WO1998032789A1 - Article poreux a groupement fonctionnel de surface et son procede de preparation - Google Patents

Article poreux a groupement fonctionnel de surface et son procede de preparation Download PDF

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Publication number
WO1998032789A1
WO1998032789A1 PCT/US1997/014269 US9714269W WO9832789A1 WO 1998032789 A1 WO1998032789 A1 WO 1998032789A1 US 9714269 W US9714269 W US 9714269W WO 9832789 A1 WO9832789 A1 WO 9832789A1
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Prior art keywords
article
porous article
porous
functionality
exterior
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PCT/US1997/014269
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English (en)
Inventor
Steven L. Koontz
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United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
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Priority claimed from US08/858,219 external-priority patent/US6022902A/en
Application filed by United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration filed Critical United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
Priority to AU40654/97A priority Critical patent/AU4065497A/en
Publication of WO1998032789A1 publication Critical patent/WO1998032789A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1692—Other shaped material, e.g. perforated or porous sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/544—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being organic
    • G01N33/545—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/041—Microporous
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/50—Conditioning of the sorbent material or stationary liquid
    • G01N30/52—Physical parameters
    • G01N2030/524—Physical parameters structural properties
    • G01N2030/528—Monolithic sorbent material

Definitions

  • the discharge used in the inventive process is a plasma discharge.
  • photons generated by the radical forming conditions, and particularly ultraviolet radiation do not contact the precursor porous article.
  • the surface-functionalized porous article having carbonyl and carboxylic acid groups may be reacted with a reducing agent, so that hydroxyl groups are the predominant functional group bonded to the polymers which form the surface of the article.
  • chemical agents that react with and cap (neutralize, eliminate) surface free radical sites and/or peroxides are contacted with the surface functionalized porous article.
  • Such chemical agents include ammonia, dimethyl sulfide and other gases known in the art to cap/react with/neutralize free radical or peroxides on a polymer surface.
  • analysis for surface functional groups introduced by the process described above shows that the same useful functional group concentration is present throughout the entire interstitial surface of the porous solid.
  • the exterior pore surfaces preferably have the same or essentially the same morphology and functional group concentration as the internal pore surfaces.
  • the internal and exterior pore surfaces of the porous articles of the invention show essentially the same morphology by SEM as the starting porous material for the process.
  • the exterior pore surfaces and internal pore surfaces contain little or no degradation from: 1) UV/VUV photochemical degradation, 2) ion and electron impact processes, 3) chemical etching.
  • Porous articles useful in, and formed according to the present invention are formed, in whole or part, of organic polymer, i.e., carbon and hydrogen containing polymers.
  • the porous article is formed entirely from organic polymer.
  • the porous article may be a composite of inorganic material and organic polymer.
  • a preferred composite article has a surface that is entirely formed of organic polymer, and more preferably has a bulk matrix that is predominately organic polymer.
  • Hydrophobic polymers include hydrocarbons, PTFE, polyacrylonitrile, polyetherimide, polysulfone, and polyethersulfone.
  • the repeating unit preferably contains more carbon atoms that non-carbon atoms (excluding hydrogen and halogen atoms).
  • polymers containing heteroatoms which may be used according to the present invention are well known in the art, and are listed in, e.g., The Polymer Handbook (supra).
  • the inventive process is generally applicable to all organic polymers.
  • the polymer from which the article is formed may have any molecular weight, molecular weight distribution, stereochemical configuration or conformation, degree of crosslinking, density, tensile strength, extent of entanglement, glass transition temperature (although this should be above room temperature, so that the article is a solid at room temperature), tacticity, melt viscosity and color, among other properties that characterize polymers.
  • the polymer has a relatively high molecular weight, on the order of 1,000,000 daltons or more (number average molecular weight).
  • the polymer has a relatively high molecular weight, there tends to be a greater degree of entanglement among the polymer chains. This greater degree of entanglement tends to inhibit the polymer chains from moving around within the article. Consequently, functionality which is initially introduced to the surface of a porous article will tend to remain at that surface for a longer period of time when the average molecular weight of the polymer chains is relatively high.
  • polyethylene is a preferred polymer from which the article is formed.
  • So-called ultra-high molecular weight polyethylene is a preferred polyethylene.
  • UHMWPE is described in, e.g., U.S. Patent No. 5,531,899.
  • Polyethylene is typically characterized in terms of its density, and both high density and low density polyethylene may be used to form the porous article.
  • the porous article may be macroporous, in which case the article has a pore size of about 20 microns to about 2000 microns, preferably about 20 to 500 microns.
  • a preferred porous article has an effective pore size of about 1 to about 50 microns.
  • Porosity may be determined according to ASTM D276-72, and pore size distribution may be determined according to ASTM F316-70.
  • the porosity of the article can also be characterized in terms of pore volume. Thus, the porosity may be defined as the pore volume divided by the total volume of the article. In percentage terms, porosity refers to the pore volume as defined above, multiplied by 100.
  • Porous articles may be made by methods which are well known in the art. The variety of techniques which are described in Resting, Robert E., Synthetic Polymeric Membranes, John Wiley & Sons, New York, 1985, pp. 237-309, which is hereby incorporated herein by reference, are exemplary.
  • the pores may be introduced by mechanical perforation, by the introduction of pore producing agents (e.g., porogens) during the matrix forming process, through various phase separation techniques, or other methods. Indeed, the manner in which the article is made porous is not especially important to the practice of the present invention. However, the properties of the porous material should be selected so that the article has the necessary porosity, strength, durability and other properties which render it suitable for the intended application.
  • the porous article is preferably self-supporting.
  • the porous article may have essentially any shape.
  • the article may be in the shape of a cube, block, sphere, tube, rod or cylinder, sheet, disc, membrane, film, monolith or the like.
  • Articles in the form of a block/cube or rod/cylinder are preferred for many applications, and may be obtained from Porex Technologies USA (Fairburn, GA).
  • a preferred article in the form of a film is porous polyethylene film, e.g., CELGARDTM K-878, which is commercially available from Celanese Corporation (Norristown, NJ).
  • Microporous polymeric films which may be treated according to the invention are described in, e.g., U.S. Patent Nos. 3,839,516; 3,801,404; 3,679,538; 3,558,764 and 3,426,754.
  • the invention provides a process wherein reactive gas-phase radicals and a porous article (hereinafter “the specimen") are present within a single reactor, such that the radicals contact the specimen and create functionality throughout the surface of the specimen.
  • the radicals are generated from a source gas, in a non-equilibrium, low pressure environment, and delivered to the specimen by at least one of convective and diffusional transport.
  • the radicals are generated from the source gas by exposing the source gas to so-called "radical forming conditions" as created by, for example, a radiofrequency (RF), microwave or direct current discharge (any of which will create a gas plasma discharge), laser sustained discharges, UV laser photolysis, high-powered UV/VUV lamp driven photolysis, high energy electron beams, and other high-intensity ionizing or radical forming radiation sources. While any of these radical forming conditions may be used to generate the reactive radicals, gas plasma discharge is a preferred technique.
  • RF radiofrequency
  • microwave or direct current discharge any of which will create a gas plasma discharge
  • laser sustained discharges any of which will create a gas plasma discharge
  • UV laser photolysis high-powered UV/VUV lamp driven photolysis
  • high energy electron beams high-intensity ionizing or radical forming radiation sources.
  • gas plasma discharge is a preferred technique.
  • the source gas according to the present invention comprises oxygen, ammonia, or a mixture of nitrogen and hydrogen.
  • oxygen and ammonia are not used simultaneously, and the mixture of nitrogen and hydrogen is not used with either oxygen or ammonia.
  • These source gases may be used in pure form (i.e., above about 95% purity) or in dilute forms, where suitable diluent gases include helium, argon and nitrogen.
  • Diluted source gases afford the advantage that reactive radicals that are generated from dilute oxygen, nitrogen or ammonia demonstrate fewer recombination events, thus providing for a longer-lasting and higher concentration of reactive radicals in the reactor.
  • the energy transferred from an excited metastable species formed from a diluent gas, e.g., Ar* can increase the yield of the reactive radical.
  • 10% oxygen in argon at a pressure of 2 Torr provides about the same ability to functionalize a porous specimen as does pure oxygen.
  • Argon is a preferred diluent gas because the metastable electronic excited state of argon promotes dissociation of molecular oxygen or ammonia by collisional energy transfer, and so promotes in-plasma dissociation kinetics.
  • dilute gases having about 10% concentration of oxygen or ammonia are preferred according to the invention.
  • the reactor of the invention converts the oxygen (O 2 ) to atomic oxygen radical (Oj).
  • the minimum concentration of atomic oxygen radical within the reactor is preferably at least 1 x 10 13 atoms/cc, as measured by N0 chemiluminescent titration (as described in, e.g., Kaufman, F., Progress in Reaction Kinetics, vol. 1, Pergamon Press, London, pp. 1-39, 1961).
  • hydroxyl radicals will also typically react with the specimen.
  • the minimum concentration of atomic hydrogen radical within the reactor is preferably at least 1 x 10 16 atoms/cc at a temperature of 298°C, as measured by NO chemiluminescent titration (as described in Kaufman 1961, supra) and calculated from the pressure rise seen on ignition of the plasma source. This minimum value is preferably maintained regardless of the working pressure.
  • the preferred reactor provides an environment which precludes, or at least substantially precludes, contact between the specimen and undesirable by-products.
  • the reactor allows the undesirable by-products to undergo natural decay prior to their contacting the specimen.
  • the preferred reactor and operation thereof provides that a specimen is exposed to an environment wherein the rate of decay of desired gas-phase atomic and molecular radicals is much less than the decay rate of undesirable by-products.
  • remote plasma and “downstream plasma” generally refer to an environment wherein the substrate being modified by the plasma is located such that the substrate is not exposed to plasma- derived species that can cause collateral damage to the substrate.
  • Remote or downstream plasma techniques described in the literature, which are directed, for example, to etching processes in the semiconductor industry, or otherwise modifying the surface of a substrate, may be used in the process of the present invention so long as they achieve little (less than 10% mass loss) or essentially no (less than 1% mass loss) collateral damage to the substrate while achieving complete functionalization of the surface of the porous article.
  • remote plasma techniques described in the literature typically separate the specimen being treated from direct contact with the glow discharge plasma, it is not always the case that the specimen is spared contact with light that is emitted from the glowing discharge.
  • photons emitted from the excited gas, and particularly UV radiation do not contact the porous article.
  • the apparatus 32 may also consist of an ASTEX S-250 microwave power supply in conjunction with an ASTEX DPC24 plasma head which creates a cavity wherein the plasma is formed.
  • the ASTEX components are available from Applied Science and Technology, Inc., Worburn, MA. Either of these configurations may be used with any source gas of the invention.
  • These power supplies are typically operated at (FCC- approved) 2.450 MHz, although the FCC also approves the use of 13 MHz band for industrial processing, and this could also be employed in the present invention.
  • sidearms 38 are shown in Figure 2.
  • the exhaust section 18 of the flow chamber 12 is in fluid communication with a vacuum pump 34 via line 36 positioned therebetween.
  • a catalytic atomic oxygen or atomic hydrogen probe (shown by feature 58) may be positioned within the discharge section 18, to thereby measure the concentration of the atomic oxygen exiting the flow chamber 12.
  • a suitable catalytic atomic oxygen probe may be prepared by wrapping fine silver wire or thin foil around a low thermal rated type J or K thermocouple probe (from, e.g., Omega Scientific).
  • a palladium probe may be used to measure hydrogen.
  • a capacitance monometer connection (shown by feature 56) may also, or alternatively, be connected to the discharge section 18 in order to measure the pressure within section 18.
  • the reactor 10 is constructed and operated so that no significant radial concentration gradients of reactive gas-phase radicals exist within the sidearms. This is achieved, in part, by positioning the specimens within sidearms so that they are not subject to the direct flow of the glow discharge plasma generated by the discharge generating apparatus. The specimens are thus positioned so as not to be in direct contact with the plasma and so that photons from the plasma cannot reach the specimen.
  • surface-functionalized porous articles may be prepared having pore volumes which are within 10% of the pore volume of the precursor porous article, and are preferably within 5% of the initial pore volume.
  • surface-functionalized porous articles may be prepared having pore volumes which are within 5% of the pore volume of the precursor porous article, and are preferably within 1% of the initial pore volume.
  • Remote plasma treatment according to the invention is achieved by proper selection of the reactor, including reactor dimensions and the materials from which the reactor is constructed, and proper selection of reactor operating conditions. These selections are not independent, and thus one selection must be made in view of the other. The following guidelines are useful in developing reaction conditions useful in the present invention.
  • the selections are made so that the diffusional relaxation time (a characteristic time for gas diffusion to eliminate gas radical concentration gradients) of the reactive radicals within the sidearms is much smaller than the characteristic decay time(s) of the gas-phase radicals as resulting from the sum of all surface and gas-phase loss processes.
  • diffusional relaxation and decay times will depend on the dimensions of the sidearms, the reactivity of the materials from which the sidearms were constructed, the reactivity of the specimen, the total working pressure within the reactor, as well as the temperature within the reactor.
  • the upper and lower limits on the working gas pressure are determined by the need to provide enough of the specific reactive gaseous radicals of interest to complete the desired surface chemistry on the specimen in a reasonably short length of time.
  • a reaction time of 1 minute or so, for a sample that is about 1 cm thick, is typical, although this time is highly dependent on the porosity of the specimen, and the average diameter of the pores. Highly porous samples, with small pore diameters, which characterizes many membranes, may require a reaction time on the order to 60 minutes or so. If the pressure is too high, for instance more than about 10 Torr (1300 Pa), then gaseous radical recombination reactions proceed at an undesirably fast rate, and rapidly deplete the reactive radical population.
  • the pressure is too low, say less than 0.1 Torr, then the number of gas phase radicals in the sidearm is too low to be practically useful.
  • a working gas pressure between about 0.1 and 10 Torr (roughly 10 to 1300 Pa) is thus practically useful, with gas pressures of about 0.5 to 5 Torr (roughly 50 to 500 Pa) being preferred regardless of the source gas.
  • An important factor limiting the use of higher pressures is the increasing heat capacity of the gases at higher pressures. It is known that plasma discharges at atmospheric pressure produce high enthalpy gas streams which may vaporize metals and destroy polymers via purely thermal processes. Accordingly, as the pressure increases inside a reactor according to the invention, the temperature of the flowing gases increases, rapidly approaching the thermal limits of the apparatus.
  • a working temperature of less than about 350 K is preferred, with a temperature range of about 250 K to about 325 K being more preferred, and a temperature range of about 275-310 K being still more preferred, when oxygen is the source gas.
  • the activation energy for sample decomposition is very much greater than the activation energy for the desired reaction. Accordingly, ammonia allows for a wider latitude in the selection of the working temperature because the rate of the desired reaction will almost always be much greater than the rate of the undesired decomposition reactions.
  • a working temperature of about 275 K to about 400 K is preferred when using ammonia as the source gas, with a working temperature of about 300 K to about 375 K being more preferred, and a working temperature of about 325 K to about 350 K being still more preferred. While temperatures higher than 400 K can be used with ammonia, very little increase in the desired reaction rate is observed compared with using 300 K, and thus for reasons of economy and safety, a lower temperature is preferred. At temperatures lower than about 275 K, the rate of specimen functionalization using ammonia becomes undesirably slow from a commercial point of view.
  • the convective flow time between the end of the plasma zone (feature 30 in Figure 1) and the beginning of the remote plasma treatment section (feature 32 in Figure 1) is preferably greater than 1 x 10 "4 seconds when the operating pressure is on the order of 1-2 Torr.
  • Adjustments to the total mass flow rate of the gas and the pumping speed of the vacuum system allows variation of both the total pressure within the reactor and the residence time of the radicals. In general, as the mass flow rate is increased for a constant pump speed, the convective flow time of the radicals increases and the pressure increases.
  • the sidearms 38 are constructed and operated so that no significant radial concentration gradients exist and a uniform dose of reactive gas-phase radical is thereby delivered to the specimen surface 49 which is held or secured transversely in the specimen holder 40.
  • the elimination of radial concentration gradients in the sidearms 38 is determined according to well known gaseous chemical kinetic analysis, by determining the relative magnitude of two characteristic relaxation times, T d i/f and T rcm , where T ⁇ t ff is the characteristic diffusional relaxation time for the sidearm 38 and T rcm is the time required for all reactive radicals in a sidearm to recombine.
  • Tdif R 2 /D wherein R is the radius of the sidearm 38 and D is the diffusion coefficient of the reactive radical (about 120 cm /s in air at 65 Pa when the reactive radical is atomic oxygen). Diffusion coefficient values for other gases and pressures may be obtained from the published literature, and/or calculated based on basic gas kinetic theory.
  • the chemical recombination (relaxation) time, T rcm is determined according to the equation:
  • r c is the fraction of reactive radicals which recombine or are otherwise lost upon striking the sidearm surface.
  • a description of radical recombination may be found in, e.g., Smith, W.V. "The surface recombination of H atoms and OH radicals” J. Chem. Phys. 11:110-124 (March, 1943) and Krongelb, S. et al. "Use of paramagnetic-resonance techniques in the study of atomic oxygen recombinations" J. Chem. Phys. 31(5):1196-1210 (November, 1954), both hereby incorporated herein by reference.
  • r c is the probability of the loss of a reactive radical from the population of reactive radicals, due to any first order or pseudo first order process.
  • first order and pseudo first order processes include an atom or radical striking the sidearm wall or specimen within the sidearm, as well as the recombination of reactive radicals.
  • the value of r c is about 3.2 x 10 " in the case of atomic oxygen, and 2 x 10 " for hydrogen, with a sidearm constructed from glass.
  • the parameter "v” is the mean thermal speed of the reactive radical (about 6.3 x 10 crn/s at 300 K for atomic oxygen, about 6.5 x 10 cm/s at 300 K for ammonia and about 25.2 x 10 cm/s at 300 K for hydrogen).
  • the sidearm reactor as described herein can be used to provide a predetermined, uniform dose rate of reactive radicals across a specimen surface.
  • the rate at which a specimen is functionalized depends on the surface flux of the reactive radicals. Dose rate can be estimated by analytical solution of the following partial differential equation describing the diffusional transport and first order or pseudo-first order reactive radical reaction processes:
  • k c is the rate constant for loss of reactive radical from the gas in the sidearm conduit from all first order processes
  • C is the concentration of the reactive radical
  • r is radial position of the specimen from the longitudinal axis of the sidearm conduit
  • z is an axial position (distance from the sidearm conduit entrance to the main gas chamber) with the boundary conditions:
  • a and B are constants determined by application of the boundary conditions as follows:
  • an exposure time on the order of seconds is typically sufficient to achieve essentially complete surface functionalization of a porous polyethylene disc (having, e.g., a thickness of 1/16 inch (1.6 mm) and a diameter of 0.75 inch (19 mm) and a nominal pore size on the order of 20 microns). Reducing the exposure time can provide a partially functionalized specimen.
  • degradation of such a disc using remote plasma treatment according to invention requires an exposure time on the order of hours (1-10) to achieve even a 5% mass loss.
  • functionalization of even the innermost interstitial regions of a porous specimen is much faster than degradation of the specimen, using remote plasma treatment according to the invention.
  • the porous article having surface functionality according to the present invention may be obtained by treating a porous article as described above with remotely-generated gas-phase radicals, also as described above.
  • the porous article has an exterior surface, a bulk matrix, and pores which extend from the exterior surface into the bulk matrix. The pores are surrounded by, and thus define, the pore surface.
  • the bulk matrix and surface of the (pre-treated) article is formed, at least in part and preferably in whole, of organic polymer, i.e., polymers having carbon and hydrogen atoms.
  • the gas-phase radicals reach the article and diffuse through the pores of the article, the exterior and interstitial surfaces become modified with functional groups such as amino, hydroxyl, carbonyl and carboxyl groups.
  • the diffusion of the gas-phase radicals from the exterior surface through the interstitial volume of the article proceeds in a distinct front.
  • the interstitial surfaces of the pores become functionalized by the introduction of amino, hydroxyl, etc. groups.
  • the pore surface retains its initial structure and functionality.
  • the reaction front is allowed to pass through the entirety of the article, the entire surface of the article gains functional groups.
  • the functionalized porous article according to the present invention may be characterized in several way.
  • scanning electron microscopy SEM
  • complete surface functionalization of a porous polymer article can be achieved with no appreciable change in the surface morphology, where no appreciable change means that no change in morphology is observed as determined by scanning electron microscopy at a magnification of 50X, and preferably less than 2000X.
  • SEM scanning electron microscopy
  • a relative measure of the amount of functionality that has been imparted to the surface of the porous article may be obtained by using any of x-ray photoelectron spectroscopy (XPS), infrared spectroscopy or chemical analysis.
  • XPS x-ray photoelectron spectroscopy
  • the functionalized article is useful because the initially introduced functionality (e.g., amino or hydroxyl groups) provides chemical handles which may be elaborated into biomolecules and other application-specific chemical groups. Accordingly, the chemical reactivity of the surface, after treatment according to the invention, is a very useful descriptor of the articles of the invention.
  • the amount of reactive surface functionality on a functionalized article according to the invention will depend on the conditions under which the chemical reactivity is measured. Some swelling of the porous article will occur if the article is placed into an appropriate solvent. The swollen surface will tend to be more reactive with chemical reagents because more of the initially introduced functional groups will be accessible to the chemical reagents.
  • the amount of bound deoxyribonucleoside is determined by absorbance at 498 nm after treatment with 70% aqueous perchloric acid, toluenesulfonic acid in acetonitrile, commercial deblock preparations, or the like, to release the DMT group from the support.
  • the surface- functionalized porous article having carbonyl and carboxylic acid groups may be reacted with a reducing agent, so that hydroxyl groups are the predominant functional group bonded to the polymers which form the surface of the article.
  • chemical agents that react with and cap (neutralize, eliminate) surface free radical sites and/or peroxides may be contacted with the surface functionalized porous article.
  • Such chemical agents include ammonia, dimethyl sulfide and other gases known in the art to cap/react with/neutralize free radical or peroxides on a polymer surface.
  • Hindered amine light stabilizers such as the IrganoxTM products (e.g., IrganoxTM 1076 and 1010) sold by Ciba-Geigy (Tarrytown, New York) and CyanoxTM 2246 from American Cyanamid (Wayne, NJ), as well as antioxidants such as 2,6-di-tert-butyl-4-methylphenol (BHT) and NonoxTM CI from Imperial Chemical Industries, Great Britain, may also be used to cap these surface radicals or peroxides.
  • IrganoxTM products e.g., IrganoxTM 1076 and 1010
  • CyanoxTM 2246 from American Cyanamid (Wayne, NJ)
  • antioxidants such as 2,6-di-tert-butyl-4-methylphenol (BHT) and NonoxTM CI from Imperial Chemical Industries, Great Britain, may also be used to cap these surface radicals or peroxides.
  • the functionalized porous article preferably has the following properties. It is inert in that it will not degrade upon contact with chemicals to which it is exposed when it is used as a solid-phase support for a synthesis procedure. It should be "sturdy" in that it maintains its integrity during use. Thus, the article should not break into pieces if, for example, it is placed into a solution with a rotating mechanical stirrer. Also, if placed into a tall column, the lower portion of the article should not become crushed and perhaps plug a screen that holds up the article (in instances where a screen is used to support the article). Other properties are also desired. The article should have a high surface area to volume ratio.
  • a polytetrafluoroethylene reinforced silicone membrane sold under the trade name SILON by Bio-Med Sciences, Inc. of Bethlehem, PA is uniformly treated with atomic oxygen in an atomic oxygen reactor having a specimen holding sidearm.
  • the membrane initially has a hydrophobic surface which after treatment acquires hydrophilic hydroxyl functionality as follows: Before After
  • Discs were similarly exposed to 5 x 10 14 //cm atomic oxygen atoms in the sidearm reactor for periods of time ranging from three seconds to ten minutes to characterize development of hydrophilicity as reflected in the amount of water uptake of the exposed samples. An amount of water sufficient to wet the hydrophilic portion was dropped onto the surface of each disc, and any excess was removed by pipet. The increase in mass due to water uptake was recorded, and the results based on an average of three specimens are presented in Table 3.
  • the reactor was essentially identical to the side-arm reactor described above.
  • the mass flow rate of the 10 percent ammonia in argon working gas was 132 standard cubic centimeters of gas per minute.
  • the plasma source was an air-cooled Evenson cell operated at 70 Watts of forward RF power and 3 Watts of reflected RF power at 2.45 GHz.
  • a second identical sample of the functionalized porous UHMWPE was reacted with: 1) the D-1557 probe (1 mg/ml in dry acetone, 1% pyridine) followed by, 2) thorough washing with dry acetone and, 3) reaction with a 20 wt% solution of a 4 generation PAMAM StarburstTM dendrimer (amino terminated) for 3 days.
  • the terminal amino groups on the dendrimer react with the sulfonic acid esters formed by reaction of D-1557 with the surface R-OH groups to produce D-NH-(dendrimer), thereby immobilizing the dendrimer on the surfaces of the oxygen FDRC porous polymer.
  • Subsequent analysis of the oxygen FDRC porous polymer using the FITC method of Example 3 above revealed that on the order of 0.2 micromoles per gram of primary amine function had been introduced by coupling the dendrimer to the surface.
  • Porex® X-4920 (Porex Technologies) was treated by remote plasma discharge using ammonia as the source gas, according to the general process described above, to create an amine-functionalized porous polymer according to the present invention.
  • a sample of 0.2 micron particle size poly(styrene-co-vinylamine) was coupled to the amine-functionalized Porex® X-4920 using trichloro-s-triazine as the coupling agent.
  • the resulting novel structure ' of matter and its inventive method of preparation are aspects of the present invention.
  • This novel structure provides a covalently-bound high-capacity supermolecular surface phase that may be used for biomolecule (e.g., DNA) synthesis or chromatography.
  • remote plasma discharge can be used to introduce functionality, e.g., amine groups, to polystyrene, without the concomitant formation of benzylamine groups (which is a common byproduct that occurs during prior art processes wherein Friedel-Crafts alkylation provides chloromethylation of the aromatic rings, and those chloromethyl groups are reacted to form aminomethyl groups)
  • functionality e.g., amine groups
  • benzylamine groups which is a common byproduct that occurs during prior art processes wherein Friedel-Crafts alkylation provides chloromethylation of the aromatic rings, and those chloromethyl groups are reacted to form aminomethyl groups
  • the funtionalized polystyrene of this invention can be used in various applications including chromatography and DNA synthesis.
  • polystyrene beads Two hundred milligram samples of polystyrene beads (Pharmacia Biotech BA 5301, Batch 37, 29-5-97) were placed into each of two glass trays having a surface of about 4 inches by 6 inches. The polystyrene beads were distributed across the bottom of the glass trays, and then the trays were placed into a chamber where they were exposed to remote plasma according to the present invention. A source gas of 10%) ammonia / 90%) argon was used at a flow rate 685 seem. The pressure inside the reaction chamber before activating the plasma was 4.80 torr.
  • the plasma generator (ASTEX AX2000/DPC 25) was turned on to provide a radio frequency power at 2.4 GHz frequency of 100 Forward watts and 4 Reflected watts, and pressure inside the reactor increased by 0.33 torr to 5.13 torr.
  • the polystyrene beads were exposed to the amine radicals for 6 hours, followed by 20 minutes of contact with static source gas at 400 torr.
  • the treated beads contained on the order of 100 ⁇ mole amine groups/g of beads.
  • a second titration procedure found that the beads contained 250 ⁇ mole amine groups/g of beads, however this titration method did not consider the shift in pKa value due to the possible aromatic position of the NH groups.
  • the beads contained about 700 ⁇ mole amine groups/g of beads.
  • the present invention provides a composition comprising amine- functionalized polystyrene, with the proviso that no amine groups bonded to a primary carbon are present as part of the polystyrene structure.
  • Polystyrene refers to a grade of polystyrene from Corning-Costar (Corning, NY) which they recommend for use in the manufacture of cell and tissue culture plates disks, and which was molded at Johnson Space Center, without the aid of a mold release agent;
  • PEEK is 2 micron pore size PEEK frits from UPCHURCH SCIENTIFIC, Oak Harbor, WA (Part No. A-712-02, P/S No. 00065870);
  • PC is polycarbonate track etch membrane, 1.0 ⁇ m pore size, lot no. AH72AN110016 from Osmonics Inc.
  • Each of the 6 polymer samples identified above was rinsed thoroughly with iso-propanol followed by methanol, and then air dried for four hours under vacuum.
  • the samples were then treated by flowing discharge radical chemistry (FDRC) using 10% ammonia in argon as the source gas, a source gas flow rate of 398 seem, and a treatment time of four hours at 25 °C.
  • FDRC discharge radical chemistry
  • the samples were positioned on 4 inch by 6 inch glass sample trays during the treatment.
  • the pressure inside the reaction chamber before activating the plasma was 2.99 torr.
  • the plasma generator (ASTEX AX2000/DPC 25) was turned on to provide a radio frequency power at 2.4 GHz frequency of 100 Watts of forward power and 4 Watts of reflected power, and pressure inside the reactor increased by 0.23 torr to 3.22 torr. After the four hour FDRC treatment, the samples were exposed to 10% ammonia in argon under a static pressure of 400 torr for a period of 30 minutes.
  • EXAMPLE 8 GRAFT POLYMERIZATION Disks of Porex® X-4920, Porex Technologies USA (Fairburn, GA) made from ultra-high molecular weight polyethylene having 20 ⁇ m pore size, and a size of 3 /. inch diameter and 1/16 inch thickness were subjected to FDRC as disclosed herein, using oxygen as the source gas.
  • the flow rate of insulors breathing oxygen was 198 seem, the pressure was 1.89 torr, the treatment time was two hours at 25°C.
  • a plasma generator (ASTEX AX2000/DPC 25) was used to provide a radio frequency power at 2.4 GHz frequency of 100 Watts of forward power and 4 Watts of reflected power. After the two hours of FDRC treatment, the samples were exposed to ambient air for about 5 minutes, and then cut in half and weighed. These weights are reported as "Before" in Table 7.
  • the weighed disks were then placed into a thoroughly deoxygenated 5 wt% solution of acrylamide in water (which had been deoxygenated in an argon-purged glove box, using an argon purge), contained in 15 cc screw-cap polypropylene centrifuge tubes.
  • the reagents listed in Table 7 were then spiked into the indicated tubes.
  • "O 2 F.R. X-4920” means a sample of X-4920 treated by oxygen FRDC as described above.
  • the initiator spike was 50 ⁇ L of 10% w/v ammonium persulfate in water.
  • the catalyst spike was 10 ⁇ L of tetramethyleneethylenediamine (TEMED).
  • the Mohr's sulfate spike was 100 ⁇ L of 0.22 M Fe(SO 4 ) 2 '6H 2 0.
  • the copper sulfate spike was 100 ⁇ L of 0.056 M CuSO 4 .
  • the methylene blue spike was 100 ⁇ L of 0.08 M methylene blue.
  • the final volume in each tube was about 10 mL in all cases. Reagent stock solutions were all thoroughly deoxygenated by an argon purge. The various test solutions in the tubes were sealed (screw cap tightened and then encased in parafilm) and then placed in a 60°C ' waterbath overnight.
  • the invention provides new types of solid-phase supports for the separation and purification of organic and biochemicals by adsorptive, absorptive and chromatographic processes.
  • the present invention permits the realization of novel, useful and practical separation media which cannot be achieved using the methods of the prior art.
  • the invention also provides new types of solid phase supports for chemical syntheses.

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Abstract

Des articles organiques poreux ne présentant aucun groupement fonctionnel de surface peuvent être traités par décharge de plasma à distance pour ainsi introduire un groupement fonctionnel à la surface de l'article. Ce groupement fonctionnel est introduit à travers toute la surface de l'article, y compris la surface extérieure et les surfaces des pores. Cette fonctionnalisation entraîne peu ou pas de détérioration de l'article organique poreux. Des groupes amino-hydroxyle, carbonyle, et carboxyle peuvent être introduits dans l'article. Ainsi, un article poreux hydrophobe essentiellement inerte, constitué par exemple de polyéthylène, peut présenter une modification de surface telle que cette dernière devienne hydrophyle. La décharge de plasma à distance ne provoque pratiquement aucune modification des propriétés générales de l'article organique. Ce processus de décharge de plasma à distance est de préférence réalisé de sorte qu'aucun photon et notamment aucun rayonnement ultraviolet ne soit transmis à l'article poreux par la luminescence plasmatique. L'article fonctionnalisé en surface peut s'utiliser, par exemple, comme support solide lors de la synthèse organique ou de la purification chromatographique de produits organiques ou biochimiques.
PCT/US1997/014269 1997-01-27 1997-08-13 Article poreux a groupement fonctionnel de surface et son procede de preparation WO1998032789A1 (fr)

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US8247039B2 (en) 2005-06-02 2012-08-21 Institut “Jo{hacek over (z)}ef Stefan” Method and device for local functionalization of polymer materials
US20150369802A1 (en) * 2014-06-18 2015-12-24 GVS North America, Inc. Biomolecule Binding Composite Surfaces, Methods Of Making Such Surfaces, Devices Incorporating Such Surfaces, And Methods Of Using Such Surfaces In Biomolecule Binding Assays, And Devices Therefor
CN113797894A (zh) * 2021-10-08 2021-12-17 华中科技大学 负载型多孔炭材料及其制备方法与其在烟气脱砷的应用

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JPH02208333A (ja) * 1989-02-08 1990-08-17 Tonen Corp 親水性ポリオレフイン多孔膜及びその製造方法
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8247039B2 (en) 2005-06-02 2012-08-21 Institut “Jo{hacek over (z)}ef Stefan” Method and device for local functionalization of polymer materials
US20150369802A1 (en) * 2014-06-18 2015-12-24 GVS North America, Inc. Biomolecule Binding Composite Surfaces, Methods Of Making Such Surfaces, Devices Incorporating Such Surfaces, And Methods Of Using Such Surfaces In Biomolecule Binding Assays, And Devices Therefor
CN113797894A (zh) * 2021-10-08 2021-12-17 华中科技大学 负载型多孔炭材料及其制备方法与其在烟气脱砷的应用
CN113797894B (zh) * 2021-10-08 2023-02-14 华中科技大学 负载型多孔炭材料及其制备方法与其在烟气脱砷的应用

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