Free radical polymerization of poly(ethylene glycol) diacrylate macromers: Impact of macromer hydrophobicity and initiator chemistry on polymerization efficiency

被引:25
作者
Dai, Xiaoshu [2 ]
Chen, Xi [1 ]
Yang, Laura [1 ]
Foster, Sarah [1 ]
Coury, Arthur J. [1 ]
Jozefiak, Thomas H. [1 ]
机构
[1] Genzyme Corp, Biomat Sci & Engn, Framingham, MA 01701 USA
[2] Worcester Polytech Inst, Dept Mat Sci & Engn, Worcester, MA 01609 USA
关键词
Poly(ethylene glycol); Hydrogel; Free radical; Redox initiator; Photo-initiator; MECHANICAL-PROPERTIES; NETWORK STRUCTURE; REACTION-KINETICS; HYDROGELS; RELEASE; PHOTOPOLYMERIZATION; DEGRADATION; BEHAVIOR; SOLUTES;
D O I
10.1016/j.actbio.2011.01.005
中图分类号
R318 [生物医学工程];
学科分类号
0831 ;
摘要
A series of poly(ethylene glycol)-co-poly(lactide) diacrylate macromers was synthesized with variable PEG molecular weights (10 or 20 kDa) and lactate contents (0 or 6 lactates per end group) These macromers were polymerized to form hydrogels by free radical polymerization using either redox or photochemical initiators. The extent of polymerization was determined by monitoring the compressive modulus of the resulting hydrogels and by quantitative determination of unreacted acrylate after exhaustive hydrolysis of the gel. Polymerization efficiency was found to depend on the lactate content of the macromer, with higher lactate macromers giving more efficient polymerization. For redox-initiated polymerization using ferrous gluconate/t-butyl hydroperoxide Initiator, macromers containing approximately six lactate repeats per end group required lower concentrations of initiator to reach high conversion than lactate-free macromers Photochemical polymerization with alpha,alpha-dimethoxy-alpha-phenylacetophenone (Irgacure 651 (R)) was found to be less efficient than redox polymerization, requiring the addition of N-vinyl-2- pyrrolidone (NVP) as a co-monomer to achieve conversions comparable with redox polymerization. When conditions were optimized to provide near complete conversion for all gels, the presence of lactate repeat units in the hydrogel was generally found to reduce swelling and increase the compressive modulus. Calculated values of molecular weight between cross-links ((M-c) over bar) and mesh size using Flory-Rehner theory showed that macromer molecular weight had the greatest Impact on the network structure of the gel. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
引用
收藏
页码:1965 / 1972
页数:8
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