WO1996006838A1 - Polymer membrane having osmotic properties - Google Patents

Polymer membrane having osmotic properties Download PDF

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Publication number
WO1996006838A1
WO1996006838A1 PCT/SE1995/000669 SE9500669W WO9606838A1 WO 1996006838 A1 WO1996006838 A1 WO 1996006838A1 SE 9500669 W SE9500669 W SE 9500669W WO 9606838 A1 WO9606838 A1 WO 9606838A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
base foil
amines
acid chloride
trifunctional acid
Prior art date
Application number
PCT/SE1995/000669
Other languages
English (en)
French (fr)
Inventor
Peter Henning Hagqvist
Osborn HÄRMESTAD
Original Assignee
Ab Electrolux
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 Ab Electrolux filed Critical Ab Electrolux
Publication of WO1996006838A1 publication Critical patent/WO1996006838A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/26—Sulfur atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a polymer membrane .having osmotic properties, and to a method for its manufacture. More specifically, the invention relates to a polymer membrane which includes a base foil on which there is formed a semipermeable outer layer of a specific polymer that includes one or more specific diamines. The invention also relates to novel specific diamines that are used when producing the semipermeable outer layer, and to the use of an inventive membrane in water purification processes using reverse osmosis.
  • the purification of water with the aid of reverse osmosis is a simple method which does not require the use of complicat ⁇ ed, space-consuming and expensive apparatus, as in the case of conventional water purification processes, and the reverse osmosis process has therefore been used widely in recent years.
  • the reverse osmosis method has already obtained wide use in individual dwellings that are located remote from conventional water purification plants, and the use of such methods and processes can be expected to find wide use in the developing countries in particular.
  • the pure water By applying a sufficiently high pressure to that side of the membrane on which the contaminated water is located, the pure water can be caused to be pressed through the membrane pores and out into the solution with a lower concentration of dissolved substances, while the dissolved substances remain on the contaminated side of the membrane and can be removed therefrom.
  • Reverse osmosis can also be referred to as a type of filtering process on a molecular scale.
  • the properties of the semipermeable membrane used are of decisive importance to the practical purification of water with the aid of reverse osmosis. It is necessary for the membrane to exhibit a sufficient chemical resistance to the substances that may be present in the water (e.g. chlorine), and also to have a sufficient mechanical strength to withstand the pressures applied, which are often relatively high and may reach about 10 MPa.
  • the requirements of high separation factors, high rates of flow and high mechanical strength are often contradictory.
  • the membrane In order to achieve a high rate of flow, the membrane must be as thin as possible, resulting in a greater risk that pinholes will form and therewith greatly reduce the separation factor, besides impairing the mechanical strength of the membrane.
  • a thin surface layer having semipermeable properties is of en mounted on a thicker plastic membrane having coarser pores, this membrane func ⁇ tioning as a carrier.
  • the composite membrane may possibly be mounted on a further carrier, such as a woven carrier or a wire net, in order to further enhance the mechanical strength.
  • EP-B1-0 015 149 describes the manufacture of a microporous membrane on which a semipermeable surface layer is applied. This patent specification also contains a large number of additional references to the state of the art.
  • the thin surface layer is formed on the surface of the membrane.
  • One method involves moulding a layer of the polymer used for the surface layer on the surface of the membrane from a solution of the polymer.
  • this results solely in a purely mechanical connection which has been found to be unsatisfactory with regard to adhesion strength.
  • Another method of forming the surface layer is to polymerize suitable monomers of the surface layer on the membrane so as to form a polymer layer, and then primarily a polyamide layer.
  • the primary achievement of this method is a polyamide which adheres to the membrane surface solely through addition forces, in other words a mechanical bond.
  • the method is performed in a liquid and it is necessary to subsequently leach out unreacted chemicals. This is unsuitable from an environmental aspect.
  • Another method of producing the surface layer involves supplying the monomers in a solvent together with a photo- initiator which is decomposed by UV-light and/or heat.
  • the polymerization reaction is initiated by exposing the mixture to UV-light or to heat, so that the initiator decomposes and forms free radicals which, in turn, initiate the polymeriza ⁇ tion process.
  • This method also requires non-reacted material to be subsequently washed out in a leaching bath.
  • the present invention removes the aforesaid drawbacks and provides a membrane having osmotic properties which fulfil the aforesaid requirements to a great degree.
  • a membrane which has osmotic properties and which includes a permeable base foil having formed on the surface thereof an outer layer having semipermeable properties.
  • the invention is character ⁇ ized in that the surface layer is comprised of an interphase polymerization product of a trifunctional acid halide and at least one of the amines having the formulae
  • the permeable base foil is comprised of gelled polysulfone or microcrackled polyole- fin, and then particularly polyethylene.
  • the base foil may optionally be mounted on a further carrier.
  • the trifunc ⁇ tional acid halide is an acid chloride and then particularly 1,3,5-trimesoyl chloride of the formula
  • trifunctional acid halides can also be used, however. Such compounds are known in the art or can be produced by methods known from the literature.
  • the amines having the aforesaid formulae I and II are novel compounds and are also objects of the invention. They can be produced by methods known from the literature.
  • the amine I can be produced by reacting 2,4- dinitrophenylsulfonyl chloride with morpholine, and thereaf ⁇ ter reducing the nitro groups in the resultant intermediate compound to amino groups.
  • the amine II can be produced by first reacting 2,4-dinitrophenylsulfonyl chloride with N- methylaniline and thereafter chlorosulfonating the resultant sulfone anilide with chlorosulfonic acid. The thus obtained sulfonyl chloride is reacted with morpholine, whereafter the nitro groups are reduced to amino groups.
  • the starting materials used are known compounds.
  • the membrane carrier material used is a base foil produced from a permeable plastic material. This base foil may, in turn, be applied to a further carrier, such as a woven material or net, in order to be able to withstand the often considerable pressure differences that prevail between the two sides of the membrane.
  • a base foil material that has been found particularly suitable in this regard is a polysulfone layer which has been given a particular pore structure by gelation in water.
  • Microcrackled polymer film is another suitable base foil material.
  • a microcrackled polymer film is characterized by having a large number of microscopic through-penetrating slits or cracks which give the film its requisite porosity.
  • the microcrackled base foil is preferably comprised of a polyolefin, such as polyethylene or polypropylene or a copolymer thereof.
  • a suitable base foil is a microcrackled polyethylene film retailed by PPG Industries in the U.S.A. under the trade name TESLIN ® .
  • Such films have earlier found use within the clothing and printing indus ⁇ tries, although they have not earlier been used for any purpose related to the present invention.
  • the polyethylene film will suitably have a thickness of 175 ⁇ m, although other thicknesses are conceivable and can be readily determined by the person skilled in this art with knowledge of those requirements associated with the use intended.
  • the semipermeable surface layer is produced on the base foil by interphase polymerization of a trifunctional acid halide, particularly 1,3,5-trimesoyl chloride, and at least one of the amines having the aforesaid formulae I and II.
  • a trifunctional acid halide particularly 1,3,5-trimesoyl chloride
  • the surface of the base foil is first brought into contact with at least one of the amines and thereafter with the trifunctional acid halide.
  • the two reaction components are normally added dissolved in an appropriate solvent.
  • the trifunctional acid halide is preferably dissolved in a liquid hydrocarbon, for instance hexane, or a perfluoro chlorohydrocarbon, for instance trifluorotrichloroethane.
  • a liquid hydrocarbon for instance hexane
  • a perfluoro chlorohydrocarbon for instance trifluorotrichloroethane.
  • Such chlorofluoro solvents are known under the registered name FREON ® accompanied by an index which denotes the degree of substitution and the number of halogen atoms of each type in the molecule.
  • the concentration of acid halide in the solution can vary between 0.1 and 2 percent by weight, and is normally between 0.2 and 1 percent by weight.
  • the amine or the amines are normally used in aqueous solution in a concentration of up to 7 percent by weight, and then normally between 1.5 and 3 percent by weight.
  • the base foil is not allowed to dry after the first application of the amine solution and before the solution of a trifunctional acid halide is applied. It is necessary for a film of liquid to remain on the surface in order for the interphase polymerization process to take place.
  • the solutions may be applied to the surface of the base foil with the aid of various spreading and coating methods.
  • the simplest and most suitable method is to dip the base foil into the amine solution and then into the solution of trifunctional acid halide. This will ensure that irregular surfaces on the base foil will also be covered completely, which constitutes one of the main advantages afforded by the invention.
  • the base foil may be held dipped in the amine solution for about 2 minutes, for instance. The base foil is then removed from the solution and any visible droplets may be removed, although while ensuring that a film of liquid remains constantly on the surface of the foil.
  • the base foil coated with the liquid film is then dipped into the trifunc- tional acid halide solution and held submerged for about 30 seconds, whereafter the foil is removed and allowed to dry in air.
  • the aforesaid dipping times are not critical.
  • the coated membrane When the coated membrane has dried, it is leached in water to remove any remaining non-reacted reactants, and is then ready for use.
  • AMINE II 1.56 g of the compound E (3.2 mmol) is slurried in 60 ml of 99% ethanol and 10 ml methylene chloride. 1.5 g of palladium on carbon is added and the mixture is hydrated for 2 hours and the reaction mixture is then allowed to stand in a hydrogen gas atmosphere for a further 12 hours. The catalyst is then filtered off and the solvent evaporated. 1.06 g (78% yield) of N- (2' ,4' -diaminophenyl sulfonyl) N methyl-4-anilido sulfonyl morpholide (amine II) is obtained in the form of white crystals having a melting point of 167.5-171.5°C.
  • the carrier material or base foil is used a nonwoven polyester fabric coated with polysulfone, the polysulfone layer having been given a specific pore structure by gelling in water.
  • the carrier material was dipped into a 2% aqueous solution of amine I and/or amine II for 2 minutes. The material is then removed from the solution and visible droplets are removed by running a rubber roller over the carrier. The carrier material is then dipped for 30 seconds into a 0.3% solution of 1, 3, 5-trimesoyl chloride in hexane or a per- chlorofluorohydrocarbon, such as trifluorotrichloroethane. The membrane is then allowed to dry in air and thereafter leached in water at room temperature for 2 hours in order to wash off any unreacted reaction components that may have been present .
  • This process results in a membrane having osmotic properties well suited for use in reverse osmosis water purification processes.
  • the carrier material a polyester fabric coated with polysulfone wherein the sulphone layer has been given a specific pore structure by gelling in water.
  • the carrier material is dipped into a 3%-aqueous solution of amine I and/or amine II for 2 minutes. The material is then removed from the solution and visible droplets on the surface are removed by blowing hot air at 60°C onto the surface. The surface of the material must not be allowed to dry, however, as a film of liquid on the surface is a requisite for enabling interphase polymerization to be achieved.
  • the carrier material is then dipped for 30 seconds into a 0.5%- solution of 1,3,5-trimesoyl chloride in a perfluoro chlorohydrocarbon or hexane. The membrane is then allowed to dry in air and is thereafter leached in water at room temperature for 2 hours, in order to wash off any unreacted reaction components that may have been present.
  • the result is a membrane having osmotic properties well suited for use in reverse osmosis water purification process- es.
  • TESLIN microcrackled polyethylene foil retailed under the trade name TESLIN by PPG Industries, U.S.A.
  • the carrier material is dipped into an aqueous solution of 1.5% amine I and 1.5% amine II for 2 minutes. The material is then removed from the solution and visible droplets on the surface are removed by blowing hot air at 60°C onto the surface. The surface of the material must not be allowed to dry, since a film of liquid on the surface is a requisite for achieving interphase polymerization.
  • the carrier material is then dipped into a 0.5% solution of 1,3, 5-trimesoyl chloride in hexane or perfluorohydrocarbon. The membrane is then dried in air and thereafter leached in water at room temperature for 2 hours, in order to wash away any unreacted reaction components that may have been present.
  • This process results in a membrane having osmotic properties well suited for use in reverse osmosis water purification processes.
  • the inventive membrane having osmotic properties can be used in a purely conventional manner in a typical water purification apparatus by means of reverse osmosis. Such apparatus and their construction and modus operandi are well known to the person skilled in this art. It will be observed, however, that although the purification of water by means of reverse osmosis is a preferred area of use of the inventive membrane, the inventive membrane is not limited solely to this use.
  • the inventive membrane can be used within any field in which a semipermeable membrane is required in osmotic processes, and those modifications to the properties of the membrane required for a specific application can be readily determined by the person skilled in this art who has knowledge of the invention, and on the basis of simple routine experiments if so required.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/SE1995/000669 1994-08-31 1995-06-07 Polymer membrane having osmotic properties WO1996006838A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9402893A SE503195C2 (sv) 1994-08-31 1994-08-31 Morfolindiamin, interfaspolymer baserad på denna amin, membran med osmotiska egenskaper innefattande denna polymer, sätt att framställa membranet samt användning av detta vid vattenrening.
SE9402893-3 1994-08-31

Publications (1)

Publication Number Publication Date
WO1996006838A1 true WO1996006838A1 (en) 1996-03-07

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Application Number Title Priority Date Filing Date
PCT/SE1995/000669 WO1996006838A1 (en) 1994-08-31 1995-06-07 Polymer membrane having osmotic properties

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SE (1) SE503195C2 (sv)
WO (1) WO1996006838A1 (sv)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9079870B2 (en) * 2012-10-31 2015-07-14 Indian Institute Of Science Education And Research-Pune Thiol mediated/activated prodrugs of sulfur dioxide (SO2) having anti-bacterial activity
CN108451939A (zh) * 2018-05-14 2018-08-28 兰州大学 2,4-二硝基苯磺酰胺类化合物的用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015149A1 (en) * 1979-02-22 1980-09-03 FilmTec Corporation Interfacially synthesized reverse osmosis membrane, process for the preparation thereof and its use in a process for removing solute from solute-containing water
EP0102752A1 (en) * 1982-08-02 1984-03-14 E.I. Du Pont De Nemours And Company Polyamide of disulfonated diamine and permselective membrane thereof
WO1990010494A1 (en) * 1987-06-08 1990-09-20 Allied-Signal Inc. Chlorine-resistant semipermeable membranes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015149A1 (en) * 1979-02-22 1980-09-03 FilmTec Corporation Interfacially synthesized reverse osmosis membrane, process for the preparation thereof and its use in a process for removing solute from solute-containing water
EP0102752A1 (en) * 1982-08-02 1984-03-14 E.I. Du Pont De Nemours And Company Polyamide of disulfonated diamine and permselective membrane thereof
WO1990010494A1 (en) * 1987-06-08 1990-09-20 Allied-Signal Inc. Chlorine-resistant semipermeable membranes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9079870B2 (en) * 2012-10-31 2015-07-14 Indian Institute Of Science Education And Research-Pune Thiol mediated/activated prodrugs of sulfur dioxide (SO2) having anti-bacterial activity
CN108451939A (zh) * 2018-05-14 2018-08-28 兰州大学 2,4-二硝基苯磺酰胺类化合物的用途

Also Published As

Publication number Publication date
SE9402893D0 (sv) 1994-08-31
SE503195C2 (sv) 1996-04-15
SE9402893L (sv) 1996-03-01

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