Hydrophilic Polymeric Acylphospine Oxide Photoinitiators/Crosslinkers for in Vivo Blue-Light Photopolymerization

• Published in: Biomacromolecules 2001, Vol.2 (4), p.1271-1278
• Main Authors: de Groot, Jacqueline H, Dillingham, Keith, Deuring, Henk, Haitjema, Henk J, van Beijma, Folkert J, Hodd, Kenn, Norrby, Sverker
• Format: Article
• Language: English
• Subjects: Biocompatible Materials - chemical synthesis; Biocompatible Materials - chemistry; Cross-Linking Reagents; Hydrogels - chemical synthesis; Light; Oxides; Phosphines - chemistry; Phosphines - radiation effects; Photochemistry; Polymers - chemical synthesis; Polymers - chemistry; Solubility
• ISSN: 1525-7797; 1526-4602
• DOI: 10.1021/bm015584r

Three vinyl-functionalized phosphine oxide photoinitiating monomers have been synthesized:  4-vinylbenzoyldiphenylphosphine oxide (VBPO), 2,6-dimethyl-4-vinylbenzoyldiphenylphosphine oxide (DMVBPO), and 2,4,6-trimethylbenzoylphenyl-4-vinylphenylphosphine oxide (TMBVPO). VBPO was copolymerized with vinylpyrrolidone or vinyl acetate (PPI-1a) and dimethylacrylamide (PPI-1b). DMVBPO and TMBVPO were both copolymerized with dimethylacrylamide (PPI-2 and PPI-3, respectively). The choice of vinylphosphine oxide and comonomer(s) had a significant influence on the properties of the resulting PPI. PPI-1a was not stable in solution in 2-hydroxyethyl methacrylate (HEMA), whereas the VBPO-dimethylacrylamide (DMA) copolymer (PPI-1b) was stable in HEMA but not stable in aqueous solutions. PPI-2 was both soluble and stable in water up to 22 months. PPI-1a was as effective as trimethylbenzoyldiphenylphosphine oxide (TPO, BASF Lucirin). PPI-2 was more effective in the polymerization of HEMA/water mixtures than PPI-3. PPI-2 and PPI-3 acted as self-cross-linking species, resulting in the formation of hydrogels; PPI 3 was more effective in this. PPI-2 was very effective in forming hydrogels based on poly(ethylene glycol) diacrylate.