一种新型骨内固定聚合物不饱和聚酯酰胺树脂的合成与性能评价

A new type of bone internal fixation polymer:Synthesis and property evaluation of unsaturated polyester amide resin

背景:采用高强度、高模量可控降解吸收性骨内固定物代替目前临床使用的生物稳定性金属内固定物,可避免金属内固定物弹性模量过高、引起炎症反应、需二次手术去除等弊端。目的:合成不饱和聚酯酰胺树脂,观察不同引发-促进剂对其室温初凝时间影响及深度交联后的高聚物力学及降解性能。方法:以顺丁烯二酸酐、邻苯二甲酸酐、乙二醇、1,2-丙二醇、新戊二醇、己内酰胺等为原料,利用熔融缩聚法,合成出一类不饱和聚酯酰胺树脂预聚物,并对其进行了表征,然后以乙酸乙烯酯为交联剂,加入一定量的引发-促进剂室温预交联,后热处理深度交联出高强度,可完全降解的聚酯酰胺高聚物,观察不同引发-促进剂对不饱和聚酯酰胺树脂室温初凝时间影响及深度交联后的高聚物力学及降解性能。结果与结论:合成的不饱和聚酯酰胺树脂低聚物具有很好的性能,满足交联需要;不同类的引发-促进剂对室温预交联的不饱和聚酯酰胺树脂凝胶时间影响不同,交联的机制也不同;对热处理深度交联后的树脂高聚物在模拟体液中降解发现它们具有很好的力学强度保持率,初步结果证明此材料可以开发成一种可完全降解骨内固定材料。

BACKGROUND：High strength,high modulus controllable degradable and absorbable internal fixation bone substitutes the metal implant which is currently clinically used and present with biological stability,thus avoiding the metal implant from inflammation,too high elastic modulus,and requirement to perform secondary operation.OBJECTIVE：To synthesize unsaturated polyester amide resin and to observe the influence of various initiator-accelerants on its initial setting time at room temperature,as well as polymer mechanics and degradation properties after cross-linking.METHODS：Using maleic anhydride,phthalic anhydride,ethylene glycol,1,2-propanediol,neopentyl glycol,caprolactam,unsaturated polyester amide resin prepolymer was synthesized with melt polycondensation method,and was then characterized.Using vinyl acetate as the cross-linking agent,adding a certain amount of initiator-accelerants for pre-crosslinking agent at room temperature,followed by heat treatment,the high-strength,fully degradable polyester amide polymer was deeply cross-linked.The influence of various initiator-accelerants on initial setting time of unsaturated polyester amide resin at room temperature,as well as polymer mechanics and degradation properties after cross-linking,were observed.RESULTS AND CONCLUSION：The synthesized,unsaturated polyester amide resin oligomer has a good performance,which can meet the requirement of cross-linking;different types of initiator-accelerants exhibited various impacts on the gel time of unsaturated polyester amide resin pre-crosslinking at room temperature.The mechanism underlying crosslinking was different;Following the heat treatment of the deep cross-linking,resin ionomer degraded in simulated body fluid,indicating good mechanical strength retention capacity.Preliminary results show that this material can be developed into a fully degradable bone internal fixation material.