Cross-linked polyvinyl pyridine coated glass particle catalyst support and aqueous composition or polyvinyl pyridine adducted microspheres

• US 4,259,223 A
• Filed: 10/02/1978
• Issued: 03/31/1981
• Est. Priority Date: 03/29/1976
• Status: Expired due to Term

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Rembaum, Alan, Volksen, Willi, Gupta, Amitava
• Primary Examiner(s): Lesmes, George F.
• Assistant Examiner(s): Varndell, Jr., R. Eugene
• Application Number:
  US05/947,516
• Time in Patent Office: 911 Days
• Field of Search: 428/402, 428/407, 428/403, 428/406, 204/159.15, 204/159.22, 260/29.6 H, 260/29.6 SQ, 252/301.35, 252/426, 252/428, 252/477, 525/351, 525/386
• US Class Current: 523/122
• CPC Class Codes: B01J 2231/321 Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
• CPC Class Codes: B01J 2531/822 Rhodium
• CPC Class Codes: B01J 31/06 containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• CPC Class Codes: B01J 31/068 Polyalkylene glycols
• 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 31/181 Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
• CPC Class Codes: B01J 31/20 Carbonyls
• CPC Class Codes: C08F 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: Y10T 428/2996 Glass particles or spheres
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Claims

1. A composition comprising a suspension in aqueous acidic media of quaternized polymeric microspheres adducted to acid substituted natural biopolymer and organic fluorescent dyes containing a sulfonic or carboxyl group;

said microspheres consisting essentially of discrete beads, at least 80% of which have a uniform diameter from 100 A to 60 microns having a surface area of at least 1 m² /g and consisting essentially of addition copolymerized monomer mixture containing 70 to 80% vinyl pyridine, 10 to 30% of an addition copolymerizable, water soluble, monounsaturated comonomer selected from acrylamide, methacrylamide, acrylic acid, methacrylic acid or compounds of the formula;

##STR2## where R¹ is hydrogen or lower alkyl of 1-8 carbon atoms;

R² is alkylene of 1-12 carbon atoms and Z is --OH or ##STR3## where R³ or R⁴ are individually selected from H, lower alkyl or lower alkoxy of 1-8 carbon atoms, and 5 to 30% of a water soluble, addition copolymerizable polyvinyl cross-linking agent, said beads including a hard, cross-linked hydrophobic vinyl pyridine copolymeric core and a hydrophilic, monounsaturated comonomer copolymeric sheath.

2. An composition according to claim 1 in which the fluorescent dyes are selected from fluorescein isothiocyanate or rhodamine isothiocyanate.

3. An composition according to claim 1 in which the biopolymer is selected from at least one member of the group consisting of RNA, DNA, viruses or bacteria.

4. A composition according to claim 1 in which the cross-linking agent is selected from ethylene glycol dimethacrylate, trimethylol-propane-trimethacrylate, N,N'"'"'-methylene-bis-acrylamide or hexahydro-1,3,5-triacryloyl-s-triazine.

5. A composition according to claim 4 in which the vinyl pyridine is 2-vinyl pyridine, the comonomer is selected from hydroxyethylmethacrylate, acrylamide or methacrylamide and the cross linking agent is bis-methacrylamide.

6. A catalyst support consisting essentially of a polymer coated porous glass particle having a diameter below 1000 microns, a pore diameter from 50 to 500 nm, a polymer to glass ratio of 1 to 40% by weight and in which the polymer is present on the surface of the particles as a film of agglomerated microspheres consisting of an addition polymerized polymer containing 70 to 80% vinyl pyridine and the remainder being water-soluble, addition copolymerizable polyvinyl cross-linking agent.

7. A catalyst support according to claim 6 in which the cross-linking agent is selected from ethylene glycol dimethacrylate, trimethylol-propane-trimethacrylate, N,N'"'"'-methylene-bis-acrylamide or hexahydro-1,3,5-triacryloyl-s-triazine.

8. A support according to claim 6 in which the particle diameter is from 10 microns to 150 microns, the pore diameter is from 100 nm to 150 nm and the polymer/glass ratio is from 5% to 20% by weight.

9. A support according to claim 8 in which the polymer to glass ratio is about 10% by weight.