Milner Richard
Smith & Nephew Research Centre, York Science Park, Heslington, York YO10 5DF, United Kingdom.
J Biomed Mater Res B Appl Biomater. 2004 Feb 15;68(2):180-5. doi: 10.1002/jbm.b.20019.
Commercially available acrylic bone cements are two-component systems based on the polymerization of methyl methacrylate around poly(methyl methacrylate) particles. When benzoyl peroxide (BPO), which is the initiator, in the powder component meets accelerator (N,N-dimethyl-p-toluidine (DMpT)) in the liquid component, radicals are produced, initiating the polymerization. This solidifies the cement. In this work, kinetic expressions have been developed that describe the relationship between bone cement setting time on the one hand, and BPO and DMpT concentrations on the other. Changes in setting time with ambient temperature follow a complex relationship, because both the polymerization process (initiation, propagation, and termination) and the swelling and dissolution of the polymer particles contribute to setting. The contribution of polymer swelling and dissolution to the setting process was determined by developing a relationship between the doughing time, which is substantially independent of DMpT or BPO concentrations, and ambient temperature. A value of 64 kJ mol(-1) was found for the activation energy for this process. An activation energy for the overall setting process of 68 kJ mol(-1) was determined from setting-time measurements over several ambient temperatures. This indicates that the sensitivity of setting time to temperature depends more on swelling and dissolution than on the polymerization process.
市售的丙烯酸骨水泥是基于聚甲基丙烯酸甲酯颗粒周围甲基丙烯酸甲酯聚合反应的双组分体系。当粉末组分中的引发剂过氧化苯甲酰(BPO)与液体组分中的促进剂N,N - 二甲基对甲苯胺(DMpT)相遇时,会产生自由基,引发聚合反应。这会使骨水泥固化。在这项工作中,已经建立了动力学表达式,该表达式一方面描述了骨水泥凝固时间与另一方面BPO和DMpT浓度之间的关系。凝固时间随环境温度的变化遵循复杂的关系,因为聚合过程(引发、传播和终止)以及聚合物颗粒的溶胀和溶解都对凝固有贡献。通过建立面团化时间(其基本上与DMpT或BPO浓度无关)与环境温度之间的关系,确定了聚合物溶胀和溶解对凝固过程的贡献。发现该过程的活化能为64 kJ mol(-1)。通过在几个环境温度下测量凝固时间,确定了整个凝固过程的活化能为68 kJ mol(-1)。这表明凝固时间对温度的敏感性更多地取决于溶胀和溶解,而不是聚合过程。