通过添加小分子尿素制备了聚己内酯(PCL)/尿素复合物,以期改变PCL的结晶性能。利用显微熔点、X射线衍射(XRD)、差示扫描量热法(DSC)、偏光显微镜(POM)等手段研究了PCL/尿素复合物的熔程、结晶度、结晶形态以及结晶过程,通过傅里叶变换红外光谱仪分析了PCL/尿素复合物的结构。结果表明:PCL及其复合物的结晶形态均为球晶,复合物球晶的密集程度较纯PCL明显增加,随着尿素含量增加,球晶尺寸变小;PCL/尿素复合物的结晶度相比纯PCL略有降低;尿素的加入使PCL熔程变窄。这是由于尿素与PCL间产生了氢键,并起到了成核剂的作用。
PCL/urea complex was prepared by adding small molecular urea to improve the crystallinity of PCL.The melting range,crystallinity,crystal morphology and crystallization process of complex were studied by micro-melting point,X-ray diffraction (XRD),differential scanning calorimetry (DSC) and polarizing microscopy (POM).The structure of complexe was studied by fourier transform infrared spectroscopy (FT-IR).The results showed that the crystal morphology of PCL and its complex were spherulite,and the density of spherulite in complex was higher than pure PCL.The size of spherulite became smaller with the increase of urea content.The crystallinity of complex was slightly lower than pure PCL.The adding of urea narrowed the melting range of PCL.This was due to the hydrogen bonding between urea and PCL,and urea played a role in the nucleating agent.
[1] Coombes A G A,Rizzi S C,Williamson M,et al.Precipitation casting of polycaprolactone for applications in tissue engineering and drug delivery[J].Biomaterials,2004,25(2):315-325.
[2] PotrČT,Baumgartner S,Roškar R,et al.Electrospun polycaprolactone nanofibers as a potential oromucosal delivery system for poorly water-soluble drugs[J].Eur J Pharm Sci,2015,75:101-113.
[3] Karuppuswamy P,Venugopal J R,Navaneethan B,et al.Polycaprolactone nanofibers for the controlled release of tetracycline hydrochloride[J].Mater Lett,2015,141:180-186.
[4] Pilipchuk S P,Monje A,Jiao Y,et al.Integration of 3D printed and micropatterned polycaprolactone scaffolds for guidance of oriented collagenous tissue formation in vivo[J].Adv Healthc Mater,2016,5(6):676-687.
[5] Chen C H,Chen S H,Shalumon K T,et al.Prevention of peritendinous adhesions with electrospun polyethylene glycol/polycaprolactone nanofibrous membranes[J].Colloid Surface B,2015,133:221-230.
[6] Gao X,Song J,Zhang Y,et al.Bioinspired design of polycaprolactone composite nanofibers as artificial bone extracellular matrix for bone regeneration application[J].ACS Appl Mater Inter,2016,8(41):27594-27610.
[7] Lanfranconi M,Alvarez V A,Ludueña L N.Isothermal crystallization of polycaprolactone/modified clay biodegradable nanocomposites[J].J Therm Anal Calorim,2016,126(3):1273-1280.
[8] López J V,Pérez-Camargo R A,Zhang B,et al.The influence of small amounts of linear polycaprolactone chains on the crystallization of cyclic analogue molecules[J].RSC Adv,2016,6(53):48049-48063.
[9] Yilgör E,Isik M,Söz C K,et al.Synthesis and structure-property behavior of polycaprolactone-polydimethylsiloxane-polycaprolactone triblock copolymers[J].Polymer,2016,83:138-153.
[10] 乔从德,蒋世春,姬相玲,等.聚ε-己内酯薄膜的受限结晶行为研究[J].高分子学报,2006(8):964-969.
[11] Borsacchi S,Paderni K,Messori M,et al.Insights into shape-memory poly(ε-caprolactone) materials by solid-state NMR[J].Macromolecules,2014,47(11):3544-3552.
[12] Alvarado-Tenorio B,Romo-Uribe A,Mather P T.Microstructure and phase behavior of POSS/PCL shape memory nanocomposites[J].Macromolecules,2011,44(14):5682-5692.
基金资助
国家自然科学基金(21473126)
PDF
(4365KB)
