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1.
Poly(l ‐lactic acid)/crosslinked polyurethane (PLLA/CPU) blends which were prepared via reactive blending of PLLA with poly(?‐caprolactone) (PCL), glycerol and 4,4′‐methylenediphenyl diisocyanate showed excellent toughness. The effects of the composition of the mixture and degree of crosslinking of CPU on the toughness of the PLLA/CPU blends (80/20 w/w) were studied in detail. Dynamic mechanical analysis and rheological measurements were used to characterize the structure of the in situ formed CPU in the PLLA matrix. A novel netlike phase structure was observed when the average molecular weight of PCL and degree of crosslinking were 1 kDa and 10%, respectively. The impact strength of the blend was enhanced from 2.2 kJ m?2 for pure PLLA to 62.4 kJ m?2; meanwhile, the elongation at break was increased to 489.8%. Therefore, the mechanical properties of PLLA/CPU blends can be easily tailored by tuning the composition of the mixture and the degree of crosslinking of CPU. © 2018 Society of Chemical Industry  相似文献   

2.
Poly(L ‐lactic acid) (PLLA) has good biocompatibility, biodegradability and physical properties. However, one of the drawbacks of PLLA is its brittleness due to the stiff backbone chain. In this work, a largely improved tensile toughness (extensibility) of PLLA was achieved by blending it with poly(ε‐caprolactone) (PCL). To obtain a good dispersion of PCL in the PLLA matrix, blends were prepared via a solution‐coagulation method. An increase in extensibility of PLLA of more than 20 times was observed on adding only 10 wt% of PCL, accompanied by a slight decrease in tensile strength. However, annealing of the samples led to a sharp decrease of extensibility due to phase separation and a change of crystalline structure. To conserve the good mechanical properties of PLLA/PCL blends, the blends were crosslinked via addition of dicumyl peroxide during the preparation process. For the crosslinked blend films, the extensibility was maintained nearly at the original high value even after annealing. Morphological analysis of cryo‐fractured and etched‐smoothed surfaces of the PLLA/PCL blends was carried out using scanning electron microscopy. Differential scanning calorimetry and polarized light microscopy experiments were used to check the possible change of crystallinity, melting point and crystal morphology for both PLLA and PCL after annealing. The results indicated that the combination of solution‐coagulation and crosslinking resulted in a good and stable dispersion of PCL in the PLLA matrix, which is considered as the main reason for the observed improvement of tensile toughness. Copyright © 2010 Society of Chemical Industry  相似文献   

3.
The poly(ε‐caprolactone) (PCL)/starch blends were prepared with a coextruder by using the starch grafted PLLA copolymer (St‐g‐PLLA) as compatibilizers. The thermal, mechanical, thermo‐mechanical, and morphological characterizations were performed to show the better performance of these blends compared with the virgin PCL/starch blend without the compatibilizer. Interfacial adhesion between PCL matrix and starch dispersion phases dominated by the compatibilizing effects of the St‐g‐PLLA copolymers was significantly improved. Mechanical and other physical properties were correlated with the compatibilizing effect of the St‐g‐PLLA copolymer. With the addition of starch acted as rigid filler, the Young's modulus of the PCL/starch blends with or without compatibilizer all increased, and the strength and elongation were decreased compared with pure PCL. Whereas when St‐g‐PLLA added into the blend, starch and PCL, the properties of the blends were improved markedly. The 50/50 composite of PCL/starch compatibilized by 10% St‐g‐PLLA gave a tensile strength of 16.6 MPa and Young's modulus of 996 MPa, respectively, vs. 8.0 MPa and 597 MPa, respectively, for the simple 50/50 blend of PCL/starch. At the same time, the storage modulus of compatibilized blends improved to 2940 MPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

4.
Two series of biodegradable polymer blends were prepared from combinations of poly(L ‐lactide) (PLLA) with poly(?‐caprolactone) (PCL) and poly(butylene succinate‐co‐L ‐lactate) (PBSL) in proportions of 100/0, 90/10, 80/20, and 70/30 (based on the weight percentage). Their mechanical properties were investigated and related to their morphologies. The thermal properties, Fourier transform infrared spectroscopy, and melt flow index analysis of the binary blends and virgin polymers were then evaluated. The addition of PCL and PBSL to PLLA reduced the tensile strength and Young's modulus, whereas the elongation at break and melt flow index increased. The stress–strain curve showed that the blending of PLLA with ductile PCL and PBSL improved the toughness and increased the thermal stability of the blended polymers. A morphological analysis of the PLLA and the PLLA blends revealed that all the PLLA/PCL and PLLA/PBSL blends were immiscible with the PCL and PBSL phases finely dispersed in the PLLA‐rich phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

5.
Ethylene‐methyl acrylate‐glycidyl methacrylate copolymer (E‐MA‐GMA) is employed to improve the impact toughness of poly(l ‐lactic acid) (PLLA)/thermoplastic polyurethane (TPU) blends by reactive melt‐blending. The reaction and miscibility between the components are confirmed by Fourier transform infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. A super‐tough PLLA/TPU/E‐MA‐GMA multiphase blend (75/10/15) exhibits a significantly improved impact strength of 77.77 kJ m?2, which is more than 17 times higher than that of PLLA/TPU (90/10) blend. A co‐continuous‐like TPU phase structure involving E‐MA‐GMA phase at the etched cryo‐fractured surface and the high‐orientated matrix deformation at the impact‐fractured surface are observed by scanning electron microscopy. The high‐orientated matrix deformation induced by the co‐continuous TPU phase structure is responsible for the super toughness of PLLA/TPU/E‐MA‐GMA blends.  相似文献   

6.
Poly(lactic acid) (PLA) blended with poly(ε‐caprolactone) (PCL) was prepared with various reactive processing agents. Four isocyanates‐lysine triisocyanate (LTI); lysine diisocyanate (LDI); 1,3,5‐tris(6‐isocyanatohexyl)‐1,3,5‐triazinane‐2,4,6‐trione (Duranate TPA‐100); 1,3,5‐tris(6‐isocyanatohexyl)biuret (Duranate 24A‐100)‐and an industrial epoxide‐trimethylolpropane triglycidyl ether (Epiclon 725)‐were used as reactive processing agents. PLA/PCL blended in the presence of LTI had the highest torque in a mixer test. The test specimens were prepared by injection molding. The mechanical properties, thermal properties, molecular weight, melt viscosity, phase behavior, and morphology were investigated using tensile strength, impact strength, differential scanning calorimetry, melt mass‐flow rate measurements, capillary rheometery, gel permeation chromatography, laser scanning confocal microscopy (LSCM), and visco‐elasticity atomic force microscopy (VE‐AFM). The impact strength increased considerably at 20 wt% PCL. The nominal tensile strain of PLA/PCL blended with LTI increased by 270%. The MFR values of PLA/PCL blends decreased with increasing LTI. Similar results were observed for shear viscosity. LSCM measurements showed that the diameters of PCL were dispersed about 0.4 μm in the presence of LTI. VE‐AFM showed that spherical particles with diameters of 50 nm were PCL‐rich domain. These results indicate that isocyanate groups of LTI react with both terminal hydroxyl or carboxyl groups of polymers, and the compatibility of PLA/PCL blends improves with LTI by reactive processing. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

7.
A small amount of acrylonitrile‐butadiene‐styrene (ABS) core shell copolymer particles are used to improve the toughness of poly(l ‐lactide) (PLLA) matrix. The incorporation of ABS copolymer dramatically increased the elongation yield at break of PLLA. For PLLA blend with 6.0 wt % ABS copolymer particles, the elongation yield at break increased by 28 times and the notched impact strength improved by 100% comparing with those of neat PLLA. Fourier transformed infrared (FTIR) and dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) measurement results indicated that the special polarity interaction between ester group of PLLA matrix and nitrile group of PSAN shell phase enhanced the interfacial adhesion between PB rubber phase and PLLA matrix and promoted the fine dispersion of ABS particles in PLLA matrix. Meanwhile, ABS core shell particles also showed a certain extent of effects on the crystallinity behavior of PLLA. A small amount of ABS particles became the nucleating sites, and then the degree of crystallinity of PLLA/ABS blends increased. However, the notched impact of PLLA blends decreased because of the aggregation of more ABS particles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42554.  相似文献   

8.
In this paper, the tensile deformation and fracture toughness of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends, obtained by dynamic packing injection moulding, have been comprehensively investigated in different directions of rectangle samples, including longitudinal, latitudinal and oblique directions relative to the flow direction. Two kinds of EVA were used with VA content 16 wt% (16EVA) and 33 wt% (33EVA) to control the interfacial interactions. The results indicate that molecular orientation and interfacial interaction play very important roles to determine the tensile behaviour and fracture toughness. Biaxial‐reinforcement of tensile strength was seen for HDPE/16EVA blends but only uniaxial‐reinforcement was observed for HDPE/33EVA blends. The difference is caused by the different interfacial interactions as highlighted by the peel test, scanning electron microscopy (SEM) observation as well as theoretical evaluation. Very high impact strength, decreasing with increasing EVA content, was observed when the fracture propagation is perpendicular to the shear flow direction, while a low impact strength, increasing slightly increasing with EVA content, was seen when the fracture propagation is parallel to the shear flow. The fracture of oblique samples is always along the flow direction instead of along the impact direction or tensile direction. The tensile behaviour and fracture toughness are discussed on the basis of the formation of transcrystalline zones, orientation of EVA particles and matrix toughness of HDPE in different directions. Copyright © 2004 Society of Chemical Industry  相似文献   

9.
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   

10.
Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry  相似文献   

11.
Enhancing matrix crystallization has been demonstrated to be an effective method to simultaneously improve the impact toughness and heat resistance of poly(l-lactide) (PLLA) modified with flexible polymers, such as poly(ε-caprolactone) (PCL). Unfortunately, increasing PLLA matrix crystallinity alone cannot guarantee the enhancement of impact toughness in most cases, so other structural parameters should be considered. In this work, taking PLLA/PCL (80/20) blend as an example, the combined roles of matrix crystallization and impact modifier particle size in the toughening have been investigated. PLLA matrix crystallinity was controlled by adding a highly effective nucleating agent and PCL particle size was tailored by varying processing conditions while maintaining constant interfacial adhesion. It is interesting to find that toughening is efficient only if matrix crystallinity and particle size are well matched. With the significant increase of matrix crystallinity, an evident decrease of optimum particle size for toughening PLLA has been identified for the first time. Therefore, suitable particle size is the precondition for highly crystalline matrix to work effectively in the toughening because only small particles (0.3–0.5 μm) are effective in trigger shear yielding mechanism of the matrix needed for good toughness, whereas relatively large particles (0.7–1.1 μm) are only capable of toughening amorphous matrix effectively by initiating multiple crazing of the matrix. Importantly, our findings can be used to well explain the reason for the different roles of matrix crystallization in the toughening of different PLLA blends reported in the literature. Furthermore, the heat resistance of the blend with a highly crystalline matrix is much better than that of the blend with an amorphous one as expected. This work could not only provide a new insight into the synergistic roles of matrix crystallization and modifier particle size in the toughening of PLLA but also set up a universal framework for designing high-performance PLLA products with both good impact toughness and high heat resistance.  相似文献   

12.
Three kinds of reactive toughening agents of bamboo plastic composites are studied in this article. The bio‐fiber keeps high polarity for the hydroxyl groups of the surface, while polypropylene (PP) matrix resin phase is nonpolar. So, the interfacial compatibility between matrix and enhanced phase is poor. The anhydride in maleic anhydride grafted polypropylene can react with the hydroxyls. A large number of hydroxyl groups on the fiber surface are reduced, and the interfacial bond strength is improved. Three reactive toughening agents: glycidyl methacrylate grafted poly(ethylene‐1‐octene), maleic anhydride grafted poly(ethylene‐octene), and poly(ethylene‐butylacrylate‐glycidyl methacrylate) are chosen to improve the impact toughness. The mechanical properties, compatibility, phase structure, water absorption, and thermal properties of PP blends are all investigated. When the content of toughening agents are controlled between 6% and 8%, not only the impact strength is greatly improved but also the other properties of PP are less affected, which makes the composites with comprehensive and practical applications. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

13.
In this work, the effect of poly(l ‐lactide) (PLLA) components on the crystallization behavior and morphology of poly(?‐caprolactone) (PCL) within PCL/PLLA blends was investigated by polarized optical microscopy, DSC, SEM and AFM. Morphological results reveal that PCL forms banded spherulites in PCL/PLLA blends because the interaction between the two polymer components facilitates twisting of the PCL lamellae. Additionally, the average band spacing of PCL spherulites monotonically decreases with increasing PLLA content. With regard to the crystallization behaviors of PCL, the crystallization ability of PCL is depressed with increase of the PLLA content. However, it is interesting to observe that the growth rate of PCL spherulites is almost independent of the PLLA content while the overall isothermal crystallization rate of PCL within PCL/PLLA blends decreases first and then increases at a given crystallization temperature, indicating that the addition of PLLA components shows a weak effect on the growth rate of the PCL but mainly on the generation of nuclei. © 2018 Society of Chemical Industry  相似文献   

14.
This article describes the compatibility of two semicrystalline polymers, poly(ε‐caprolactone) (PCL) and poly(l‐lactic acid) (PLLA). The compatibility of the PCL/PLLA blends was enhanced by the compatibilizing effect of the poly(l,l‐lactide‐co‐ε‐caprolactone) [P(lLA‐co‐εCL)]. A discussion details the effect of the concentration of the compatibilizing agent, the copolymer of l,l‐lactide and ε‐caprolactone of a 50/50 mol ratio [P(lLA‐co‐εCL)], on the compatibility and the crystallization behavior of the blends of PCL and PLLA. It was found that the addition of P(lLA‐co‐εCL) could suppress the crystallization of PLLA at its Tc and induced the concurrent crystallization of PLLA and PCL. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 226–231, 2000  相似文献   

15.
Poly(l ‐lactic acid) (PLLA) was blended with a series of four‐armed poly(? ‐caprolactone)‐block ‐poly(d ‐lactic acid) (4a‐PCL‐b ‐PDLA) copolymers in order to improve its crystallization rate and mechanical properties. It is found that a higher content of 4a‐PCL‐b ‐PDLA copolymer or longer PDLA block in the copolymer lead to faster crystallization of the blend, which is attributed to the formation of stereocomplex crystallites between PLLA matrix and PDLA blocks of the 4a‐PCL‐b ‐PDLA copolymers. Meanwhile, the PDLA block can improve the miscibility between flexible PCL phase and PLLA phase, which is beneficial for improving mechanical properties. The tensile results indicate that the 10% 4a‐PCL5kb ‐PDLA5k/PLLA blend has the largest elongation at break of about 72% because of the synergistic effects of stereocomplexation between enantiomeric PLAs, multi‐arm structure and plasticization of PCL blocks. It is concluded that well‐controlled composition and content of 4a‐PCL‐b ‐PDLA copolymer in PLLA blends can significantly improve the crystallization rate and mechanical properties of the PLLA matrix. © 2017 Society of Chemical Industry  相似文献   

16.
Poly(L ‐lactide), that is, poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their blend (50/50) films containing different amounts of poly(L ‐lactide‐co‐ε‐caprolactone) (PLLA‐CL), were prepared by solution casting. The effects of added PLLA‐CL on the enzymatic hydrolysis of the films were investigated in the presence of proteinase K and Rhizopus arrhizus lipase by use of gravimetry. The addition of PLLA‐CL decreased the proteinase K–catalyzed hydrolyzabilities of the PLLA and PLLA/PCL (50/50) films as well as the Rhizopus arrhizus lipase‐catalyzed hydrolyzability of the PCL and PLLA/PCL (50/50) films. The decreased enzymatic hydrolyzabilities of the PLLA and PCL films upon addition of PLLA‐CL are attributable to the fact that the PLLA‐CL is miscible with PLLA and PCL and the dissolved PLLA‐CL must disturb the adsorption and/or scission processes of the enzymes. In addition to this effect, the decreased enzymatic hydrolyzabilities of the PLLA/PCL (50/50) films upon addition of PLLA‐CL can be explained by the enhanced compatibility between the PLLA‐rich and PCL‐rich phases arising from the dissolved PLLA‐CL. These effects result in decreased hydrolyzable interfacial area for PLLA/PCL films. The decrement in proteinase K–catalyzed hydrolyzability of the PLLA film upon addition of PLLA‐CL, which is miscible with PLLA, was in marked contrast with the enhanced proteinase K–catalyzed hydrolyzability of the PLLA film upon addition of PCL, which is immiscible with PLLA. This confirms that the miscibility of the second polymer is crucial to determine the proteinase K–catalyzed hydrolyzabilities of the PLLA‐based blend films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 412–419, 2003  相似文献   

17.
The preparation of poly(l ‐lactic acid) (PLLA) with high mechanical and ideal flame‐retardant properties is a great challenge. Herein, a simultaneous toughness and flame‐retardant PLLA composite was successfully fabricated by using a one‐step process which introduces 4,4′‐methylenediphenyl diisocyanate and ammonium polyphosphate (APP) into PLLA/poly(ε‐caprolactone) blends. SEM, Fourier transform infrared spectroscopy and TGA were adopted to confirm that APP participated in the in situ reaction during the melt process. The impact strength was increased to 13.5 kJ m?2 from 1.0 kJ m?2 for L8P2A5 composite, indicating the toughening effect of reactive blending. The cone calorimeter test, limiting oxygen index and vertical burning test results indicate that the flame‐retardant properties of the composites are enhanced with increasing APP content. This work provides a method to prepare PLLA with high mechanical properties and enhanced flame retardancy. © 2020 Society of Chemical Industry  相似文献   

18.
Blends of poly (ε‐caprolactone) (PCL)/polylactide (PLA) were prepared by solution‐casting method to study their thermal and rheological properties. Differential scanning calorimetry thermographs have shown two separate melting peaks in the blends, which are indicative of immiscible structure at all compositions. Scanning electron microscopy images show droplet morphology of PCL into PLA matrix up to 40 wt% of PCL. Above this concentration, the co‐continuous morphology starts to appear, which becomes again droplet morphology for blends with concentration of PCL higher than about 60 wt%. The viscoelastic properties of the various blends were investigated using rotational rheometry. The enhancement of the elastic modulus of blends at small frequencies at which terminal zone behavior is expected, is a signature behavior of immiscible systems due to the presence of interface and contribution to the stress from interfacial tension. Two emulsion models were used to predict the viscoelastic properties of the blends from the corresponding properties of their pure components that led to the determination of the interfacial tension of PCL/PLA in agreement with experimental findings. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers  相似文献   

19.
Reactive blending is an innovative method for the improvement of compatibility of polymer blend. In this work, poly ( L-lactic acid) and poly (butylene succinate) (PLLA/PBS) blends were prepared by melt blending to ameliorate the toughness of PLLA. Triphenyl phosphite (TPP) was introduced into the PLLA/PBS blends (80/20 by weight) to enhance their compatibility via reactive blending. The effects of TPP on the morphology and properties of PLLA/PBS blends were studied systematically. The increased torque during melt blending demonstrated that the compatibilizer successfully reacted with PLLA and PBS. The mechanical properties of the blends were exceedingly improved only with 0.5 wt% TPP. A reduction tendency of size of the dispersed phase was observed due to the improvement of compatibility. The DSC and DMA results indicate that the T g of PLLA decreased at a slow rate with the increasing content of TPP. This work provided a simple approach for preparing a kind of high toughed PLLA material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48646.  相似文献   

20.
The miscibility, morphology and tensile properties of three blend systems of poly(ε‐caprolactone) (PCL) with poly(vinyl chloride) (PVC) and with two chlorinated PVCs (CPVCs) with different chlorine contents (63 wt% and 67 wt% of Cl) have been studied. Based on the shifts of single glass transition temperature, the Gordon–Taylor K parameter is calculated as a measurement of interaction strength between PCL and (C)PVCs. Higher K values are found for blends of (C)PVCs with higher chlorine content, together with the interaction χ parameters estimated from the melting point depression results. The morphology observed with polarized light microscopy shows that spherulites exist in blends rich in PCL (≥50 wt%) only. Wide angle X‐ray diffraction studies indicate that the crystal structure of PCL is independent of the Cl content of (C)PVCs. The tensile properties of various blends exhibit a minimum as the PCL content increases. The elongation at break increases with increasing PCL content. © 2000 Society of Chemical Industry  相似文献   

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