Grafted methylenediphosphonate ion exchange resins

• US 5,712,347 A
• Filed: 04/03/1997
• Issued: 01/27/1998
• Est. Priority Date: 02/06/1995
• Status: Expired due to Term

• Current Assignee: ARCH Development Corporation (University of Chicago), The University Of Tennessee Research Corporation (University of Tennessee)
• Original Assignee: ARCH Development Corporation (University of Chicago), The University Of Tennessee Research Corporation (University of Tennessee)
• Inventors: Gatrone, Ralph C., Trochimcznk, Andrzej W., Horwitz, E. Philip, Alexandratos, Spiro
• Primary Examiner(s): Zitomer, Fred
• Application Number:
  US08/829,998
• Time in Patent Office: 299 Days
• Field of Search: 525/340, 525/403, 525/538, 521/30, 521/32, 521/33, 521/34
• US Class Current: 525/340
• CPC Class Codes: B01J 39/12 Compounds containing phosphorus
• CPC Class Codes: C08F 8/40 Introducing phosphorus atoms or phosphorus-containing groups

Abstract

An ion exchange resin is disclosed that is comprised of an insoluble copolymer onto which are grafted pendent groups that provide 1.0 to about 10 mmol/g dry weight phosphorous. The pendent groups have the formula ##STR1## wherein R is hydrogen, a cation or mixtures thereof; and R¹ is hydrogen or an C₁ -C₂ alkyl group. The resin also contains zero to about 5 mmol/g dry weight of pendent aromatic sulfonate groups. Processes for making and using an ion exchange-resin are also disclosed.

Claims

1. A process for using tetra-C₁ -C₈ alkyl methylenediphosphonate carbanion to prepare an ion exchange resin comprised of an insoluble cross-linked copolymer containing grafted pendent tetra-C₁ -C₈ alkyl methylenediphosphonate groups comprising the steps of:

(a) forming a reaction mixture by admixing insoluble cross-linked copolymer particles containing about 10 to about 95 mole percent copolymerized vinylbenzyl halide or glycidyl acrylate or methacrylate monomer and a sufficient amount of tetra-C₁ -C₈ alkyl methylenediphosphonate carbanion in a hydrocarbon solvent to form 1.0 to about 10 mmol/g of said pendent groups,, said particles being sized to pass through a 4 millimeter sieve opening and be retained on a sieve having an opening of about 0.004 millimeters;

(b) maintaining said reaction mixture at a temperature of about 25°

to about 250°

C. for a time period sufficient for an ion exchange resin with said amount of pendent groups to form as product; and

(c) recovering said product containing pendent tetra-C₁ -C₈ alkyl methylenediphosphonate groups.

2. The process according to claim 1 wherein said tetra-C₁ -C₈ alkyl methylenediphosphonate is tetraisopropyl methylene diphosphonate.

3. The process according to claim 1 wherein said insoluble cross-linked copolymer contains reacted monomers selected from the group consisting of styrene, ethyl styrene, vinyltoluene, vinylxylene, acrylonitrile, a C₁ -C₈ alkyl acrylate or methacrylate, a vinyl C₁ -C₈ acyl ester, vinylchloride, a C₁ -C₈ alkyl vinyl ether, a vinyl benzyl halide and glycidyl acrylate or methacrylate.

4. The process according to claim 1 wherein said insoluble cross-linked copolymer contains a reacted cross-linking agent selected from the group consisting of divinylbenzene, trimethylolpropane triacrylate or trimethyacrylate, erythritol tetraacrylate or tetramethacrylate, erythritol tetraacrylate or tetramethacrylate, 3,4-dihydroxy-1,5-hexadiene and 2,4-dimethyl-1,5-hexadiene.

5. The process according to claim 1 wherein said product contains about 2 to about 7 mmol/g phosphorous after hydrolysis of the tetra-C₁ -C₈ alkyl groups.

6. The process according to claim 1 wherein said insoluble cross-linked copolymer particles are generally spherical in shape.

7. The process according to claim 1 including the further step of hydrolyzing the tetra alkyl ester product recovered in step (c).

8. The process according to claim 3 wherein said insoluble cross-linked copolymer particles contain at least 10 mole percent reacted monomers that contain an aromatic ring and including the further steps of

(d) sulfonating the recovered product of step (c) to form an ion exchange resin having about 0.1 to about 4 mole percent pendent aromatic sulfonate groups;

(e) hydrolyzing the tetra-C₁ -C₈ alkyl phosphonate groups to form an ion exchange resin having pendent aromatic sulfonate and methylenediphosphonic acid groups as a second product; and

(f) recovering said second product.

9. An aqueous composition comprising in admixture,

(a) water-having a pH value of about 1 or less,

(b) a plurality of ion exchange resin particles, said particles being sized to pass through a 4 millimeter sieve opening and be retained on a sieve having an opening of about 0.004 millimeters, said resin comprising an insoluble copolymer onto which are grafted pendent groups that provide phosphorous at 1.0 to about 10 mmol/g dry weight, said pendent groups having the formula ##STR6## wherein R is hydrogen, a cation or mixtures thereof;

and R¹ is hydrogen or an C₁ -C₂ alkyl group;

said resin also containing zero to about 5 mmol/g dry weight of pendent aromatic sulfonate groups, said mmol/g values based on said polymer where R is hydrogen; and

(c) a plurality of cations that include at least one polyvalent cation having an atomic number of 90 or more.

10. The aqueous composition according to claim 9 wherein said ion exchange resin particles contain about 2 to about 7 mmol/g phosphorous.

11. The aqueous composition according to claim 9 wherein said ion exchange resin particles contain about 0.1 to about 4 mmol/g dry weight of said pendent aromatic sulfonate groups.