Method of making a dope comprising hydrophilized PVDF and .alpha.-alumina, and a membrane made therefrom

• US 6,024,872 A
• Filed: 05/14/1999
• Issued: 02/15/2000
• Est. Priority Date: 07/01/1997
• Status: Expired due to Fees

• Current Assignee: Zenon Environmental Incorporated (Veolia Environnement SA)
• Original Assignee: Zenon Environmental Incorporated (Veolia Environnement SA)
• Inventors: Bai, Jinhua, Mahendran, Mailvaganam, Goodboy, Kenneth Paul
• Primary Examiner(s): Kim, John
• Assistant Examiner(s): Ward, Richard W.
• Application Number:
  US09/312,149
• Time in Patent Office: 277 Days
• Field of Search: 525/326.2, 525/326.3, 525/372, 524/430, 524/545, 524/104, 524/437, 210/500.25, 210/500.26, 210/500.42
• US Class Current: 210/500.25
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 2325/36 Hydrophilic membranes
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/04 Tubular membranes
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/1071 Woven, non-woven or net mesh
• CPC Class Codes: B01D 69/1411 containing dispersed material in a continuous matrix
• CPC Class Codes: B01D 71/34 Polyvinylidene fluoride
• CPC Class Codes: C08K 9/02 Ingredients treated with inorganic substances
• CPC Class Codes: C08L 27/16 Homopolymers or copolymers or vinylidene fluoride
• CPC Class Codes: Y10T 428/249979 Specified thickness of void-containing component [absolute or relative] or numerical cell dimension

Abstract

A filtration membrane for micro- or ultra-filtration is formed from a complex of PVDF and calcined α-alumina ("α-Al") particles, in which complex the particles are reacted and dispersed. The suspended complex is then mixed with a hydrophilic polymer such as polyvinyl alcohol (40%-90% hydrolyzed) referred to herein as HPVA, which reacts with the complex imparting hydrophilicity to the polymer. The novel membrane provides about 50% higher specific flux than a membrane made with the same polymer but without the α-Al particles. Unexpectedly, the net flux is improved by treating the membrane with a solution of sodium hypochlorite which fails to remove the HPVA from the novel membrane but does remove it from the prior art membrane which does not contain the α-Al. The preferred membrane comprises a macroporous support coated on its outer surface with a thin tubular asymmetric semipermeable film of polymer containing less than about 50% by weight of α-Al particles.

Claims

1. A dope for making a filtration membrane, said dope being produced from a complex of calcined α

-alumina particles and polyvinylidene difluoride (PVDF) in a solvent for said PVDF, said complex being formed by dispersing at least 1 part by weight, but less than 50 parts by weight of said particles per 100 parts by weight of said particles and PVDF, in a solvent for said PVDF, said particles having a primary particle size in the range from about 0.1 μ

m to about 5 μ

m, said complex being reacted with a hydrophilic polymer which is added to the dope in a minor amount by weight relative to said PVDF, said hydrophilic polymer having reactive nucleophilic groups adapted to react with said complex and impart hydrophilicity to said membrane.

2. A method for making a dope to be used to make a filtration membrane, said method comprising,

preparing a complex consisting essentially of calcined α

-alumina particles in a solvent for polyvinylidene difluoride (PVDF), said complex being formed by dispersing less than 50 parts by weight of said particles per 100 parts by weight of said particles and PVDF, in a solvent for said PVDF, said particles having a primary particle size in the range from about 0.1 μ

m to 5 μ

m;

adding a hydrophilic polymer in a minor amount by weight relative to said PVDF said hydrophilic polymer having reactive nucleophilic groups adapted to react with said complex and impart hydrophilicity to a film formed from said dope;

said dope having a viscosity sufficient to provide a continuous coating on a support, said particles being present in said dope in an amount at least 1 percent by weight of the combined weight of said PVDF, said hydrophilic polymer and said particles.

3. The method of claim 2 wherein said dope has a viscosity in the range from about 8,000 cp to about 50,000 cp at 22°

C. for a microfiltration membrane and said particles are present in an amount less than 15 percent by weight of said combined weight.

4. The method of claim 2 wherein said dope has a viscosity in the range from about 50,000 cp to about 120,000 cp at 22°

C. for an ultrafiltration membrane and said particles are present in an amount less than 20 percent by weight of said combined weight.

5. A filtration membrane made from the dope produced in claim 2.