Composite membranes, processes for their preparation and their use

• US 4,968,430 A
• Filed: 03/22/1989
• Issued: 11/06/1990
• Est. Priority Date: 04/07/1988
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Nerger, Dittmar, Hildenbrand, Karlheinz, Dhein, Rolf, Meister, Willi
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US07/327,211
• Time in Patent Office: 594 Days
• Field of Search: 210/640, 210/500.27, 210/490, 210/651, 210/654, 210/500.41, 210/500.29, 55/16, 55/68, 55/158, 427/245, 427/246
• US Class Current: 210/640
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 61/362 Pervaporation
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1214 Chemically bonded layers, e.g. cross-linking
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 71/54 Polyureas; Polyurethanes
• CPC Class Codes: C07C 7/144 using membranes, e.g. selective permeation

Abstract

Composite membranes of a macroporous filler-containing membrane of at least two incompatible polymers and a pore-free polyurethane membrane applied there to exhibit an improved action in the removal of benzenes optionally suhstituted by lower alkyl radicals, hydroxyl, chlorine or bromine from their mixtures with aliphatic and/or cycloaliphatic hydrocarbons, alcohols, ethers, ketones and/or carboxylic acid esters or from effluent.

Claims

1. Composite membranes, comprising (i) a macroporous filler-containing membrane of at least two incompatible polymers and (ii) a pore-free polyurethane (PU) membrane applied to (i) said composite membranes, being prepared by (a) dispersing an insoluble filler in a solution containing said at least two incompatible polymers, the amounts of said polymers being such as which would normally lead to phase separation in the solution to form a homogeneous casting solution, (b) processing said solution into membranes and carrying out precipitation coagulation thereof and (c) applying a pore-free PU membrane to the macroporous filler-containing membrane so obtained.

2. Composite membranes according to claim 1, wherein two or three incompatible polymers selected from the group consisting of polyurethanes, polyacrylonitrile, polyvinyl acetate, polystyrene polysulphone, polyvinylidene fluoride, polyamide, polyhydantoin and ethylene/vinyl acetate copolymers containing at least 50% by weight of vinyl acetate are used for (i).

3. Composite membranes according to claim 1, wherein one ore more fillers selected from the group consisting of talc, microcrystalline cellulose, zeolites, bentonites, SiO₂, TiO₂ and BaSO₄ are used.

4. Composite membranes according to claim 1, additionally containing a support material onto which (i) and then (ii) are applied.

5. Composite membrane according to claim 1, wherein the pore-free membrane (ii) is a crosslinked acrylate/polyurethane blend.

6. Composite membranes according to claim 5, wherein the acrylates are one or more esters of acrylic acid or methacrylic acid with aliphatic, cycloaliphatic or araliphatic diols and/or polyols having three of more OH groups, the diols having 4-12 C atoms.

7. Composite membranes according to claim 6, wherein the acrylates are butane-1,4-diol acrylate, butanediol bis-methacrylate, trimethylolpropane trisacrylate, trimethylolpropane trimethylacrylate, pentaerythritol tetraacrylate of pentaerythritol tetramethacrylate, or urethane acrylates.

8. Composite membranes according to claim 7, wherein the acrylate is trimethylolpropane trisacrylate.

9. Composite membrane according to claim 1, wherein a support material which remains on the composite membrane is used as the carrier substrate for casting the solution containing the incompatible polymers and fillers during production of the composite membranes in the form of films.

10. A process for removing benzene, said benzene being optionally mono-, di- or trisubstituted by chlorine, bromine, hydroxyl or C₁ -C₄ -alkyl, from aliphatic and/or cycloaliphatic hydrocarbons, alcohols, ethers, ketones and/or carboxylic acid esters or from effluent by permeation through a composite membrane the improvement wherein said removal is carried out using the composite membrane according to claim 1.