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1.
The influence of processing conditions during melt extrusion on the degradation of poly(L ‐lactide) (PLLA) has been investigated. PLLA polymer was processed by melt extrusion in a double screw extruder at 210 and 240°C. For each extrusion temperature, two screw rotation speeds, 20 and 120 rpm, were used. To investigate the influence of moisture on the thermal degradation during processing, the PLLA granules were dried at 100°C for 5 h and then either extruded directly or conditioned at 65% RH, 20°C for 24 h prior to extrusion. The results show that a decrease in molecular weight measured as number‐average (Mn) molecular weight occurs for all combinations of process parameters used. At processing temperature of 210°C, the change in molecular weight for the dry granules was shown to be dependent on the residence time (i.e., screw rotation speed) in the melt. By changing the screw rotation speed from 120 to 20 rpm at 210°C, Mn decreased from 33,600 to 30,200 g/mol. When the processing temperature was increased to 240°C, the dry granules showed an Mn of 25,600 and 13,600 g/mol when extruded at 120 and 20 rpm, respectively. Mn for the conditioned specimens extruded at 210°C was 18,400 g/mol when processed at 120 rpm and 12,300 g/mol at 20 rpm. When processed at 240°C, 20 rpm, Mn is independent of whether the granules were dry or moist prior to extrusion. It is probably due to the fact that the degradation at 240°C is so extensive that the presence of moisture in the polymer does not contribute further to the degradation process. The stress and strain at break decreased due to degradation and were dependent on the molecular weight of the samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2128–2135, 2001 相似文献
2.
Sunny M. Ogbomo Kent Chapman Charles Webber Robert Bledsoe Nandika A. D'Souza 《应用聚合物科学杂志》2009,112(3):1294-1301
Bast fibers from stems of kenaf (Hibiscus cannabinus, L.), a warm‐season tropical herbaceous annual plant, were dispersed into poly‐L ‐lactide (PLLA) matrix by melt‐mixing followed by compression molding. Low fiber fractions (1–5%) were investigated. The composites showed a slight lowering of thermal stability when evaluated by thermogravimentric analysis. X‐ray diffraction and differential scanning calorimetry indicated an influence of kenaf on the crystallization of PLLA. The fiber dispersion in the polymer matrix was established by polarized optical microscopy. Scanning electron microscopy showed good fiber–matrix adhesion as revealed by the combination of dispersion, interaction, and crystallinity, which enabled an increase in the mechanical properties of the composite that scaled with concentration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
3.
Linear (1‐arm) and star‐shaped (4‐, 6‐, and 16‐arm) poly(D,L ‐lactide)s (PDLLs) were synthesized by ring‐opening polymerization in bulk of D,L ‐lactide monomer. Hydroxyl end‐group compounds and stannous octoate were used as the initiator and catalyst, respectively. The intrinsic viscosity and glass transition temperature (Tg) of the PDLLs decreased steadily as the branch arm number increased for similar molecular weights. However, the intrinsic viscosity and Tg values of the linear PDLL were less than the star‐shaped PDLL for similar each PDLL arm lengths. Ibuprofen, a poorly water soluble model drug was entrapped in the PDLL microspheres. All drug‐loaded PDLL microspheres were prepared by the oil‐in‐water emulsion solvent evaporation method, were spherical in shape, and had a smooth surface with fine dispersibility. In vitro drug release behaviors indicated that the drug release from the microspheres with higher branch arm number was faster than from those with lower branch arm number. Moreover, the drug release from the star‐shaped PDLL microspheres was slower than that of the linear PDLL microspheres for similar PDLL arm lengths. The drug release behavior could be adjusted through both the branch arm number and arm length of PDLL. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
4.
Microspheres consisting of carbonated hydroxyapatite (CHAp) nanoparticles and poly(L ‐lactide) (PLLA) have been fabricated for use in the construction of osetoconductive bone tissue engineering scaffolds by selective laser sintering (SLS). In SLS, PLLA polymer melts and crystallizes. It is therefore necessary to study the crystallization kinetics of PLLA/CHAp nanocomposites. The effects of 10 wt% CHAp nanoparticles on the isothermal and nonisothermal crystallization behavior of PLLA matrix were studied, using neat PLLA for comparisons. The Avrami equation was successfully applied for the analysis of isothermal crystallization kinetics. Using the Lauritzen‐Hoffman theory, the transition temperature from crystallization Regime II to Regime III was found to be around 120°C for both neat PLLA and PLLA/CHAp nanocomposite. The combined Avrami‐Ozawa equation was used to analyze the nonisothermal crystallization process, and it was found that the Ozawa exponent was equal to the Avrami exponent for neat PLLA and PLLA/CHAp nanocomposite, respectively. The effective activation energy as a function of the relative crystallinity and temperature for neat PLLA and PLLA/CHAp nanocomposite under the nonisothermal crystallization condition was obtained by using the Friedman differential isoconversion method. The Lauritzen‐Hoffman parameters were also determined from the nonisothermal crystallization data by using the Vyazovkin‐Sbirrazzuoli equation. CHAp nanoparticles in the composite acted as an efficient nucleating agent, enhancing the nucleation rate but at the same time reducing the spherulite growth rate. This investigation has provided significant insights into the crystallization behavior of PLLA/CHAp nanocomposites, and the results obtained are very useful for making good quality PLLA/CHAp scaffolds through SLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
5.
Triacetin (TAC) is known as a lubricant of poly(L ‐lactide) (PLLA), and it is used to improve the mechanical properties of PLLA. However, the compatibility of TAC with PLLA and the morphological changes induced by the addition of TAC to PLLA have not been clarified. This study investigates the effects of the addition of TAC on the morphological changes and physical properties of PLLA. We prepared the PLLA films containing a given amount of TAC by solvent‐cast blending with chloroform under a low temperature. From the investigation of the mechanical properties of the blends, it is found that the glass‐transition temperature of PLLA is remarkably decreased with an increasing amount of TAC, the blend films exhibit high elastic recovery, and the degree of the recovery increases linearly with the amount of TAC. The morphological changes exhibiting high elastic recovery are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 474–480, 2003 相似文献
6.
Poly(L‐lactide)‐poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. The reaction was carried out under mild conditions, using dicyclohexylcarbodiimide as the coupling agent and dimethylaminopyridine as the catalyst. The resulting copolymers were characterized by various analytical techniques, such as GPC, viscometry, 1H‐NMR, FTIR, DSC, X‐ray diffractometry, and contact angle measurement. The results indicated that these copolymers presented outstanding properties pertinent to biomedical use, including better miscibility between the two components, low crystallinity, and hydrophilicity. Moreover, the properties of the copolymers can be modulated by adjusting the block length of the two components or the reaction conditions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1729–1736, 2002; DOI 10.1002/app.10580 相似文献
7.
Pengju Pan Bo Zhu Weihua Kai Shin Serizawa Masatoshi Iji Yoshio Inoue 《应用聚合物科学杂志》2007,105(3):1511-1520
Bio‐based polymer composite was successfully fabricated from plant‐derived kenaf fiber (KF) and renewable resource‐based biodegradable polyester, poly(L ‐lactide) (PLLA), by melt‐mixing technique. The effect of the KF weight contents (0, 10, 20, and 30 wt %) on crystallization behavior, composite morphology, mechanical, and dynamic mechanical properties of PLLA/KF composites were investigated. It was found that the incorporation of KF significantly improves the crystallization rate and tensile and storage modulus. The crystallization of PLLA can be completed during the cooling process from the melt at 5°C/min with the addition of 10 wt % KF. It was also observed that the nucleation density increases dramatically and the spherulite size drops greatly in the isothermal crystallization with the presence of KF. In addition, with the incorporation of 30 wt % KF, the half times of isothermal crystallization at 120°C and 140°C were reduced to 46.5% and 28.1% of the pure PLLA, respectively. Moreover, the tensile and storage modulus of the composite are improved by 30% and 28%, respectively, by the reinforcement with 30% KF. Scanning electron microscopy observation also showed that the crystallization rate and mechanical properties could be further improved by optimizing the interfacial interaction and compatibility between the KF and PLLA matrix. Overall, it was concluded that the KF could be the potential and promising filler for PLLA to produce biodegradable composite materials, owing to its good ability to improve the mechanical properties as well as to accelerate the crystallization of PLLA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 相似文献
8.
Poly(ethylene glycol)‐poly(L ‐lactide) diblock and triblock copolymers were prepared by ring‐opening polymerization of L ‐lactide with poly(ethylene glycol) methyl ether or with poly(ethylene glycol) in the presence of stannous octoate. Molecular weight, thermal properties, and crystalline structure of block copolymers were analyzed by 1H‐NMR, FTIR, GPC, DSC, and wide‐angle X‐ray diffraction (WAXD). The composition of the block copolymer was found to be comparable to those of the reactants. Each block of the PEG–PLLA copolymer was phase separated at room temperature, as determined by DSC and WAXD. For the asymmetric block copolymers, the crystallization of one block influenced much the crystalline structure of the other block that was chemically connected to it. Time‐resolved WAXD analyses also showed the crystallization of the PLLA block became retarded due to the presence of the PEG block. According to the biodegradability test using the activated sludge, PEG–PLLA block copolymer degraded much faster than PLLA homopolymers of the same molecular weight. © 1999 John Wiley amp; Sons, Inc. J Appl Polym Sci 72: 341–348, 1999 相似文献
9.
Wei Bai Zhi‐ping Zhang Qing Li Dong‐Liang Chen He‐Chun Chen Na Zhao Cheng‐Dong Xiong 《Polymer International》2009,58(2):183-189
BACKGROUND: Poly(para‐dioxanone) (PPDO) is a biodegradable polyester with excellent biodegradability, bioabsorbability, biocompatibility and mechanical flexibility. However, its high cost and relatively fast degradation rate have hindered the development of commercial applications. Blending with other polymers is a simple and convenient way of modifying the properties of aliphatic polyesters. Poly(D ,L ‐lactide) (PDLLA) is another polyester that has been extensively studied for biomedical applications due to its biocompatibility and suitable degradation rate. However, to our knowledge, blends of PPDO/PDLLA have not been reported in the literature. RESULTS: A series of biodegradable polymers were blended by solution co‐precipitation of PPDO and PDLLA in various blend ratios. The miscibility, morphology and thermal properties of the materials were investigated. DSC curves for all blends revealed two discrete glass transition temperatures which matched the values for pure PPDO and PDLLA. SEM images of fracture surfaces displayed evidence of phase separation consistent with the DSC results. The contact angles increased with the addition of PDLLA. CONCLUSION: PPDO/PDLLA blends exhibit two distinct glass transition temperatures that remain nearly constant and correspond to the glass transition temperatures of the homopolymers for all blend compositions, indicating that blends of PPDO and PDLLA are immiscible. Images of the surface obtained using SEM were also suggestive of a two‐phase material. The crystallinity of the PPDO phase in the blends was affected by the PDLLA content. The mechanical properties of the blends changed dramatically with composition. Adding PDLLA makes the blends less hydrophilic than PPDO. Copyright © 2008 Society of Chemical Industry 相似文献
10.
Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (Tg's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by 13C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. 13C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001 相似文献
11.
为了改善聚乳酸(PLLA)的组织相容性及细胞亲和性,提高盐酸乌拉地尔生物利用率,文中在催化剂4-(二甲胺基)吡啶与N,N'-二环己基碳酰亚胺共同作用下,将含亲水基团的碱性聚电解质壳聚糖(CS)与PLLA共聚,制备了聚乳酸-壳聚糖接枝共聚物(PLCS),采用溶剂挥发法制备盐酸乌拉地尔PLCS微球并对其结构进行了表征,同时对微球的包封率和药物释放进行了测试。通过有机相加入乙醇的方法可以提高微球对药物的包封率。结果表明,当无水乙醇与三氯甲烷的体积比为1∶2时,制得的微球包封率最高,达到34.86%。体外药物释放结果表明,PLCS微球具有明显的缓释作用,其释药动力学满足Higuchi方程。 相似文献
12.
A series of biodegradable polylactide‐based polyurethanes (PLAUs) were synthesized using PLA diol (Mn = 3200) as soft segment, 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI) as hard segment, and 1,4‐butanediol as chain extender. The structures and properties of these PLAUs were studied using infrared spectroscopy, differential scanning calorimetry, tensile testing, and thermomechanical analysis. Among them, the MDI‐based PLAU has the highest Tg, maximum tensile strength, and restoration force, the TDI‐based PLAU has the lowest Tg, and the IPDI‐based PLAU has the highest tensile modulus and elongation at break. They are all amorphous. The shape recovery of the three PLAUs is almost complete in a tensile elongation of 150% or a twofold compression. They can keep their temporary shape easily at room temperature (20 °C). More importantly, they can deform and recover at a temperature below their Tg values. Therefore, by selecting the appropriate hard segment and adjusting the ratio of hard to soft segments, they can meet different practical demands for shape memory medical devices. Copyright © 2007 Society of Chemical Industry 相似文献
13.
Hybrids of poly(L‐lactide)/organoclay (PLACHs) have been prepared via a melt‐compounding process using poly(L‐lactide) (PLLA) and three types of surface‐treated montmorillonite modified with ammonium salts (M1, trimethyl octadecyl‐; M2, dimethyl dioctadecyl‐, and M3, bis(4‐hydroxy butyl) methyl octadecyl‐ammonium). The dispersed state of the clay particles in the PLLA matrix was examined by use of wide‐angle X‐ray diffraction, transmission electron microscopy, and polarizing optical microscopy. On melt‐compounding PLLA and two organoclays (M1, M2) modified with the surfactants both carrying homogenous alkyl chains, we obtained intercalated hybrids with relatively uniform dispersion of nanometer‐sized clay particles. On the other hand, the organoclay (M3) modified with a surfactant carrying alkyl chains end‐capped with hydroxyl groups yielded the composite with flocculated particles. The flocculation of the particles originates from the hydrogen bonding among the hydroxyl groups of the component surfactant, those of the clay edge and those of both ends of PLLA chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2711–2720, 2004 相似文献
14.
Optically active poly(L ‐phenyllactic acid) (Ph‐PLLA), poly(L ‐lactic acid) (PLLA), and poly(L ‐phenyllactic acid‐co‐L ‐lactic acid) with weight‐average molecular weight exceeding 6 × 103 g mol?1 were successfully synthesized by acid catalyzed direct polycondensation of L ‐phenyllactic acid and/or L ‐lactic acid in the presence of 2.5–10 wt % of p‐toluenesulfonic acid. Their physical properties and crystallization behavior were investigated by differential scanning calorimetry, thermogravimetry, and polarimetry. The absolute value of specific optical rotation ([α]) for Ph‐PLLA (?38 deg dm?1 g?1 cm3) was much lower than that of [α] for PLLA (?150 deg dm?1 g?1 cm3), suggesting that the helical nature was reduced by incorporation of bulky phenyl group. PLLA was crystallizable during solvent evaporation, heating from room temperature, and cooling from the melt. Incorporation of a very low content of bulky phenyllactyl units even at 4 mol % suppressed the crystallization of L ‐lactyl unit sequences during heating and cooling, though the copolymers were crystallizable for L ‐phenylactyl units up to 6 mol % during solvent evaporation. The activation energy of thermal degradation (ΔEtd) for Ph‐PLLA (200 kJ mol?1) was higher than that for PLLA (158 kJ mol?1). The ΔEtd for the copolymers increased with an increase in L ‐phenyllactyl unit content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
15.
Ye Tian Chong Dai Huaiyu Ding Qingze Jiao Lihua Wang Yanqiao Shi Biqian Liu 《Polymer International》2007,56(7):834-839
The fabrication of honeycomb‐patterned films from amphiphilic poly(L ‐lactide)‐block‐poly(ethylene glycol) (PLEG) in a high‐humidity atmosphere is reported. The influence of the solution concentration on pattern formation was investigated. Moreover, by comparing the different conditions of fabricating regular structures between PLEG and poly(phenylene oxide), the mechanism of the regular pattern formation was studied. Finally, by adding sodium dodecylsulfate to a concentrated solution of 1 g L?1 PLEG? CHCl3 which otherwise could not form regular pores, we found that regular pores could be obtained. The PLEG honeycomb films are expected to be of use in cell culture, tissue engineering and many other areas. Copyright © 2007 Society of Chemical Industry 相似文献
16.
Jorge Luis Escobar Ivirico Manuel Salmerón‐Sánchez José Luis Gómez Ribelles Manuel Monleón Pradas 《Polymer International》2011,60(2):264-270
New biodegradable block copolymer networks were synthesized from methacrylate‐terminated poly(L ‐lactide) (mLA) and polycaprolactone (mCL) macromers. This allowed the realization of a series of materials in which the macromer ratio can be used to tailor the physical and mechanical properties of the materials. The synthesis of the macromers was characterized using Fourier transform infrared (FTIR) spectroscopy and 1H NMR spectroscopy. Poly(mCL) and poly(mLA) networks were prepared by photopolymerization of the macromers, and copolymers were also prepared from the two macromers in various proportions. The phase microstructure of the new systems and the network architecture were investigated using differential scanning calorimetry, FTIR spectroscopy, dynamic mechanical analysis and thermogravimetry studies. Copyright © 2010 Society of Chemical Industry 相似文献
17.
Temenuzhka Yovcheva Mariya Marudova Asya Viraneva Elena Gencheva Nikola Balabanov Georgi Mekishev 《应用聚合物科学杂志》2013,128(1):139-144
Electret stability of poly(L ‐lactide) (PLA) films, gamma‐irradiated up to 100 kGy has been investigated by measuring the surface potential during the storage period. PLA samples—40‐μm thick films—were prepared by the casting method and then irradiated in a 60Co radiation facility at a dose rate of 0.25 kGy/h. The structural changes during the irradiation were estimated by viscometric, differential scanning calorimetry and scanning electron microscope measurements. Random chain scission and appearance of end radicals are the most probable results of the irradiation process. After irradiation, the samples were charged in a corona discharge system and surface potential was measured by the method of the vibrating electrode with compensation. The values of the surface potential of the irradiated samples were higher in comparison with the non‐irradiated samples. This effect could be related to the degradation of the macromolecules and changes in the crystal state of PLA during the irradiation. Both of the mentioned factors lead to structural defects that increase the number of discrete trapping levels. The effect of low pressure on the surface potential drop was also investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
18.
Hideto Tsuji Tamami Yamada Masakazu Suzuki Shinichi Itsuno 《Polymer International》2003,52(2):269-275
Blended films of poly(L ‐lactide) [ie poly(L ‐lactic acid)] (PLLA) and poly(?‐caprolactone) (PCL) without or mixed with 10 wt% poly(L ‐lactide‐co‐?‐caprolactone) (PLLA‐CL) were prepared by solution‐casting. The effects of PLLA‐CL on the morphology, phase structure, crystallization, and mechanical properties of films have been investigated using polarization optical microscopy, scanning electron microscopy, differential scanning calorimetry and tensile testing. Addition of PLLA‐CL decreased number densities of spherulites in PLLA and PCL films, and improved the observability of spherulites and the smoothness of cross‐section of the PLLA/PCL blend film. The melting temperatures (Tm) of PLLA and PCL in the films remained unchanged upon addition of PLLA‐CL, while the crystallinities of PLLA and PCL increased at PLLA contents [XPLLA = weight of PLLA/(weight of PLLA and PCL)] of 0.4–0.7 and at most of the XPLLA values, respectively. The addition of PLLA‐CL improved the tensile strength and the Young modulus of the films at XPLLA of 0.5–0.8 and of 0–0.1 and 0.5–0.8, respectively, and the elongation at break of the films at all the XPLLA values. These findings strongly suggest that PLLA‐CL was miscible with PLLA and PCL, and that the dissolved PLLA‐CL in PLLA‐rich and PCL‐rich phases increased the compatibility between these two phases. © 2003 Society of Chemical Industry 相似文献
19.
Changyu Han Junjia Bian Hao Liu Lijing Han Shusheng Wang Lisong Dong Shan Chen 《Polymer International》2010,59(5):695-703
A silane‐grafting water‐crosslinking approach was developed to crosslink poly(L ‐lactide) (PLLA) by grafting vinylalkoxysilane onto PLLA using dicumyl peroxide, followed by silane hydrolysis to form siloxane linkages between PLLA chains. The degree of silane grafting onto PLLA was qualitatively characterized using Fourier transform infrared spectroscopy and quantitatively determined using inductively coupled plasma mass spectrometry. Crosslinked PLLA films were obtained by curing of silane‐grafted PLLA in hot water. Gel fractions were evaluated in order to calculate the crosslinking reaction kinetics and crosslinking density. Various techniques were used to investigate the effect of silane water‐crosslinking on the thermomechanical properties, hydrolysis resistance and biodegradation of PLLA. In addition to an improvement in thermal stability and mechanical properties, hydrolysis resistance was significantly enhanced as a result of silane water‐crosslinking of PLLA. Moreover, the biodegradation of silane water‐crosslinked PLLA was retarded compared with neat PLLA. Copyright © 2010 Society of Chemical Industry 相似文献
20.
The crystalline structure of poly(L ‐lactide) (PLLA) have been found to quite depend on the crystallization temperatures (Tcs), especially in the range of 100?120°C, which is usually used as the crystallization temperature for the industrial process of PLLA. The analysis of wide‐angle X‐ray diffraction and Fourier transformed infrared spectroscopy revealed that 110°C is a critical temperature for PLLA crystallization. At Tc < 110°C and Tc ≥ 110°C, the α′ and α crystals were mainly produced, respectively. Besides, the structural feature of the α′‐form was illustrated, and it was found that the α′‐form has the larger unit cell dimension than that of the α‐form. Moreover, the crystallization kinetics of the α′ and α crystals are different, resulting in the discontinuousness of the curves of spherulite radius growth rate (G) versus Tc and the half time in the melt‐crystallization (t1/2) versus Tc investigated by Polarized optical microscope and Differential scanning calorimetry, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献