Degradable thiol-ene polymers

• US 7,288,608 B2
• Filed: 10/10/2002
• Issued: 10/30/2007
• Est. Priority Date: 10/10/2001
• Status: Active Grant

• Current Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Inventors: Bowman, Christopher, Hacioglu, Bilge, Anseth, Kristi, Nuttelman, Charlie
• Primary Examiner(s): Zimmer; Marc S.
• Application Number:
  US10/269,916
• Publication Number:
  US 20030144373A1
• Time in Patent Office: 1,846 Days
• Field of Search: None
• US Class Current: 525/535
• CPC Class Codes: A01N 25/04 Dispersions, emulsions, suspoemulsions, suspension concentrates or gels foams A01N25/16
• CPC Class Codes: A61K 47/34 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers A61K47/10 takes precedence
• CPC Class Codes: A61L 2300/62 Encapsulated active agents, e.g. emulsified droplets
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/38 containing added animal cells organs or tissue containing native cells A61L27/36
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: A61L 27/54 Biologically active materials, e.g. therapeutic substances A61L27/227 takes precedence
• CPC Class Codes: C05G 5/23 Solutions
• CPC Class Codes: C05G 5/37 layered or coated with a polymer
• CPC Class Codes: C08G 2261/126 block
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: C08G 81/00 Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers involving only carbon-to-carbon unsaturated bond reactions C08F299/00 ; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42
• CPC Class Codes: C08G 81/025 containing polyether sequences
• CPC Class Codes: C08G 81/027 containing polyester or polycarbonate sequences
• CPC Class Codes: C08J 2329/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C08J 2367/04 Polyesters derived from hydroxy carboxylic acids, e.g. lactones C08J2367/06 takes precedence
• CPC Class Codes: C08J 2371/02 Polyalkylene oxides
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: C08L 2205/05 containing polymer components which can react with one another
• CPC Class Codes: C08L 2666/22 : Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 71/02 : Polyalkylene oxides
• CPC Class Codes: C08L 81/02 : Polythioethers; Polythioether-ethers
• CPC Class Codes: C08L 83/00 : Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 89/00 : Compositions of proteins; Compositions of derivatives thereof foodstuff preparations A23J3/00
• CPC Class Codes: Y10S 524/916 : Hydrogel compositions
• CPC Class Codes: Y10S 525/936 : Encapsulated chemical agent

Abstract

A thiol-ene polymeric material is disclosed. The material is produced by the photopolymerization of reactants having thiol and olefin moieties. The material can incorporate encapsulated components, including cells. Additionally, the material can be derivatized by reacting the polymeric material with components such as proteins.

Claims

1. A polymeric material comprising repeating units of the formula:

—

[—

S—

R₁—

S—

C—

C—

R₂—

C—

C]—

wherein R₁ and R₂ are independently selected from the group consisting of poly(lactic acid) (PLA), polyglycolide (PGA), copolymers of PLA and PGA, poly(vinyl alcohol) (PVA), poloxamines, polyanhydrides, polyorthoesters, poly(hydroxy acids), polydioxanones, polycarbonates, polyaminocarbonates, poly(vinyl pyrrolidone), poly(ethyl oxazoline), polypeptides, polysaccharides, carbohydrates, proteins, copolymers thereof, and blends thereof, and at least one of R₁ and R₂ are degradable.

2. The polymeric material, as claimed in claim 1, wherein R₁ and R₂ are independently selected from the group consisting of:

poly(lactic acid), poly(vinyl alcohol), and mixtures thereof.

3. The polymeric material, as claimed in claim 1, wherein the polymeric material is biocompatible.

4. The polymeric material, as claimed in claim 1, wherein the material has a minimum dimension of at least about 4 cm.

5. The polymeric material, as claimed in claim 1, wherein said polymeric material further comprises repeating units of the formula:

—

[—

S—

R₃—

S—

C—

C—

R₄—

C—

C—

]—

wherein R₃ and R₄ are linkers different from R₁ and R₂ and are independently selected from the group consisting of;

poly(lactic acid) (PLA), polyglycolide (PGA), copolymers of PLA and PGA, poly(vinyl alcohol) (PVA), poly(ethylene glycol) (PEG), poly(ethylene oxide), poly(ethylene oxide)-co-poly(propylene oxide) block copolymers, poloxamines, polyanhydrides, polyorthoesters, poly(hydroxy acids), polydioxanones, polycarbonates, polyaminocarbonates, poly(vinyl pyrrolidone), poly(ethyl oxazoline), carboxymethyl cellulose, hydroxyalkylated celluloses, polypeptides, polysaccharides, carbohydrates, proteins, copolymers thereof, and blends thereof.

6. A branched polymeric material comprising units having at least one of the formulas:

R₁—

[—

S—

C—

C—

R₂]_p and

R₂—

[—

C—

C—

S—

R₁]_q

wherein R₁ and R₂ are independent branch points independently selected from the group consisting of poly(lactic acid) (PLA), polyglycolide (PGA), copolymers of PLA and PGA, poly(vinyl alcohol) (PVA), poloxamines, polyanhydrides, polyorthoesters, poly(hydroxy acids), polydioxanones, polycarbonates, polyaminocarbonates, poly(vinyl pyrrolidone), poly(ethyl oxazoline), polypeptides, polysaccharides, carbohydrates, proteins, copolymers thereof, and blends thereof and at least one of R₁ and R₂ are degradable, and p and q are independently integers greater than two.

7. A branched polymeric material comprising units having a formula selected from the group consisting of:

8. A branched polymeric material comprising units having a formula selected from the group consisting of: