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

• US 4,917,800 A
• Filed: 07/19/1988
• Issued: 04/17/1990
• 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): SPEAR JR, FRANK
• Application Number:
  US07/221,307
• Time in Patent Office: 637 Days
• Field of Search: 210/490, 210/654, 264/49, 204/157.15, 204/157.6, 540/122, 540/145
• US Class Current: 210/490
• 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: G01N 27/3335 the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001
• 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 membranes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanine derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

Claims

1. A thin film composite membrane comprising a microporous polymeric membrane support and an 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 can initiate photochemical redox reactions,

N_F is a linkable or crosslinkable monomeric or ologiomeric moiety that cannot initiate photochemical redox reactions,

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 redox reactivity as M_F and M_F^'"'"'.

2. The thin film composite membrane of claim 1 wherein M_F and M_F^'"'"' are selected from the group consisting essentially of porphyrins and phthalocyanines and derivatives thereof.

5. The composition of matter of claim 1 wherein the form of said interfacial polymerization reaction product is an ultrathin film chemically asymmetric membrane wherein there is a predominance of X groups of hydrolyzed X groups at or near one surface of said membrane and a predominance of Y groups of hydrolyzed Y groups at or near the other surface of said membrane.

7. The composition of matter of claim 5 or 6 wherein in the form of said interfacial polymerization reaction product is an ultrathin film chemically asymmetric membrane wherein said 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.

3. A composition of matter comprising 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 composition of matter of claim 3 wherein the form of said interfacial polymerization reaction product is an ultrathin film chemically asymmetric membrane wherein said membrane contains 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.

4. A thin film composite membrane comprising a micorporous polymeric membrane support and an ultrathin membrane comprising 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 ##STR8## 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.

8. A method of making a polymer containing recurring linked and crosslinked groups selected from M_F and M_F^'"'"' wherein M_F and M_F^'"'"' are prepolymeric moieties that can initiate photochemical redox reactions, comprising:

(a) forming a first solution of M_F X_m in a first liquid;

(b) forming a second solution containing a second prepolymeric compound selected from M_F X_n , M_F^'"'"' Y_n and N_F Y_n in a second liquid which is immiscible with said first liquid;

(c) combining said first and second solutions so as to form an interface between the two; and

(d) reacting M_F X_m and said second prepolymeric compound at the interface of said first and second solutions wherien X and Y are different groups which are mutually reactive in an interfacial polymerization reaction, N_F is a linking or a crosslinking group, and m and n are integers ≧

2.

9. The method of claim 8 wherien said interfacial polymerization reaction is a condensation reaction.

10. The method of claim 8 wherein X and Y are selected from NH₂, CH₂ NH₂, SH, OH, COHal, COOH, NCO and SO₂ Hal, and Hal is halide.

11. The method of claim 8 wherein M_F is selected from the group consisting of porphyrins and phthalocyanines and derivatives thereof.

12. The method of claim 8 wherein the interface between said first and second solutions is at the surface pores of a microporous polymeric membrane support.

13. The method of claim 8 wherein the form of the polymer made is an ultrathin film chemically asymmetric membrane containing a predominance of X groups or hydrolyzed X groups at or near one surface of said membrene and a predominance of Y groups or hydrolyzed Y groups at or near the other surface of said membrane.

14. THe method of claim 13 wherein said ultrathin film 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.

15. A method of making a polymer containing recurring linked and crosslinked groups of porphyrins, phthalocyanines and derivatives thereof comprising:

(a) forming a first solution of a first reactive compound of the formula ##STR9## 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 halide;

(b) forming a second solution of a second reactive compound that is reactive with said first reactive compound in an interfacial polymerization reaction, said second solution being immiscible with said first solution;

(c) combining said first and second solutions so as to form an interface between the two; and

(d) reacting said first and second reactive compounds at the interface of said first and second solutions.

16. The method of claim 15 wherein the interface between said first and second solutions is at the surface pores of a microporous polymeric membrane support.

17. The method of claim 15 wherein the form of the polymer made is an ultrathin film chemically asymmetric membrane containing 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.

18. The method of claim 17 wherein said ultrathin film 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.