聚己内酯的制备及改性研究进展

综述了PCL(聚己内酯)合成的研究进展,介绍了引发ε-CL(ε-己内酯)开环聚合的几种引发体系(如活泼氢引发体系、稀土金属引发体系、碱金属引发体系和酶催化引发体系等)和辅助手段,并探讨了PCL的多种改性方法(PCL与淀粉共混改性、PCL与壳聚糖共聚改性、PCL与聚乳酸共混或共聚改性、PCL与聚醚共混或共聚改性、PCL与其他高分子材料共混或共聚改性)。最后对PCL的改性研究方向进行了展望。     

聚己内酯材料的改性及在3D打印中的应用

主要综述了通过物理和化学方法制备改性聚己内酯(PCL)的方法和所制备的改性PCL的性能,并且对PCL材料在3D打印领域中的应用也进行了介绍。由于PCL具有较好的生物相容性和韧性,并且改性的PCL也具有较为理想的强度,相应的3D打印产品可用到组织工程领域。另外,化学改性的PCL还具有一定的功能性。     

可生物降解聚己内酯材料共混改性研究进展

可生物降解材料由于其无毒、对环境友好、良好的生物相容性等特点,广泛应用于包装、医药、农业等领域。其中,聚己内酯(PCL)材料是发展较早的可生物降解材料,但纯PCL材料性能较差且价格高,限制了其广泛应用。本文揭示出共混改性是改善PCL材料性能、降低成本的有效途径,其包括PCL与合成高分子材料、天然高分子材料和无机粒子等共混改性,并对PCL材料的未来发展进行了展望。     

PLA/PCL纳米复合材料研究进展

综述了近年来聚乳酸(PLA)/聚己内酯(PCL)纳米复合材料的研究进展,重点介绍了PLA/PCL/碳纳米管、PLA/PCL/石墨烯、PLA/PCL/有机改性蒙脱土、PLA/PCL/埃洛石纳米管、PLA/PCL/纳米二氧化钛、PLA/PCL/羟基磷灰石,以及PLA/PCL/天然高分子等纳米复合材料的制备和性能.分析表明,...     

PLA/PCL/HL560生物基医用复合可降解材料的制备与性能

以可降解亲水剂HL560和聚己内酯(PCL)对聚乳酸(PLA)进行改性处理,研究了添加HL560前后PLA性能的变化情况,以及在HL560作用下PCL含量的变化对改性材料力学性能、加工性能、热行为、亲水性和降解行为的影响.结果表明,添加质量分数15％PCL和5％HL560的改性材料弯曲弹性模量比纯PLA提高46.1％,...     

形状记忆材料聚己内酯复合材料性能研究

研究了形状记忆材料聚己内酯（PCL）／超细碳酸钙复合材料的基础性能,研究结果表明,采用超细碳酸钙改性PCL,可以在保持PCL原有形状记忆性能基本不变的情况下,有效地提高复合材料的刚性.     

聚己内酯/硫酸钙晶须复合材料的力学性能研究

将硫酸钙晶须(CSW)与聚己内酯(PCL)进行共混,研究了CSW用量对PCL力学性能的影响。用硅烷偶联剂对CSW进行表面处理,研究了偶联剂用量对PCL/CSW复合材料力学性能的影响。结果表明:改性后的CSW在PCL基体中分散均匀,PCL/CSW复合材料的拉伸强度提高了25.3%,冲击强度提高了20.4%。     

聚己内酯/α-磷酸锆纳米复合多孔膜的制备及降解行为研究

利用3-氨丙基三乙氧基硅烷(APTES)对α-磷酸锆(α-Zr P)进行有机插层改性得到有机改性磷酸锆(OZr P),通过溶液共混法和热致相分离法(TIPS)制备了一种聚己内酯(PCL)/OZr P纳米复合多孔膜。通过X射线衍射仪(XRD)和傅里叶变换红外光谱仪(FTIR)分别研究了α-Zr P改性前后的物理结构、化学变化以及改性机理。通过扫描电镜(SEM)观察纳米复合多孔膜及其不同降解时间后的表面形貌,发现膜表面形成了尺寸均匀的纳米孔洞,孔径约为200~400 nm。采用质量亏损法来表征膜材料的降解,考察PCL、PCL/OZr P纳米复合多孔膜在相同降解环境下的降解速率。结果表明:PCL及PCL/OZr P纳米复合多孔膜在碱性溶液中降解性能最佳,降解60天其质量损失率可达100%。     

热塑性改性淀粉热熔胶制备

利用自改性热塑性淀粉与接枝后的PCL为基础原料,以环烷油为增塑剂,氢化石油树脂或氢化松香树脂为增粘剂,辅以抗氧化剂,加热混合配制得到一种新型热塑性淀粉热熔胶,研究了不同改性物、不同接枝基团、不同接枝比例对热塑性淀粉热熔胶的粘接性能的影响。对涂布后胶带的初粘力和剥离强度进行测试。结果表明,当淀粉改性物由甘油、甲酰胺、尿素混合组成,加上接枝基团为PAA,接枝比例在10.8%左右的PCL,最后得到的热塑性淀粉热熔胶具有优异的初粘力、持粘力及剥离强度。     

环氧改性生物降解聚氨酯弹性体的合成和性能研究

由聚己内酯（PCL）和聚乙二醇（PEG）分别与1,6-亚甲基二异氰酸酯（HDI）合成端异氰酸酯基聚氨酯,再与缩水甘油反应制备环氧改性聚氨酯（EUP）;六亚甲基二胺（1,6-己二胺,HMDA）作固化剂,与环氧改性聚氨酯（EUP）反应合成生物降解聚氨酯弹性体。这种弹性体的生物降解率可控制,物理性能优良。常规方法进行表征。结果表明,PEG基弹性体的降解性能优于PCL基弹性体,而机械性能则低于PCL基弹性体;PCL和PEG混合制备的EUP降解性能和机械性能最佳。     

Mechanical properties of poly(ε-caprolactone) composites with electrospun cellulose nanofibers surface modified by 3-aminopropyltriethoxysilane

To enhance the reinforcement effects of regenerated cellulose nanofibers (RC-NF) in poly(ε-caprolactone) (PCL), we synthesized RC-NF-3-aminopropyltriethoxysilane (APS), the surface-modified RC-NF by APS. The RC-NF were fabricated by the saponification of electrospun cellulose–acetate nanofibers. The surface modification by APS was confirmed by the X-ray photoelectron spectroscopy (XPS). To enhance the mechanical property of PCL, the RC-NF and the RC-NF-APS were separately compounded into PCL by compression molding. It was found that, when the fiber concentration of RC-NF-APS was 17 wt %, the Young's modulus at room temperature increased from 698.0 to 744.7 MPa, whereas the storage modulus at 55 °C almost increased from 180 to 220 MPa. The micrographs of the fracture surface of the composites revealed that the surface modification prevented the pull-out of RC-NF from PCL. It was concluded that the mechanical properties of the composites were enhanced due to the improvement of the compatibility between RC-NF and PCL by the surface modification with APS. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48599.     

聚己内酯的辐射交联及改性研究

实验研究了多官能团单体(PFM)对聚己内酯(PCL)的辐射交联效应及对PCL的力学性能的影响。结果表明,在相同辐照剂量时,多官能团单体的用量越大,官能团数目越多,所生成凝胶含量越多,辐照交联效应越明显。并研究了无机羟基磷酸钙粉末(CPP)作填料时对PCL的增强作用,发现随着CPP用量的增加,共混物的拉伸强度提高,但对PCL的辐射交联没有影响。     

Functionalization of agglomerating nanodiamonds with biodegradable poly(ε-caprolactone) through surface-initiated polymerization

Nanodiamond (ND) has been widely used in various applications because of its unique and outstanding properties. However, serious aggregation of ND limits its further applications. Two approaches, namely, hexamethylene diisocyanate (HDI) modification and acyl chloride modification, were developed to graft biodegradable poly(ε-caprolactone) (PCL) from ND surface through ring-opening polymerization of ε-caprolactone (CL) initiated by tin(II) 2-ethylhexanoate. Both FTIR and Raman results reveal that the PCL chains are covalently bonded to the NDs, and the proportion by weight of PCL gains 21.47% and 24.21%, respectively, as determined by thermogravimetric analysis. The functionalized NDs with long biopolymer chains can be easily and stably dispersed in various solvents. Dynamic light scattering analysis, TEM images, dispersion stability test and CDD images demonstrate that the dispersion and hydrophobicity of NDs have been significantly improved after modification with PCL. The NDs modified by PCL provide a new method to functionalize and deaggregate ND particles, and thus a new prospect of multipurpose applications both in biomedical systems and in other fields.     

Natural weathering of spruce wood chemically modified by re-used ε-caprolactone solution

Increasing environmental pressures over the last few years have led to attention for non-biocide treatments in the wood protection field. The ε-caprolactone modification of wood by substitution or blocking of hydroxyl groups with hydrophobic poly(ε-caprolactone) (PCL) is one of the novel modification methods developed in recent years. In this study, ring-opening polymerisation of ε-caprolactone in wood cell walls was evaluated by the third and sixth re-use of recovered monomer and by oven-curing method. Spruce samples were modified by re-used ε-caprolactone and exposed to the natural weathering agents for 12 months. After weathering, the colour change, surface roughness measurements, and macroscopic and ultra-microscopic observations revealed that the modified wood had better surface properties than reference wood. Fourier-transform infrared (FTIR) analysis proved that PCL could be found on the weathered surface up to the sixth month, but very little amount was detected on the surfaces with a longer weathering period. The results clearly showed that the efficiency of PCL modification with re-use of the monomer solution was sufficient during the initial weathering periods, but efficiency was reduced after a prolonged exposure period.     

Shape memory properties of olefin block copolymer (OBC)/poly(ɛ‐caprolactone) (PCL) blends

Conventionally, the chemically crosslinked shape memory polymer (SMP) blends are hard to recycle due to their network structure. Herein, the environmental SMP blends of olefin block copolymer (OBC), a unique thermoplastic elastomer, and poly(?‐caprolactone) (PCL) were physically crosslinked. Dicumyl peroxide was used as the compatibilizer to improve their miscibility, as evidenced by the reduced dispersed domain size of PCL in the OBC matrix and the increased complex viscosity. The peroxide modified OBC/PCL blend conferred enhanced tensile properties, increased dynamic storage modulus, increased crystallization temperature, and higher recovery stress. The shape memory behaviors of OBC/PCL blends predeformed under two different predeformation temperatures (30 and 65 °C) were investigated. The recovery stress showed respective maximum peak values corresponding to their predeformation temperatures. In addition, the modified blends gave the better shape memory performance at 65 °C. Besides the peroxide modification approach, a precycle training process via prestretching the samples and reducing the mechanical hysteresis was implemented to improve shape memory performance further. This is the first work on the OBC‐based SMP blends to enhance shape memory performance by combining the chemical modification using added peroxide compatibilizer and the process modification using a precycle training process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45475.     

聚己内酯/有机蒙脱土纳米复合材料的制备与性能表征

以十六烷基三甲基溴化铵(CTAB)为有机改性剂处理钠基蒙脱土(Na-MMT),制备了有机蒙脱土(CTAB-MMT),再以CTAB-MMT为插层剂,通过熔融挤出制备了聚己内酯(PCL)/CTAB-MMT纳米复合材料。采用SEM和XRD对MMT和纳米复合材料的结构进行了表征,并测试了纳米复合材料的力学性能。结果表明:CTAB-MMT的片层结构比Na-MMT连续性更好,片层间距由原来的1.51nm增加到1.95～3.32nm;CTAB-MMT在PCL基体中分散更均匀;与纯PCL相比,PCL/CTAB-MMT纳米复合材料的拉伸强度提高了10.2%,而弯曲强度提高了19.5%。     

Thermoforming starch‐graft‐polycaprolactone biocomposites via one‐pot microwave assisted ring opening polymerization

A thermoformable starch‐graft‐polycaprolactone biocomposite was prepared by initiating ring‐open polymerization of caprolactone monomer onto starch under microwave irradiation. In this case, the thermoplastic and hydrophobic modification of starch could be realized by one‐pot grafting PCL, where the grafted PCL chains acted as the “plasticizing” tails of thermoforming and as the hydrophobic species of water‐resistance. The resultant biocomposites were injection‐molded as the sheets and their structure and properties were investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical analysis, contact angle measurement, and tensile testing. In this case, the grafted PCL chains entangled each other, and hence contributed to the strength and elongation of biocomposites. This work provided a simple strategy of one‐pot thermoplastic and hydrophobic modification of starch, and may be applied in a continuous process of modification, compounding, and molding. Meanwhile, the resultant biocomposites containing starch are believed to have a great potential application as an environment‐friendly and/or biomedical material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Bone morphogenetic protein‐2 immobilization on porous PCL‐BCP‐Col composite scaffolds for bone tissue engineering

The objective of this study was to develop novel porous composite scaffolds for bone tissue engineering through surface modification of polycaprolactone–biphasic calcium phosphate‐based composites (PCL–BCP). PCL–BCP composites were first fabricated with salt‐leaching method followed by aminolysis. Layer by layer (LBL) technique was then used to immobilize collagen (Col) and bone morphogenetic protein (BMP‐2) on PCL–BCP scaffolds to develop PCL–BCP–Col–BMP‐2 composite scaffold. The morphology of the composite was examined by scanning electron microscopy (SEM). The efficiency of grafting of Col and BMP‐2 on composite scaffold was measured by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Both XPS and FTIR confirmed that Col and BMP‐2 were successfully immobilized into PCL–BCP composites. MC3TC3‐E1 preosteoblasts cells were cultivated on composites to determine the effect of Col and BMP‐2 immobilization on cell viability and proliferation. PCL–BCP–Col–BMP‐2 showed more cell attachment, cell viability, and proliferation bone factors compared to PCL–BCP‐Col composites. In addition, in vivo bone formation study using rat models showed that PCL–BCP–Col–BMP‐2 composites had better bone formation than PCL–BCP‐Col scaffold in critical size defect with 4 weeks of duration. These results suggest that PCL–BCP–Col–BMP‐2 composites can enhance bone regeneration in critical size defect in a rat model with 4 weeks of duration. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45186.     

Influence of thermal stabilizers on diffusion of poly(ϵ-caprolactone) in poly(vinyl chloride)/poly(ϵ-caprolactone) blends

The influence of thermal stabilizers on the poly(ϵ-caprolactone) (PCL) diffusion in poly(vinyl chloride) (PVC)/PCL blends was studied with the addition of various concentrations of dibasic lead phthalate and dibutyltin dilaurate. The rate of PCL diffusion was followed by differential scanning calorimetry and IR spectroscopy in three series of experiments: the migration of PCL at the surface of the sample; the extraction of PCL in a fluid surrounding the sample; and the sorption of liquid PCL in the blend. In the last two series, mass losses and mass uptakes were measured as a function of time. As compared to the blend without additive, dibutyltin dilaurate induces an increase of the PCL rate of diffusion whereas dibasic lead phthalate gives a decrease. These trends are explained by: first, the formation of an associative complex between dibutyltin dilaurate and PVC, which can compete with the PVC/PCL interactions in the blend and thus favor the PCL migration; and, second, the modification of the T_g of the blend induced by the addition of a third component, which can modify the diffusion rate by changing the free volume fraction at the diffusion temperature. T_g decreases slightly in the presence of dibutyltin dilaurate but increases with dibasic lead phthalate. © 1996 John Wiley & Sons, Inc.     

Poly(ϵ‐caprolactone)‐functionalized carbon nanofibers by surface‐initiated ring‐opening polymerization

Carbon nanofibers (CNFs) were covalently functionalized with biodegradable poly(?‐caprolactone) (PCL) by in situ ring‐opening polymerization (ROP) of ?‐caprolactone in the presence of stannous octoate. Surface oxidation treatment of the pristine CNFs afforded carboxylic CNFs (CNF‐COOH). Reaction of CNF‐COOH with excess thionyl chloride (SOCl₂) and glycol produced hydroxyl‐functionalized CNFs (CNF‐OH). Using CNF‐OH as macroinitiator, PCL was covalently grafted from the surfaces of CNFs by ROP, in either the presence or absence of sacrificial initiator, butanol. The grafted PCL content was achieved as high as 64.2 wt %, and can be controlled to some extent by adjusting the feed ratio of monomer to CNF‐OH. The resulting products were characterized by FTIR, NMR, Raman spectroscopy, TGA, DSC, SEM, TEM, HRTEM, and XRD. Core–shell nanostructures were observed under HRTEM for the PCL‐functionalized CNFs because of the thorough grafting. The PCL‐grafted CNFs showed different melting and crystallization behaviors from the mechanical mixture of PCL and CNF‐OH. This approach to PCL‐functionalized CNFs opens an avenue for the synthesis, modification, and application of CNF‐based nanomaterials and biomaterials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007