The films composed of poly(L-lactide)(PLLA)/organoclay hybrids (PLACHs) have been prepared via a melt-compounding process, in which the organoclay paticles are uniformly dispersed in the PLLA matrix. The changes in PLLA crystal orientation for the uniaxially drawn films were studied by differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. Additionally, temperature dependence of the mechanical properties for these drawn films were examined by a dynamic viscoelastometer. After drawing the quenched PLACHs film at 90 °C, the orientation and crystallinity of PLLA crystal increased rapidly with increasing drawing ratio (λ) in the range more than 3 times. At the higher λ, the organoclay platelet particles in the PLACHs became parallel to the draw direction. The mechanical properties of drawn PLACHs were strongly dependent on both clay concentration and λ. 相似文献
A diblock copolymer system constituting both achiral and chiral blocks, polystyrene‐block‐poly(L ‐lactide) (PS‐PLLA), was designed for the examination of chiral effects on the self‐assembly of block copolymers (BCPs). A unique phase with three‐dimensional hexagonally packed PLLA helices in PS matrix, a helical phase (H*), can be obtained from the self‐assembly of PS‐rich PS‐PLLA with volume fraction of PLLA f = 0.34, whereas no such phase was found in racemic polystyrene‐block‐poly(D .L ‐lactide) (PS‐PLA) BCPs. Moreover, various interesting crystalline PS‐PLLA nanostructures can be obtained by controlling the crystallization temperature of PLLA (Tc,PLLA), leading to the formation of crystalline helices (PLLA crystallization directed by helical confined microdomain) and crystalline cylinders (phase transformation of helical nanostructure dictated by crystallization) when Tc,PLLA < Tg,PS (the glass transition temperature of PS) and Tc,PLLA ≧ Tg,PS, respectively. As a result, a spring‐like behavior of the helical nanostructure can be driven by crystallization so as to dictate the transformation (i.e., stretching) of helices and to result in crystalline cylinders. For PS‐PLLA with PLLA‐rich fraction (f = 0.65), another unique phase, a hexagonally packed core‐shell cylinder phase with helical sense (CS*), in which the PS microdomains appear as shells and PLLA microdomains appear as matrix and cores, can be found in the self‐assembly of PLLA‐rich PS‐PLLA BCPs. The formation of those novel phases: helix and core‐shell cylinder is attributed to the chiral effect on the self‐assembly of BCPs, so we named this PS‐PLLA BCP as chiral BCP (BCP*). For potential applications of those materials, the spring‐like behavior with thermal reversibility might provide a method for the design of switchable nanodevices, such as nanoscale actuators. In addition, the PLLA blocks can be hydrolyzed. After hydrolysis, helical nanoporous PS bulk and PS tubular texture can be obtained and used as templates for the formation of nanocomposites.
The electrochemically synthesized poly(p‐phenylene) film could be zone drawn by a factor of 1.57, where the orientation function (f) increased with the draw ratio (λ), regardless of the heater temperature (Th) or applied tension (σ), and reached 0.428 for the resulting film. The electrical conductivity in the drawing direction rose with f but decreased as Th became higher due to dedoping that occurred simultaneously with drawing. Young's modulus and tensile strength significantly increased to 4.5 GPa and 155 MPa by zone drawing from 1.1 GPa and 79 MPa of the as‐synthesized film. 相似文献
Polychloroprene/organoclay nanocomposites (ENC) were characterized by X-ray scattering, DSC and stretching calorimetry techniques.The infinite cluster of highly anisometric organoclay particles was likely to set on at filler volume fraction as low as ? ? 0.04. Quantitative analysis of thermoelastic behavior over the entire range of relative elongations provided additional support for the concept of strain-dependent strain amplification factor as the major parameter controlling the thermomechanical properties of the ENC. Low values of the fitting parameter C in the modified equation for the total heats of stretching were regarded as evidence for the reduced exothermal effects of external friction between organoclay nanoparticles coated with the boundary interphase. Stress relaxation behavior of the ENC was qualitatively consistent with the original assumption that after initial stretching to the highest elongation (λlim) the pre-existing infinite clusters of filler particles were broken into isolated clusters which remained structurally similar, whatever the subsequent stretching to λf < λlim. 相似文献
Porous poly(ε‐caprolactone) (PCL) films were prepared by the removal of poly(L ‐lactide) (PLLA) from phase‐separated PLLA/PCL blend films using the selective Proteinase K™‐catalyzed hydrolysis of PLLA and subsequent elution of its water‐soluble oligomers and monomer into the surrounding hydrolysis media. Polarimetry, gravimetry, and differential scanning calorimetry (DSC) confirmed the complete removal of PLLA molecules from the blend films within 5 d of the Proteinase K‐catalyzed hydrolysis and therefore the formation of porous PCL films when the initial PLLA content [XPLLA(0)(w/w) = PLLA/(PCL + PLLA)] of the blend films was in the range 0.3–0.5. The fragmentation of the blend film with XPLLA(0) = 0.7 occurred when the Proteinase K‐catalyzed hydrolysis was continued for longer than 5 d. These findings exhibited that both the PLLA‐rich and PCL‐rich phases were continuous in the blend films for XPLLA(0) ranges of 0.3–0.7 and of 0.3–0.5, respectively, and that the PCL‐rich phase became dispersed when XPLLA(0) was increased to 0.7. The dependence of enzymatic hydrolysis rate on XPLLA(0) strongly suggests that the Proteinase K‐catalyzed hydrolysis of the blend films occurs at the interfaces of PLLA‐rich and PCL‐rich phases as well as at the film surfaces. 相似文献
To obtain an effective compatibilizer for the blends of poly(L‐lactide) (PLLA) and poly(ε‐caprolactone) (PCL), the diblock copolymers PCL‐b‐PLLA with different ratios of PCL/PLLA (CL/LA) and different molecular weights (Mn) were synthesized by ring‐opening polymerization (ROP) of L‐lactide with monohydric poly(ε‐caprolactone) (PCL‐OH) as a macro‐initiator. These copolymers were melt blended with PLLA/PCL (80/20) blend at contents between 3.0 and 20 phr (parts per hundred resin), and the effects of added PCL‐b‐PLLA on the mechanical, morphological, rheological, and thermodynamic properties of the PLLA/PCL/PCL‐b‐PLLA blends were investigated. The compatibility between PLLA matrix and PCL phase was enhanced with decreasing in CL/LA ratios or increasing in Mn for the added PCL‐b‐PLLA. Moreover, the crystallinity of PLLA matrix increased because of the added compatibilizers. The PCL‐b‐PLLA with the ratio of CL/LA (50/50) and Mn ≥ 39.0 kg/mol were effective compatibilizers for PLLA/PCL blends. When the content of PCL‐b‐PLLA is greater than or equal to 5 phr, the elongations at break of the PLLA/PCL/PCL‐b‐PLLA blends all reached approximately 180%, about 25 times more than the pristine PLLA/PCL(80/20) blend. 相似文献
Block copolymers create various types of nano‐structures, e. g., spheres, rods, cubes, and lamellae. This review discloses the dynamic macromolecular organization of block copolymers comprising poly(L ‐lactide) (PLLA) and poly(oxyethylene) (PEG) that allows to simulate elaborate biological systems. The block copolymers, AB‐ (PLLA‐PEG) and ABA‐type (PLLA‐PEG‐PLLA), are synthesized by ordinary lactide polymerization to have a controlled block length. They are dispersed into an aqueous medium to prepare nano‐scale particles, consisting of hydrophobic PLLA and hydrophilic PEG in the core and shell, respectively. Then, the particles are placed on a flat substrate by the casting method. The particles are detected as discoids by AFM, having shrunk with loss of water. Heat‐treatment of these particles at 60°C (above Tg of PLLA) gives rise to a collapse into small fragments, which then aggregate into bands with nano‐size width and thickness. The PLLA‐PEG bands align parallel to each other, while the PLLA‐PEG‐PLLA bands form a characteristic network resembling the neuron system created in animal tissue. As analyzed by TEM diffraction, each is composed of α‐crystal of PLLA whose c‐axis (molecular axis) is perpendicular to the substrate surface. Based on this fact, a doubly twisted chain structure of PLLA is proposed in addition to a plausible mechanism for the self‐organization of the block copolymers. Derivatives of the PLLA‐PEG block copolymers can form far more interesting nano‐architectures. An equimolar mixture of enantiomeric copolymers, PLLA‐PEG‐PLLA and PDLA‐PEG‐PDLA, forms a hydrogel that is thermo‐responsive. The terminal‐modified poly(L ‐lactide)‐block‐polyoxyethylene monocinnamate (PLLA‐PEG‐C) forms a highly stabilized nanofiber by the photo‐reaction of the cinnamates placed in the outer layer of the nanobands. 相似文献