-Clark company is produced.
For showing characteristic of the present invention, provide following example now.
Background
Quartz reactor shown in Fig. 1 10 is used to the sample described in the sulfonation example 1～5.Quartz reactor 10 is to adopt the optical grade fused quartz product of technical glass Products Co., Ltd (Ohio) to make.Quartz reactor 10 comprises reactor shell 12, and it comprises separable top and bottom again, is respectively 14,16, so that it is inner and from wherein taking out selectively sample to be put into reactor shell 12.Top 14 comprises the vacuum interface 18 that passes through valve 22 and be connected to vacuum source 20, the gas interface 24 that process valve 28 is connected to gas source 26 again, and interface 30, it is connected to baroceptor 32 by valve 34, the electric capacity weather gauge of making by Leybold Inficon company (New York) for example, model C M100.
Surface analysis
All ESCA (electron spectroscopy for chemical analysis) data all are to measure with the M-Probe ESCA spectrometer of Surface Science instrument company.It is to finish by adopting monochromatic aluminium X ray to excite to 800 microns areas on each sample that power spectrum is measured.The charged difference of sample adopts low-yield (1 electron-volt) stream of electrons from electronics overflow rifle to compensate.
Wetted surface tension force
Wetted surface tension force system adopts Pillar technology company, and (model STT 11-1 estimates for Hartland, WI) the wetting test pack of Sheng Chaning.Wetted surface tension force is got work can be by the spontaneous fluidic surface tension value of going in the fiber non woven fabric matrix that absorbs.This wetting tension instrument meets ASTM (ASTM (American society for testing materials)) standard D2578-67.
Contact angle
Contact angle determination adopts Rame-Hart 100-06 NRL type goniometer to carry out.Contact angle is according to determining with the tangent straight line in contacted fluid drop edge, bottom thing surface.The numerical value of contact angle is to calculate according at least 3 observed data is averaged.Each drips and draws a pair of observed data.
Example 1
The sulfonation of polypropylene melt-blown material
Polypropylene melt-blown (PP MB) material of 0.5 ounce per square yard (osy) is put into quartz reactor shown in Figure 1 10, allow sample holder drop in the bottom 16, through vacuum interface 18 reactor shell 12 is evacuated to stagnation pressure and is lower than 1 * 10 -3Mmhg.After 5 minutes, via gas interface 24 usefulness rare gas elementes (nitrogen or argon gas) with the reactor shell 12 anti-pressure that are charged to 760 mmhg.Then, once more reactor shell 12 is evacuated.Implementing the operational cycle of counter filling-vacuumize repeatedly for 3 times, is 1 * 10 and finally be evacuated to stagnation pressure with reactor shell 12 -3The state of mmhg is as end.After finally vacuumizing, in reactor shell 12, introduce sulfurous gas (SO via gas interface 24 2) and oxygen (O 2) mixture, reach 200 mmhg until stagnation pressure.SO in the gaseous mixture 2With O 2The ratio of dividing potential drop be 2: 1, then, reactor is placed in the annular uv reactor (Rayonet photochemical reactor, southern New England ultraviolet company) that 16 low pressure mercury lamps are housed.The primary radiation wavelength of every lamp is 254 nanometers.Whole total output of 16 lamps by measuring at the reaction chamber central point, is 6 milliwatts/square centimeter (mW/cm 2).
The time of ultraviolet irradiation (reaction times) of each PP MB sample does not wait from 5 minutes by 15 minutes.After the uv irradiating, clean through 24 pairs of reactors of gas interface, to remove remaining SO with rare gas element (nitrogen or argon gas) 2Or SO 3
5 minute reaction times.PP MB material is a white, is that the test aqueous solution of 56 dynes per centimeter is wettable to surface tension.PP MB contrast sample is that the test aqueous solution of 35 dynes per centimeter is wettable to surface tension.Adopt ESCA that the surface analysis that this sulfonation melts and sprays PP is demonstrated following surface atom composition: 88.3% (atom) carbon, 9.2% (atom) oxygen and 2.5% (atom) sulphur.
10 minute reaction times.PP MB material is a white, and the test aqueous solution (promptly being equivalent to water) that to surface tension is 72 dynes per centimeter is for wettable.Adopt ESCA that the surface analysis of this sulfonation melt-blown material is demonstrated following surface atom composition: 88.5% (atom) carbon, 9.2% (atom) oxygen and 2.3% (atom) sulphur.
15 minute reaction times.PP MB material is extremely light brown, and the test aqueous solution (promptly being equivalent to water) that to surface tension is 72 dynes per centimeter is for wettable.Adopt ESCA that the surface analysis of this sulfonation fusion spray cloth is demonstrated following surface atom composition: 84.9% (atom) carbon, 12.1% (atom) oxygen and 3.0% (atom) sulphur.
Every kind of resulting material surface character of reaction times, comparing with contrast sample fusion-jetting polypropylene all has remarkable change.The ESCA data that obtain from per sample (p.s.) all provide the evidence of having introduced element sulphur on the respective material surface.These sulphur exist with sulphonic form.This shows that the carbon that generates in the sulfonation process-sulphur is in conjunction with having caused R-SO 3The generation of H group.
Example 2
The sulfonation of polyethylene melt-blown material
The experimental arrangement that is used for sulfonated polyethylene melt-blown material (PE MB) is identical with the content that example 1 is summarized.In this example, the PE MB sample with 6osy is placed on SO 2/ O 2Irradiation is 5 minutes in the atmosphere.
After sulfonation, the outward appearance of PE MB material is a white.This material is that the test aqueous solution (promptly being equivalent to water) of 72 dynes per centimeter is for wettable to surface tension.By contrast, the contrast PE MB sample of unsulfonated is wettable to the testing liquid of 36 dynes per centimeter only.Adopt ESCA that the surface analysis of this PE MB is demonstrated following surface atom composition: 95.4% (atom) carbon, 3.5% (atom) oxygen and 1.1% (atom) sulphur.Occurring this fact of sulphur on this surface shows that it has been introduced in the surface of this material and has gone.This sulphur exists with sulphonic form.
Example 3
Cellulosic sulfonation
Adopt with example 1 in the identical experimental arrangement of content summarized.Cellulose matrix is Whatman 1 a type filter paper.In this example, the Mierocrystalline cellulose sample is at SO 2/ O 2Accept 10 minutes irradiation in the atmosphere.
After the sulfonation, cellulose matrix is a white.Relatively fail to be disclosed in and have any difference in the cellulose matrix what the forward and backward wetted surface tension force of sulfonation carried out.The sulfonated Mierocrystalline cellulose has smell like the slight sulphur.Through washing in deionized water and after 80 ℃ of dryings, this smell has been removed effectively.
The surface composition (ESCA) of unsulfonated Mierocrystalline cellulose contrast sample, sulfonated cellulose and the sulfonated cellulose through washing is stated from table 1 in the lump.
Table 1
The cellulose surface atom is formed
Atom is formed percentage ratio (% (atom)) sample carbon oxygen sulphur fluorine unsulfonated Mierocrystalline cellulose contrast sample 59.0 40.2 0.0 0.8 sulfonation samples 59.2 38.2 0.9 1.8 sulfonated washing sample 57.2 39.4 1.2 2.2
The esca analysis of various Mierocrystalline cellulose samples clearly illustrates at cellulose surface has introduced element sulphur.These sulphur seemingly exist with sulphonic form.The existence of fluorine is attributable to the fluorine chemistry additive that exists in the Whatman filter paper, or owing to exists due to the fluorine chemistry composition at the high vacuum fat that is used for sealing the quartz reactor tube (see figure 1).
Example 4
The sulfonation of pet fiber
The experimental arrangement that is used for sulfonation polyethylene terephthalate (PET) fiber is identical with the content that example 1 is summarized.The PET fiber is placed on as example 1 described SO 2/ O 2Irradiation is 10 minutes in the atmosphere.
Sulfonated PET fiber is a white.This sulfonation PET fiber is that the test aqueous solution (promptly being equivalent to water) of 72 dynes per centimeter is for wettable to surface tension.By contrast, the contrast PET fiber of unsulfonated is wettable to the aqueous solution of 56 dynes per centimeter only, and the contact angle of observing water is greater than 90 °.Water contact angle on the sulfonated fiber is owing to drop is failed to measure by spontaneous absorption.Sulfonation PET fiber is washed and also do not changed its wetting properties 80 ℃ of dryings.
The surface composition of this PET fiber (ESCA) is stated from table 2.
Table 2
Pet sheet face atom is formed
Atom is formed 66.0 28.2 2.5 3.3 washings of percentage ratio (% (atom)) sample carbon oxygen sulphur fluorine PET contrast fiber 75.2 24.8 0.0 0.0 sulfonation PET fibers, sulfonation PET fiber 70.2 26.8 1.5 1.6
Esca analysis clearly illustrates that at the PET fiber surface has introduced element sulphur.This sulphur exists with sulphonic form.The fluorine that exists on the sulfonation fiber of sulfonation and washing is by due to the high vacuum fat that is used for the sealed silica envelope reactor.
Example 5
The sulfonation of polystyrene
The experimental arrangement that is used for sulfonated polystyrene (PS) is identical with the content of example 1 general introduction.The PS film is at SO 2/ O 2Accept 10 minutes irradiation in the atmosphere.
Compare the obvious flavescence of sulfonated polystyrene film with the contrast sample of unsulfonated.Water contact angle on the sulfonation PS film is actually 0 °, and the water droplet self defocusing is distributed on the film.Water contact angle on unsulfonated PS film is 92 °.After washing, the water-wettable of sulfonation PS film does not change.
The surface composition (ESCA) of sulfonation PS film is stated from table 3.
Table 3
The PS surface atom is formed
Atom is formed 66.5 22.2 7.6 3.7 washings of percentage ratio (% (atom)) sample carbon oxygen sulphur fluorine PS contrast film 95.7 2.6a 0.0 0.0 sulfonation PS films, sulfonation PS film 69.0 20.6 7.8 2.6
a-also detect 1.12% (atom) silicon and 0.6% (atom) chlorine.
By desirable situation, the surface composition of contrast PS film should contain the carbon of about 100% (atom).Existence at the viewed silicon in contrast sample surface, chlorine and oxygen element is what brought by the operation to film sample.Significantly improving of the atomic percentage conc of oxygen and sulphur is the remarkable evidence that sulfonation reaction has changed the PS surface greatly in the sulfonation PS film.Sulphur is that the form with sulfonic acid group exists.Equally, fluorine also is to be caused by the pollution of the high vacuum fat that is used for quartz tube reactor to the surface.
Though with regard to specific embodiments of the present invention the present invention is described in detail, know, those skilled in the art after having understood above content, can be easy to expect these embodiments allly substitute, conversion and equivalence.

Claims (20)

1. the method for sulfonating of a polymkeric substance, it comprises:
The energy that allows sulfurous gas and oxygen source be exposed to produce free radical is to generate a kind of product; And
Allow polymkeric substance contact with the product of previous step.
2. the process of claim 1 wherein that contact procedure carries out in reduced pressure atmosphere.
3. the process of claim 1 wherein that exposing step carries out in anhydrous atmosphere.
4. the process of claim 1 wherein that oxygen source comprises oxygen, oxygen supply gas or the combination of the two.
5. the process of claim 1 wherein that the energy that can produce free radical is ultraviolet ray.
6. the method for claim 5, wherein ultraviolet predominant wavelength is 254 nanometers.
7. the method for sulfonating of a polymkeric substance, it comprises:
Allow polymkeric substance contact with sulfurous gas and oxygen source to generate a kind of product; And
Allow the product of previous step be exposed to the energy that can produce free radical.
8. the method for claim 7, wherein contact procedure is carried out in reduced pressure atmosphere.
9. the method for claim 7, wherein exposing step is carried out in anhydrous atmosphere.
10. the method for claim 7, wherein oxygen source comprises oxygen, oxygen supply gas or the combination of the two.
11. the method for claim 7, the energy that wherein can produce free radical are ultraviolet rays.
12. the method for claim 11, its middle-ultraviolet lamp has the wavelength of 254 nanometers.
13. the method for claim 7, wherein sulfurous gas and oxygen are a kind of gaseous mixtures.
14. the method for claim 7, wherein exposing step is carried out in reduced pressure atmosphere.
15. the product of the method for claim 1.
16. the product of the method for claim 7.
17. give the method for the polymkeric substance of shape with water-wet behavior for one kind, it comprises:
The energy that allows sulfurous gas and oxygen source be exposed to produce free radical is to generate a kind of product; And
Allow polymkeric substance contact with the product of back.
18. give the method for the polymkeric substance of shape with water-wet behavior for one kind, it comprises:
Allow polymkeric substance contact with sulfurous gas and oxygen source to generate a kind of product; And allow the product of previous step be exposed to the energy that can produce free radical.
19. the product of the method for claim 17.
20. the product of the method for claim 18.
CN96198332A 1995-09-28 1996-08-29 Sulfonated polymers and method of sulfonating polymers Pending CN1202187A (en)

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FI107932B (en) 1999-02-16 2001-10-31 Mikael Paronen Polymer membranes and process for their preparation
FI110947B (en) 1999-04-23 2003-04-30 Danisco Finland Oy Polymer resin and its preparation
AT408227B (en) * 1999-07-22 2001-09-25 Wolfgang Dr Kern METHOD FOR MODIFYING POLYMER SURFACES

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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
BE793952A (en) * 1972-01-14 1973-05-02 Nunc As PROCESS FOR IMPROVING THE SURFACE PROPERTIES OF AN ARTICLE SHAPED FROM A PLASTIC MATERIAL
JPS515868B2 (en) * 1972-08-03 1976-02-23
US4666452A (en) * 1986-03-12 1987-05-19 Kimberly-Clark Corporation Hydrophilic surface - modified polyolefin structures
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