EP2943269A1 - Procédé de fabrication d'un article en matière plastique pourvu d'un revêtement greffé hydrophobe, et article en matière plastique - Google Patents

Procédé de fabrication d'un article en matière plastique pourvu d'un revêtement greffé hydrophobe, et article en matière plastique

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Publication number
EP2943269A1
EP2943269A1 EP13824312.6A EP13824312A EP2943269A1 EP 2943269 A1 EP2943269 A1 EP 2943269A1 EP 13824312 A EP13824312 A EP 13824312A EP 2943269 A1 EP2943269 A1 EP 2943269A1
Authority
EP
European Patent Office
Prior art keywords
substrate
solvent
initiator
reagent
membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13824312.6A
Other languages
German (de)
English (en)
Inventor
Heike Matuschewski
Uwe Schedler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PolyAn Gesellschaft zur Herstellung von Polymeren fur spezialle Anwendung und Analytik mbH
Original Assignee
PolyAn Gesellschaft zur Herstellung von Polymeren fur spezialle Anwendung und Analytik mbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PolyAn Gesellschaft zur Herstellung von Polymeren fur spezialle Anwendung und Analytik mbH filed Critical PolyAn Gesellschaft zur Herstellung von Polymeren fur spezialle Anwendung und Analytik mbH
Publication of EP2943269A1 publication Critical patent/EP2943269A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/366—Apparatus therefor
    • 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
    • B01D67/0093—Chemical modification
    • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • 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
    • C08J7/123—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/04—Hydrophobization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/38—Graft polymerization
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile

Definitions

  • the invention relates to a process for producing a plastic article comprising a polymeric substrate and a 3-dimensional, hydrophobic polymer structure covalently bonded to the substrate.
  • the invention further relates to a plastic article which can be produced by the process, which may in particular be a separating membrane.
  • surfaces of plastic articles are often not suitable for the intended use of the article or only partially suitable. For this reason, it is known to chemically or physically modify polymeric surfaces.
  • surfaces are often provided with coatings that are covalently bonded (via chemical bonds) or not covalently through physical interaction effects with the polymeric material of the article (substrate).
  • membrane separation membranes separation membranes
  • filtration membranes especially for ultra or nanofiltration
  • pervaporation membranes pervaporation membranes.
  • ultrafiltration membranes separate particles or macromolecular substances having particle diameters in the range from 0.01 to 0.1 ⁇ m, while in nanofiltration particles or molecules having diameters of from 0.001 to 0.01 ⁇ m (1 to 10 nm) are separated off.
  • the filtration membranes have corresponding pore diameters.
  • Pervaporation membranes separate two liquid media.
  • a liquid medium (mixture of several liquid components) is liberated from a minor component (eg, contaminant) which diffuses through the membrane and evaporates on the other side of the membrane.
  • a minor component eg, contaminant
  • Pervaporation membranes are virtually dense, as are nanofiltration membranes. The removal of water from organic solvents is a typical example of pervaporation.
  • the component which passes through the membrane is referred to as permeate in both filtration and pervaporation techniques, and the liquid medium remaining on the other side of the membrane is called a retentate.
  • the properties of a separation membrane must be matched to the particular separation problem. For example, to separate hydrophobic substances from a medium, hydrophobic membranes are usually required.
  • the membranes must be chemically stable in the particular environment. In particular, they must not be soluble in the media used, can swell untargeted, ie (larger amounts) liquids or solvents or gases absorb or dissolve, or react chemically with them. Also for this purpose surface modifications are often required.
  • DE 195 07 584 C2 describes a process for the surface modification of release membranes, in particular of composite membranes, which consists of a support membrane, for example of polyvinylidene fluoride, and an adhesive (not covalently) adhering coating of polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • EP 0 81 1 420 A discloses a process for applying a graft polymerization layer to a polymeric support membrane.
  • the support membrane is coated with a photoinitiator, which can generate radicals on the polymer surface by hydrogen abstraction after light excitation.
  • the membrane is placed in a solution of a monomer and subjected to UV exposure so that the monomer reacts covalently with the radicals generated on the polymer surface and polymerizes to form polymer chains bound to the membrane.
  • the invention is based on the object of proposing a process for the production of hydrophobic graft-coated plastic articles, in which the hydrophobic coating takes place with a high degree of grafting.
  • the articles thus produced, in particular separation membranes, should thus have a correspondingly high hydrophobicity.
  • the method according to the invention comprises the steps:
  • the grafting reaction in step (c) takes place with a relatively high degree of grafting, while not observing these guidelines no significant or very little grafting could be achieved.
  • the relative solubility / swellability of the substrate material in the first solvent on the one hand and the solvent-free one To be grafting reagent or the mixture of the grafting reagent and second solvent on the other hand is advantageous that when loading the substrate with the initiator in step (a) the substrate well swells in the first solvent, for which a certain (low) solubility or swellability of the substrate in this solvent is required.
  • the swelling of the substrate namely allows the penetration of the initiator into the swollen surface and thus its absorption even in near-surface deeper layers of the substrate.
  • the lower solubility / swelling of the substrate in the (solvent-free) grafting reagent or the mixture of grafting agent and the second solvent leads to a reduced swelling of the substrate surface in step (b).
  • the initiator is held on the substrate and sufficient initiator remains on the substrate surface to react with it to form a radical on the substrate.
  • the substrate is heavily swollen in step (b)
  • partial or complete washing out of the initiator from the substrate surface occurs because the solvent molecules penetrate into the polymer, cause it to swell and dissolve the initiator.
  • the initiator can thus be transported out of the substrate.
  • the solubility of the initiator in the first solvent is greater than in the grafting reagent or in the mixture of the second solvent and the grafting reagent.
  • This comparatively low solubility of the photoinitiator in the grafting reagent or in the mixture of second solvent and grafting reagent leads to a reduced washing out of the initiator from the substrate surface and thus to an improved degree of grafting.
  • the said solubility ratios are not observed, homopolymerization of the grafting reagent is obtained, rather than the desired covalent attachment to the substrate.
  • a prediction of the solubility of a first component in a second component can be made for example by means of the so-called Hansen parameters.
  • Each molecule is assigned three Hansen solubility parameters (dD, dP, dH), each given in MPa 0.5 .
  • DD is the intermolecular dispersion energy (van der Waals forces)
  • dP is the energy of intermolecular dipole forces
  • dH is the energy of intermolecular hydrogen bonds.
  • the values for dD, dP and dH of a component form a vector. The closer the vectors of two components are to one another, the greater the solubility of the components in one another.
  • the solubility can be estimated from the octanol-water partition coefficients (K 0 w or better logKow) or other parameters such as the dipole moment or E T values.
  • K 0 w or better logKow the octanol-water partition coefficients
  • E T values the dipole moment or E T values.
  • hydrophobic refers to the property of a material to repel water
  • the quantitative contact angle for the hydrophobicity or hydrophilicity of a material is the static contact angle of a drop of water on a flat surface of the material
  • materials having a contact angle of water at 25 ° C. of at least 75 ° are defined as being hydrophobic by definition and those having a contact angle of less than 75 ° are termed hydrophilic.
  • loading of the surface in steps (a) and (b) means any form of contacting the surface to be coated with the respective substance (initiator or graft reagent) Substance, coating the surface with the substance, spraying or coating the surface with the substance, etc. It is essential that a direct contact between the coating surface and the respective substance is made, so that both can interact with each other.
  • the grafting reagent is used without the addition of a solvent, i. applied in undissolved pure form on the substrate surface. Since most initiators are solids and, moreover, only relatively low surface-area concentrations of initiator are required, the initiator is used in the presence of the first solvent, in particular in the form of a solution.
  • the first solvent is at least largely removed, which in the present case means that the substrate in any case appears visually dry. In particular, the first solvent is removed to such an extent that the mass increase of the substrate caused by the solvent is at most 10%, in particular at most 5%, preferably at most 1%, based on the mass of the dry substrate.
  • the removal of the solvent leads to a further intensification of the contact of the initiator with the polymeric surface of the substrate and thus to a further increase of the generated radical density on the substrate.
  • the initiator used in step (a) of the process is suitable for generating radicals on the polymer of the substrate which form the "point of attachment" for the subsequent reaction of the grafting reagent, whereby the term “radical” is at least one "unpaired” free electron understood or a connection with such.
  • “Radicals” in the sense of the present invention include non-ionic radicals as well as ionic radicals (radical ions, ie radical cations and anions).
  • Initiators capable of forming a radical include carbonyl compounds, especially ketones, and especially ⁇ -aromatic ketones, e.g. Benzophenones, for example benzophenone dicarboxylic acid or methyl benzophenone; Fluorenones and ⁇ - and ß-naphthyl compounds and derivatives of the aforementioned compounds. Further examples of suitable radical-forming initiators are mentioned, for example, in EP 0 767 803 A. Although thermally activatable initiators can also be used in the context of the present invention, a photoinitiator which can be excited by light of a suitable wavelength is preferably used.
  • H-abstraction type photoinitiator which is suitable for abstracting hydrogen radicals from the substrate after light excitation.
  • radicals remain in the polymer material, which in turn react with the grafting reagent.
  • Suitable H-abstraction photoinitiators can be selected from the aforementioned substances, in particular from the group of ⁇ -aromatic ketones.
  • the advantage of H-abstraction photoinitiators is that they can react with polymer materials that have abstractable hydrogens, that is, with virtually all organic polymer materials.
  • the abstraction of hydrogen radicals is a particularly gentle initialization of a grafting reaction with few side reactions.
  • an aprotic solvent is preferably used as the second solvent in step (b), if present, to provide a reaction of the Avoid initiator with the solvent.
  • Polymer materials of the substrate to be coated that can be used in the present invention are not limited to specific polymers.
  • synthetic organic polymers are used, for example polyolefins, such as polyethylene, polypropylene, etc., polysulfones, polyamides, polyesters, polycarbonates, poly (meth) acrylates, polyacrylamides, polyacrylonitriles, polyvinylidene fluorides, or natural (optionally modified) organic polymers such as celluloses, amylose, agarose, as well as derivatives, copolymers or blends of said polymers.
  • polyolefins such as polyethylene, polypropylene, etc.
  • polysulfones such as polyethylene, polypropylene, etc.
  • polyamides such as polyamides, polyesters, polycarbonates, poly (meth) acrylates, polyacrylamides, polyacrylonitriles, polyvinylidene fluorides, or natural (optionally modified) organic polymers
  • natural (optionally modified) organic polymers such as celluloses, amylose, agarose, as well as derivatives, copolymers
  • polymeric grafting reagents which in particular have a weight average molecular weight of at least 400 g / mol, in particular of at least 800 g / mol, preferably of at least 2000 g / mol.
  • the molecular weight of the polymer should not exceed 50,000 g / mol, in particular 20,000 g / mol.
  • Hydrophobic grafting reagents with static contact angles of at least 75 ° are used in the process according to the invention.
  • a grafting reagent which may also comprise a mixture of more than one substance, is used which, as homopolymer, has a static contact angle of water of at least 90 ° measured at 25 ° C.
  • hydrophobic grafting reagents with a contact angle of at least 110 ° are used to achieve appropriate hydrophobicity of the surface.
  • contact angle of at least 110 ° are used to achieve appropriate hydrophobicity of the surface.
  • hydrophobic grafting reagents used with a contact angle of 160 ° maximum.
  • the process according to the invention is not restricted to certain grafting reagents and basically all polymeric or monomeric grafting reagents with corresponding hydrophobicities can be used.
  • polyolefins Poly (organo) siloxanes (silicones), for example polydimethoxysiloxane
  • Alkyl (meth) acrylates for example butyl acrylate
  • Aryl (meth) acrylates for example, phenyl acrylate, fluorinated alkyl (meth) acrylates, fluorinated aryl (meth) acrylates, or mixtures of these.
  • the monomeric or polymeric grafting reagent may have a reactive double bond, for example a (meth) acrylate group, a vinyl group or an allyl group. It suffices the presence of at least one such reactive double bond, in particular at a terminal (terminal) position of the polymer chain.
  • the grafting in the context of the invention is a so-called "grafting from” process in which the grafting reagent first reacts with the surface radicals of the substrate and then polymerizes to form a covalently bonded chain to the substrate with further grafting reagent molecules. If the grafting reagent is a low molecular weight monomer, a chain of the polymer formed from the monomer is formed on the substrate.
  • the graft reagent is a polymer
  • a main chain which has "grown” on the substrate and which is derived from the polymerized double bonds is typically formed with side chains of the polymer of the grafting reagent attached thereto to "method (also" grafting on ”) the initiator with the substrate surface and then with the usually polymeric grafting reagent, although covalently binds the substrate, but then no longer polymerized.
  • a crosslinker for crosslinking the polymer chains of the grafting reagent is loaded onto the surface of the substrate.
  • the use of a crosslinker increases the stability of the coating.
  • crosslinkers it is possible to use any substances which have at least two reactive polymerisable groups which can react with the grafting reagent.
  • the crosslinker is a substance of the same chemical basis as the grafting reagent, for example polydimethoxysiloxane having two terminal reactive groups, in particular double bonds, if the grafting reagent is polydimethoxysiloxane.
  • the crosslinker preferably has a molecular weight which is of the order of magnitude or in the range of the grafting reagent.
  • a (low molecular weight) monomeric grafting reagent preference is given to using a low molecular weight monomeric crosslinking agent and, in the case of polymeric grafting reagents, a polymeric crosslinking agent.
  • the molecular weights given for the polymeric grafting agent apply to the polymeric crosslinker.
  • the present invention is not limited to particular designs of substrates.
  • a filtration membrane having a pore structure is used as the polymeric substrate.
  • an ultrafiltration membrane having an average pore size in the range of 5 to 50 nm, preferably in the range of 10 to 30 nm, can be used.
  • a "dense" membrane is obtained by the graft coating according to the invention, which also "closes” the pores, which can be used as a nanofiltration membrane or pervaporation membrane.
  • Another aspect of the present invention relates to a plastic article comprising a polymeric substrate and a (3-dimensional) polymer structure covalently bound to the substrate, which can be produced by the process according to the invention.
  • the article is characterized by a contact angle of water on the layer at 25 ° C of at least 75 °, in particular of at least 90 ° and preferably of at least 100 °. In some embodiments, contact angles of at least 1 10 ° or more are achieved.
  • the plastic article is a filtration membrane, in particular a nanofiltration membrane or pervaporation membrane.
  • the plastic article according to the invention preferably has a grafting ungsgrad in the range of 0.25 to 10 mg graft layer per cm 2 substrate area, in particular of at least 1 mg / cm 2 substrate area.
  • the degree of grafting tends to be lower. Due to the grafting from mechanism described above, unlike the grafting to mechanism, the initiator is no longer present in the product of the invention.
  • a polyacrylonitrile (PAN) ultrafiltration membrane (manufacturer: GKSS, thickness: 200 ⁇ , average pore size: 10 nm) was coated on both sides with a solution of benzophenone (BP) in acetone (0.15 mol / l) by the membrane in the Benzophenone solution for 15 minutes. Subsequently, the membrane was removed from the solution and dried at room temperature.
  • PAN polyacrylonitrile
  • GKSS thickness: 200 ⁇ , average pore size: 10 nm
  • graft reagent solution For the graft reagent solution, cyclohexyl methacrylate (manufacturer: ABCR) (concentration: 200 g / l) was dissolved in toluene. The membrane loaded with the photoinitiator was placed on a glass plate and a thin layer of the graft reagent solution was applied to the membrane. The graft-coated membrane was left for 30-60 minutes. This was followed by UV irradiation with a radiation dose of 80 mJ / cm 2 .
  • ABCR cyclohexyl methacrylate
  • the irradiated membrane was extensively washed with isopropanol in several steps to remove non-covalently bound graft reagents and by-products to the membrane.
  • a polyacrylonitrile (PAN) ultrafiltration membrane (manufacturer: GKSS, thickness: 200 ⁇ , average pore size: 10 nm) was coated on both sides with a solution of benzophenone (BP) in acetone (0.15 mol / l) by the membrane in the Benzophenone solution for 15 minutes. Subsequently, the membrane was removed from the solution and dried at room temperature.
  • BP benzophenone
  • BP benzophenone
  • the membrane was removed from the solution and dried at room temperature.
  • cyclohexyl methacrylate (manufacturer ABCR) (concentration: 200 g / l) and monomethyl (PEG) methacrylate (manufacturer: Aldrich) (20 g / l) were dissolved in toluene.
  • the membrane loaded with the photoinitiator was placed on a glass plate and a thin layer of the graft reagent mixture was applied to the membrane. The graft-
  • the irradiated membrane was extensively washed with isopropanol in several steps to remove non-covalently bound graft reagents and by-products to the membrane.
  • a polyacrylonitrile (PAN) ultrafiltration membrane (manufacturer: GKSS, thickness: 200 ⁇ , average pore size: 10 nm) was coated on both sides with a solution of benzophenone (BP) in acetone (0.05 mol / l) by the membrane in the Benzophenone solution was loaded for 15 minutes. Subsequently, the membrane was removed from the solution and dried at room temperature.
  • PAN polyacrylonitrile
  • a graft reagent mixture of octadecyl methacrylate (manufacturer: ABCR) and Darocur TPO (manufacturer: Ciba) (concentration 1%) was prepared without addition of solvent.
  • the membrane loaded with the photoinitiator was placed on a glass plate and a thin layer of the graft reagent mixture was applied to the membrane. The graft-coated membrane was left for 30-60 minutes.
  • the irradiated membrane was extensively washed with isopropanol in several steps to remove non-covalently bound graft reagents and by-products to the membrane.
  • a polyacrylonitrile (PAN) ultrafiltration membrane (manufacturer: GKSS, thickness: 200 ⁇ , average pore size: 10 nm) was coated on both sides with a solution of benzophenone (BP) in acetone (0.05 mol / l) by the membrane in the Benzophenone solution was loaded for 15 minutes. Subsequently, the membrane was removed from the solution and dried at room temperature.
  • PAN polyacrylonitrile
  • Perfluorodecyl methacrylate manufactured by Chempur
  • concentration: 50 g / l was dissolved in decanol for the grafting reagent solution.
  • the membrane loaded with the photoinitiator was placed on a glass plate and a thin layer of the graft reagent solution was applied to the membrane. wear. The graft-coated membrane was left for 30-60 minutes.
  • the irradiated membrane was extensively washed with isopropanol in several steps to remove non-covalently bound graft reagents and by-products to the membrane.
  • a polypropylene (PP) microfiltration membrane (manufacturer: Membrana, thickness: 170 ⁇ , average pore size: 0.2 ⁇ ) was coated on both sides with a solution of benzophenone (BP) in acetone (0.05 mol / l) by the membrane was placed in the benzophenone solution for 15 minutes. Subsequently, the membrane was removed from the solution and dried at room temperature.
  • PP polypropylene
  • BP benzophenone
  • the grafting reagent used was trifluoroethyl methacrylate (manufacturer: Chempur).
  • the membrane loaded with the photoinitiator was placed on a glass plate and a thin layer of the graft reagent solution was applied to the membrane. The graft-coated membrane was left for 30-60 minutes.
  • the irradiated membrane was extensively washed with isopropanol in several steps to remove non-covalently bound graft reagents and by-products to the membrane.
  • PAN polyacrylonitrile
  • GKSS polyacrylonitrile (manufacturer: GKSS, thickness: 200 ⁇ m, mean pore size: 10 nm) was coated on both sides with a solution of benzophenone (BP) in acetone (0.035-0.15 mol / l) was placed in the benzophenone solution for 15 minutes. Subsequently, the membrane was removed from the solution and dried at room temperature.
  • PAN polyacrylonitrile
  • GKSS thickness: 200 ⁇ m, mean pore size: 10 nm
  • a graft reagent mixture of polydimethylsiloxane monomethacryloxypropyl terminated (PDMS-MMA) (manufacturer: ABCR) and the crosslinker polydimethylsiloxane-methacryloxypropyl terminated (PDMS-DMA) (manufacturer: ABCR) was prepared without addition of solvent.
  • the membrane loaded with the photoinitiator was placed on a glass plate and a thin layer of the graft reagent mixture was applied to the membrane. The graft-coated membrane was left for 30-60 minutes.
  • the graft reagent mixture of PDMS-MMA and PDMS-DMA as a solution in toluene was applied to the membrane. The graft-coated membrane was allowed to stand at room temperature for 30-60 minutes.
  • the irradiated membrane was extensively washed with isopropanol in several steps to remove non-covalently bound graft reagents and by-products to the membrane.
  • the degree of grafting of the coated membranes was determined gravimetrically. The results are shown in Tables 1 and 2. Table 1 also shows the contact angles measured with water.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Transplantation (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un article en matière plastique, cet article comprenant un substrat polymère et une structure polymère hydrophobe tridimensionnelle liée de manière covalente au substrat. Ce procédé comprend l'étape consistant à (a) charger une surface d'un substrat polymère d'un amorceur thermiquement activable, ou pouvant être excité par une lumière, lequel, une fois excité, est adapté à produire des radicaux à la surface du substrat, par conséquent sur le polymère du substrat, l'amorceur étant adsorbé à partir d'un premier solvant à la surface du substrat. Le procédé comprend également l'étape consistant à (b) charger le substrat, sur lequel l'amorceur a été adsorbé et sensiblement exempt du premier solvant, d'au moins un réactif greffé hydrophobe polymère ou monomère polymérisable, lequel présente en tant qu'homopolymère un angle de contact statique, mesuré à 25°C, avec l'eau d'au moins 75° et lequel est adapté pour réagir avec les radicaux produits à la surface du substrat, entraînant ainsi la formation d'une liaison covalente. Le réactif greffé est utilisé sans solvant ou dans un second solvant organique, la solubilité et/ou le gonflement du substrat dans le premier solvant étant plus importants que dans le réactif greffé ou que dans le mélange constitué du second solvant et du réactif greffé. Le procédé comprend également l'étape consistant à (c) exciter l'amorceur par exposition de la surface du substrat chargée de l'amorceur et du réactif greffé, à une lumière d'une longueur d'onde adaptée, ou à activer l'amorceur par apport de chaleur, de telle manière que l'amorceur produit des radicaux à la surface du substrat et que le réactif greffé forme une structure polymère (tridimensionnelle) liée de manière covalente à la surface du substrat. L'invention concerne en outre un article en matière plastique pouvant être fabriqué selon le procédé, comprenant un substrat polymère et une structure polymère hydrophobe liée de manière covalente au substrat. L'article présente un angle de contact avec l'eau, sur la structure polymère liée de manière covalente, d'au moins 75°, en particulier d'au moins 90°, de préférence d'au moins 100°, de manière particulièrement préférée d'au moins 110°.
EP13824312.6A 2013-01-08 2013-12-17 Procédé de fabrication d'un article en matière plastique pourvu d'un revêtement greffé hydrophobe, et article en matière plastique Withdrawn EP2943269A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013200120.7A DE102013200120A1 (de) 2013-01-08 2013-01-08 Verfahren zur Herstellung eines Kunststoffartikels mit hydrophober Pfropfbeschichtungsowie Kunststoffartikel
PCT/EP2013/076846 WO2014108278A1 (fr) 2013-01-08 2013-12-17 Procédé de fabrication d'un article en matière plastique pourvu d'un revêtement greffé hydrophobe, et article en matière plastique

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EP2943269A1 true EP2943269A1 (fr) 2015-11-18

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US (1) US20150353698A1 (fr)
EP (1) EP2943269A1 (fr)
JP (1) JP2016507617A (fr)
CN (1) CN104902988A (fr)
CA (1) CA2897238A1 (fr)
DE (1) DE102013200120A1 (fr)
WO (1) WO2014108278A1 (fr)

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WO2019018334A1 (fr) * 2017-07-18 2019-01-24 University Of Maryland, College Park Structures multicouches dotées de couches distinctes et leur procédés de formation
CN112739450A (zh) * 2018-03-30 2021-04-30 海德奥克赛斯控股有限公司 不对称复合膜及其制备中使用的改性基材
US12083780B2 (en) 2018-03-30 2024-09-10 Hydroxsys Holdings Limited Asymmetric composite membranes and hydrophilicitized microporous sheets of polyolefin used in their preparation
JP7133166B2 (ja) * 2018-06-20 2022-09-08 国立大学法人大阪大学 光学材料の製造方法
JP7133165B2 (ja) * 2018-06-20 2022-09-08 国立大学法人大阪大学 材料改質用変性粒子の製造方法
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US20150353698A1 (en) 2015-12-10
WO2014108278A1 (fr) 2014-07-17
DE102013200120A1 (de) 2014-07-10
JP2016507617A (ja) 2016-03-10
CN104902988A (zh) 2015-09-09
CA2897238A1 (fr) 2014-07-17

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