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聚己内酯的化学改性及其性能研究
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摘要
聚己内酯(PCL)因其优异的生物降解性和生物相容性而备受青睐,可用于药物控释、医疗器械等领域。然而,PCL因强度不高、降解缓慢、水溶性差且无功能基团,使其应用领域受限。因而,对PCL进行改性非常必要。本论文以膦腈碱(t-BuP4)为催化剂,通过己内酯(CL)与碳酸乙烯酯(DOO)或N,N-二-甲基丙烯酸二甲氨基乙酯(DEM)的共聚,SiO2纳米球引发己内酯开环聚合等方法对PCL其进行化学改性,我们研究了多种反应条件对所制备共聚物的结构和性能的影响。主要工作如下:
     以t-BuP4为催化剂,通过开环共聚,合成己内酯(CL)与碳酸乙烯酯(DOO)的无规共聚物poly(CL-co-EC-co-EO)。通过核磁(NMR)、红外(FTIR)、凝胶色谱(GPC)等测试分析表征了共聚物的结构组成,研究了聚合反应中两单体的摩尔投料比、反应温度和催化剂含量等条件对共聚物的结构组成及分子量的影响。通过广角X射线衍射(WAXD)(?)口差示扫描量热仪(DSC)我们观察了高CL含量共聚物的结晶热力学行为,同时我们也利用石英晶体微天平仪器(QCM)研究了共聚物的降解过程,发现与DOO单体共聚,显著加快了聚己内酯的降解速率,且共聚物呈均匀方式降解。
     以t-BuP4为催化剂,通过杂化共聚,合成了己内酯(CL)和N,N-二甲基丙烯酸二甲氨基乙酯(DEM)的无规共聚物poly(CL-co-DEM)。在此基础上将共聚物与磺内酯两性离子化反应,我们制备了两性离子化共聚物(或离聚物)。通过NMR、 FTIR、GPC等测试分析验证了该共聚物和离聚物的结构组成。通过WAXD和DSC我们观察了高CL含量共聚物的结晶热力学行为。和DEM杂化共聚降低了CL结构单元的排列能力,使得结晶度降低。利用激光光散射(LLS)和石英晶体微天平(QCM),我们研究了共聚物和两性离子化共聚物的自组装行为及其表面的蛋白吸附现象,证明两性离子化共聚物阻抗蛋白性能好。
     以t-BuP4为催化剂,通过表面羟基引发CL开环聚合,成功制备了SiO2表面接枝聚己内酯的复合纳米球SiO2-g-PCL,并用FTIR、NMR、TEM和光电子能谱(XPS)等方法表征了其结构形貌。同时也研究了该PCL/SiO2复合材料的结晶和降解行为,证明硅球影响PCL结晶温度(Tc)、熔融温度(Tm)和玻璃化转变温度(Tg),其降解速率明显加快且呈非均匀方式降解。而且也采用MTT技术检测了SiO2-g-PCL纳米球是生物低毒的。
     同时,为了与SiO2表面引发开环聚合对比,并开拓其相关应用,我们首先制备含胺基的纳米球SiO2-NH2,然后与葵二胺和葵二酸原位成盐,熔融缩聚制备了PA1010/SiO2-NH2(SNPA)复合材料。氨基化的硅球参与原位熔融缩聚反应,生成PA1010接枝的纳米球(SiO2-g-PA1010)。它作为物理交联剂,可均匀分散在PA1010基体中,与纯PA1010相比,PA1010/SiO2-NH2(SNPA)复合材料呈现更高的Tc和Tg,且其拉伸强度(6s)和储存模量(E')也有提高。
Poly(ε-caprolactone)(PCL), a biodegradable and biocompatible polymer, has found applications in drug delivery device, medical apparatus and other environmentally friendly materials. However, because of its slow degradation, poor water-solubility and the lack of functional groups along the polyester backbone, their biomedical applications are limited. So it is necessary to study on chemical modification and properties of PCL. In this Ph.D. thesis, we have successfully synthesized the copolymers of ε-caprolactone(CL) and1,3-dioxolan-2-one(DOO)(or N,N-dimethylaminoethyl methacrylate(DEM)) with the catalyst of metal-free phosphazene base (t-BUP4). Meantime we initiated ring-opening polymerization of e-caprolactone on SiO2nanosphere surface with the catalyst (t-BuP4). We have investigated chemical modification and properties of PCL. More specifically, we have
     1. synthesized the poly(CL-co-EC-co-EO) copolymer via ring-opening copolymerization of CL and DOO with the initiator. The copolymers have been characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), polarizing optical micrograph (POM), differential scanning calorimeter (DSC) and wide-angle X-ray diffraction (WAXD). Such poly(CL-co-EC-co-EO) copolymer is random. The effects of the monomer feed ratio, temperature and catalyst content on the polymerization have been examined. Moreover the enzymatic degradation of the copolymer with high CL content has been investigated by use of quartz crystal microbalance with dissipation (QCM-D). Our studies demonstrate that as the CL content decreases, the crystallinity and crystal size decrease, and the enzymatic degradation rate increases. The copolymer exhibits uniform degradation.
     2. successfully prepared the poly(CL-co-DEM) copolymers by hybrid copolymerization of CL and DEM, and obtained the polyampholyte by betainization of poly(CL-co-DEM) copolymer with1,3-propane sultone. The results of FTIR, NMR and GPC measurements indicate that the poly(CL-co-DEM) copolymer is random and amphiphilic. DSC and TGA results demonstrate that the copolymers have poor crystallinity, indicating that introducing of DEM disorganized CL segments. Meanwhile by dynamic laser light scattering (DLS) and QCM-D we study on the self-assembly behavior and protein adsorption of the copolymer and polyampholyte in phosphate buffered solution. The results show the polyampholyte has good protein resistance.
     3. initiated ring-opening polymerization of CL on well-defined SiO2nanosphere surface with the catalyst (t-BuP4). The surface molecular structure of the SiO2-g-PCL nanospheres was characterized by FTIR, NMR, XPS and TGA measurements. Crystallization behavior of PCL/SiO2nanocomposites was investigated by POM, DSC and WAXD measurements. The presence of SiO2affects the crystalline temperature (Tc), melting temperature (Tm) and the glass transition temperature (Tg) of PCL. Moreover the enzymatic degradation has been investigated by QCM-D and Our studies demonstrate that as the SiO2content increases, the enzymatic degradation is uneven with high rate.
     4. directly prepared Polyamide1010(PA1010) by in-situ melt poly condensation in the presence of-NH2nanospheres. The results of FTIR, NMR, XPS and TGA measurements demonstrate that the SiO2nanosphere is encapsulated by PA1010chains. WAXD and DSC measurements show that the PA1010/SiO2-NH2nanocomposites have a lower crystallinity (χc) in comparison to PA1010. In comparison to pure PA1010, the nanocomposites show higher Tc and Tg, and tensile strength and storage modulus also were improved.
引文
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