Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

• US 4,784,736 A
• Filed: 07/07/1986
• Issued: 11/15/1988
• Est. Priority Date: 07/07/1986
• Status: Expired due to Fees

• Current Assignee: Bend Research Inc. (Lonza Group AG)
• Original Assignee: Bend Research Inc. (Lonza Group AG)
• Inventors: Wamser, Carl C., Lonsdale, Harold K.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Hsing, Ben C.
• Application Number:
  US06/883,043
• Time in Patent Office: 862 Days
• Field of Search: 204/157.15, 204/157.4, 204/157.6, 204/157.52, 540/122, 540/139, 540/140, 540/145, 540/135, 540/129, 540/136, 540/131, 540/124
• US Class Current: 204/157.15
• CPC Class Codes: B01D 69/122 Separate manufacturing of ultra-thin membranes
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 69/1251 by interfacial polymerisation
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: B01J 13/16 Interfacial polymerisation
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 31/1658 immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/183 with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: B01J 35/59 Membranes
• CPC Class Codes: C08G 85/00 General processes for preparing compounds provided for in this subclass
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: H01M 14/005 Photoelectrochemical storage cells light sensitive devices H01G9/20, semiconductors sensitive to light H01L31/00
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membanes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanime derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

Claims

1. A method of initiating redox reactions comprising transporting photochemically generated electrons through an ultrathin membrane on a support, said ultrathin membrane comprising the interfacial polymerization reaction product made from at least one prepolymer of the type M_F X_m, M_F '"'"'Y_n and N_F Y_n wherein

M_F and M_F '"'"' are monomeric or oligomeric moieties that are selectively photochemically or electrochemically reactive,

N_F is a linkable or crosslinkable monomeric or oligomeric moiety that is not photochemically or electrochemically reactive,

X and Y are groups which render said prepolymers reactive in an interfacial polymerization reaction,

m and n are integers ≧

2, and wherein said interfacial polymerization reaction product possesses substantially the same selective photochemical or electrochemical reactivity as M_F and M_F '"'"'.

2. The method of claim 1 wherein the support is electrically conductive or semiconductive.

3. The method of claim 1 wherein the support is a microporous polymeric support.

4. The method of claim 1 wherein M_F and M_F '"'"' are selected from the group consisting of porphyrins and phthalocyanines and derivatives thereof.

5. The method of claim 1 wherein said ultrathin membrane comprises the interfacial polymerization reaction product of monomers that are mutually reactive in a condensation reaction, at least one of said monomers being of the formula ##STR7## wherein M is a metal ion or --H H--,

R is H, alkyl, aryl, pyridinyl, R'"'"', alkyl-R'"'"', or aryl-R'"'"',

R'"'"' is H, Hal, NH₂, CH₂ NH₂, SH, OH, COHal, COOH, NCO, or SO₂ Hal, and

Hal is a halide.

6. The method of claim 5 wherein said ultrathin membrane is chemically asymmetric.

7. The method of claim 6 wherein said chemically asymmetric membrane has a predominance of X groups of hydrolyzed X groups at or near one surface of said membrane and a predominance of Y groups or hydrolyzed Y groups at or near the other surface of said membrane.

8. The method of claim 6 wherein said chemically asymmetric membrane has a predominance of one type of R'"'"' group or hydrolyzed R'"'"' group at or near one surface of said membrane and a predominance of another type of R'"'"' group or hydrolyzed R'"'"' group at or near the other surface of said membrane.

9. The method of claim 7 or 8 wherein said chemically asymmetric membrane has a predominance of one electrical charge on one surface of said membrane and a predominance of the opposite electrical charge on the other surface of said membrane.

10. The method of claim 1 wherein said ultrathin membrane is ≦

1000 nanometers in thickness.