聚富马酸丙二醇酯复合材料热固化及3D打印应用研究

发布时间：2018-03-01 20:39

本文关键词： 聚富马酸丙二醇酯复合材料热固化 3D打印　出处：《暨南大学》2017年硕士论文　论文类型：学位论文

【摘要】：3D打印技术近年来发展迅速,代表了先进制造技术的发展方向。作为3D打印技术的基础和核心问题之一,理想的3D打印材料却远不能满足技术和应用发展的需求,特别是适合于生物医学应用的3D打印材料十分有限。聚富马酸丙二醇酯(PPF)在生物医学材料领域已有广泛应用,具备3D打印材料的基本性能,有较高的研究和应用价值。本文以PPF复合材料体系研究为重点,探讨其作为3D打印材料应用的可行性。首先,采用两步合成法,优化合成工艺,以富马酸二甲酯和1,2-丙二醇为原料,ZnCl2为催化剂、对苯二酚为阻聚剂,物料在140°C下反应12 h,获得PPF低聚物,进一步在200°C、真空条件下继续反应3 h,制备的PPF其收率达到69.4%。红外光谱、核磁共振氢谱分析证实产物结构组成,凝胶渗透色谱测得合成产物的数均分子量Mn为5408,聚合度分布指数PI为1.57。其次,系统研究了PPF材料的热固化性能。对引发剂种类及添加比例、辅助交联单体种类及添加比例和固化温度进行筛选优化,结果表明,以过氧化苯甲酰(BPO)为引发剂,N-乙烯基吡咯烷酮(NVP)为辅助交联单体,得到的PPF复合材料体系具备优良的可固化性能。另外,BPO添加比例、NVP含量以及热固化温度几个参数对PPF热固化树脂的固化时间、凝胶含量、热固化材料的热稳定性、吸湿性能、抗压强度、体外降解速率以及材料的细胞毒性的影响也进行了详细的对比研究。结果表明:以PPF为主体,PPF、NVP、BPO质量分数分别为85、15、5所组成的复合材料具有良好的流动性,在200°C下其固化时间最短(3s),固化后PPF复合材料的凝胶含量达到75.6%,压缩强度为5.57 MPa,与人体松质骨压缩强度相当。固化后的PPF复合材料在相对湿度RH为89%的环境中72 h的吸湿率仅为4.71%,体外降解72 h的溶胀度仅为18.15%,具有良好的尺寸稳定性。TG分析结果表明该复合材料在250°C以内失重率0.83%,其作为3D打印材料应用时在热固化温度(180~200°C)条件下呈现良好的热稳定性。体外模拟降解实验结果表明,PPF固化材料具有优良的生物可降解性能,其降解速率随复合材料中BPO含量的减小或NVP含量的增加而加快,可在一定范围内进行调节。体外降解4周,PPF固化树脂的降解失重率可达到13.46%。细胞毒性实验表明,PPF固化树脂材料浓度高达100 mg/mL时,材料的细胞毒性评级为Ⅰ级,对3T3细胞无毒性,满足材料的生物安全性要求。应用改进的FDM打印装置,以优化后的PPF复合材料进行3D打印成型实验,制备的人鼻3D打印构建物成型迅速,且制品表面光滑、立体结构完整、强度合适,表明该PPF复合材料可以满足3D打印制作热固化成型器件的要求,具有广阔的应用前景。
[Abstract]:3D printing technology has developed rapidly in recent years, which represents the development direction of advanced manufacturing technology. As one of the basic and core problems of 3D printing technology, the ideal 3D printing materials can not meet the needs of the development of technology and application. In particular, 3D printing materials suitable for biomedical applications are very limited. PPFs have been widely used in biomedical materials and have the basic properties of 3D printing materials. This paper focuses on the research of PPF composite system and discusses the feasibility of its application as 3D printing material. Firstly, the synthesis process is optimized by using two-step synthesis method. Using dimethyl fumarate and 1h2propanediol as catalyst, hydroquinone as inhibitor, PPF oligomer was obtained at 140 掳C for 12 h. Further reaction at 200 掳C for 3 h was carried out. The yield of PPF was 69.4%. Nuclear magnetic resonance (NMR) analysis confirmed the structure of the product. The number average molecular weight of the synthesized product was 5408, and the polymerization degree distribution index (Pi) was 1.57. secondly, the molecular weight of the synthesized product was determined by gel permeation chromatography (GPC). The thermal curing properties of PPF materials were systematically studied. The types and proportion of initiators, the types of auxiliary crosslinking monomers, the addition ratio and curing temperature were optimized. Using benzoyl peroxide (BPO) as initiator, N- vinylpyrrolidone (NVP) as auxiliary crosslinking monomer, The obtained PPF composite system has excellent curable properties. In addition, the curing time, gel content, thermal stability and hygroscopicity of PPF thermosetting resin were determined by adding the ratio of PPF and the heat curing temperature. The effects of compressive strength, degradation rate in vitro and cytotoxicity of PPF were also studied in detail. At 200 掳C, the curing time is the shortest, and the gel content of the cured PPF composites is 75.6 and the compressive strength is 5.57 MPA, which is similar to the compressive strength of human cancellous bone. The cured PPF composite is in the environment of relative humidity RH 89% for 72 h. The moisture absorption rate of the composite is only 4.71%, and the swelling degree of 72 h in vitro degradation is 18.15%. The results of TG analysis show that the weight loss rate of the composite is 0.83% within 250 掳C, and the thermal curing temperature is 180 掳C when it is used as a 3D printing material. The results of in vitro simulated degradation test showed that the PPF curing material had excellent biodegradability. The degradation rate increased with the decrease of BPO content or the increase of NVP content in the composites. The degradation weight loss rate of PPF curing resin in vitro was 13.46. The cytotoxicity test showed that when the concentration of PPF curing resin was as high as 100 mg/mL, the cytotoxicity rating of the material was grade I, and it was not toxic to 3T3 cells. In order to meet the requirements of biological safety of materials, the improved FDM printing device was used to carry out 3D printing experiments with optimized PPF composite materials. The 3D printing structures of human nose were formed rapidly, and the surface of the products was smooth and the solid structure was complete. The suitable strength shows that the PPF composite can meet the requirements of 3D printing for thermo-curing molding devices, and has a broad application prospect.
【学位授予单位】：暨南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：R318.08;TP391.73

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