无规聚甲基丙烯酸甲酯立构复合的红外光谱研究

用红外光谱研究了无规聚甲基丙烯酸甲酯的丙酮、苯、氯仿溶液成膜样品的立构复合状况。结果表明无规聚甲基丙烯酸甲酯在丙酮和苯中确能形成立构复合结构,结构的形成主要是依靠分子链中间规和等规链段的相互作用。对丙酮样品的退火实验表明,在退火过程中能够发生间规链段的自聚集现象。     

Different enantioselectivity of two types of poly(lactic acid) depolymerases toward poly(l-lactic acid) and poly(d-lactic acid)

Poly(lactic acid) (PLA) depolymerases are categorized into protease-type and lipase-type. Protease-types can hydrolyze poly(l-lactic acid) (PLLA) but not poly(d-lactic acid) (PDLA). Lipase-types, including cutinase-like enzyme (CLE) from Cryptococcus sp. strain S-2 preferentially hydrolyze PDLA. Both enzymes degraded not only PLA emulsion but also PLA film, in which amorphous region is preferentially attacked, but crystalline region can be also attacked. Stereocomplex PLA (sc-PLA) formed by 50:50 blending of PLLA and PDLA included no homo crystals, but a tiny homo crystallization peak appeared and crystallinity increased by 5% when attacked by CLE, although no significant change of molecular weight and crystalline size was found. Enantioselective degradation must occur in amorphous region of PLLA/PDLA film and preferentially hydrolyzed PDLA, resulting in a slightly excess amount of PLLA remained, which must be crystallized.     

立构复合PL(D) LA-TMC无规共聚物的制备、结构与性能

以辛酸亚锡为催化剂,通过开环聚合法制备了聚左旋乳酸-三亚甲基碳酸酯(PLLA-TMC)和聚右旋乳酸-三亚甲基碳酸酯(PDLA-TMC)无规共聚物.利用共聚物中PLLA/PDLA链段形成立构复合体,通过溶液浇注法制备了PLLA-TMC/PDLA-TMC立构复合聚乳酸材料(sc-PLA-TMC).研究结果表明,聚合物链中的柔性TMC单元可以增强L(D)LA链段的运动能力,有助于不同旋光性的LA链段形成立构复合晶体,但也使得L(D)LA链段的规整度和序列长度降低.即随着共聚物链段中柔性TMC单元摩尔含量的增加,sc-PLA-TMC中同质结晶能力降低.当TMC含量≥5%时,仅生成熔点200℃的PLLA/PDLA立构复合结晶,表明sc-PLA-TMC的耐热性有所提高.蛋白酶K降解实验表明,PL(D)LA-TMC共聚物的降解速率不但比PLLA高,而且可通过共聚物中TMC含量进行调控.     

Development of Stereocomplex Crystal of Polylactide in High-Speed Melt Spinning and Subsequent Drawing and Annealing Processes

High-speed melt spinning of racemate polylactide (r-PLA), which is a blend of equal amounts of poly(l-lactide) and poly(d-lactide) molecules, was performed up to the take-up velocity of 7.5 km/min. In the fiber structure analysis, particular attention was paid to the formation of stereocomplex crystals, because this crystal form has a melting temperature about 60° higher than the homocrystals. It was found that highly oriented and highly crystallized fibers containing the α-form and stereocomplex crystals were obtained when the take-up velocity exceeded about 4 km/min. The amount of stereocomplex crystal was higher under the spinning conditions of higher take-up velocity, lower throughput rate, and lower extrusion temperature. Under these conditions, higher tensile stress can be applied to the spinning line, and therefore, the orientation-induced crystallization is promoted. Annealing of the fibers obtained at high-take-up velocities, such as 6 km/min, which already have the crystalline structure with a certain amount of stereocomplex crystal, at a temperature between the melting temperatures of α-form and stereocomplex crystals, yielded the fiber structure mainly consisting of highly oriented stereocomplex crystal. The annealed fibers showed fairly high mechanical properties and good thermal stability.     

Stereocomplexation and Mechanical Properties of Polylactide-b-poly(propylene glycol)-b-polylactide Blend Films: Effects of Polylactide Block Length and Blend Ratio

In the present work, poly(propylene glycol)(PPG) was block copolymerized to form polylactide-poly(propylene glycol)-polylactide(PL-PPG-PL) triblock copolymers for preparing flexible stereocomplex PL(sc PL) blend films. The sc PL blend films were prepared by solution blending of poly(L-lactide)-PPG-poly(L-lactide)(PLL-PPG-PLL) and poly(D-lactide)-PPG-poly(D-lactide)(PDL-PPG-PDL) triblock copolymers before film casting. The influences of PL end-block lengths(2×10~4 and 4×10~4 g/mol) and blend ratios(75/25, 50/50 and 25/75 W/W) on the stereocomplexation and mechanical properties of the blend films were evaluated. From DSC and WAXD results, the 50/50 blend films had complete stereocomplexation. Phase separation between the sc PL and PPG phases was not observed from their SEM images. The tensile stress and elongation at break increased with the sterecomplex crystallinities and PL end-block lengths. The PPG middle-blocks enhanced elongation at break of the sc PL films. The results showed that the PL-PPG-PL triblock structures did not affect stereocomplexation of the PLL/PDL block blending. In conclusion, the phase compatibility and flexibility of the sc PL films were improved by PPG block copolymerization.     

The chiral effects on the responses of osteoblastic cells to the polymeric substrates

In order to study the chiral effects of polylactides on responses of osteoblastic cells, poly(l-lactide) (PLLA), poly(d-lactide) (PDLA), poly(dl-lactide) (PDLLA) and the stereocomplex of PLLA and PDLLA (SC) films with different stereoforms were prepared. The surface properties of the four polylactide films were tested and the osteoblastic ROS 17/2.8 cells were cultured on the films. The protein adsorption behaviors of fibrinogen and bovine serum albumin on films were studied. The cell proliferation, total protein amount, DNA content and alkaline phosphatase activity of osteoblastic ROS 17/2.8 cells were evaluated. The results showed that the protein adsorption was dependant on the type of proteins. The observation of cell morphologies revealed that the PDLA film provide an unfavorable surface for cell attachment. The total protein amount, DNA content and ALP activity were closely related to the stereoforms of polylactide films. All the levels of total protein amount, DNA content and ALP activity of ROS 17/2.8 cells on PDLA film were decreased. The racemic stereocomplex of PLLA and PDLA showed relatively higher positive effects on both cell growth and proliferation.     

Can Classic Avrami Theory Describe the Isothermal Crystallization Kinetics for Stereocomplex Poly(lactic acid)?

Classic Avrami model and its modifications have found diverse applications in describing the thermal and phase behaviors of inorganic metals and organic polymers.The direct introduction of classic Avrami equation to offer quantitative analyses of crystallization kinetic parameters for enantiomeric poly(lactic acid) (PLA) blends may,however,lead to contradictory conclusions.As revealed by this study,during the characterization of isothermal melt and cold crystallization for stereocomplex PLA containing equal-weight poly(L-lactic acid) and poly(D-lactic acid),the kinetic parameters yielded by Avrami equation are not in line with the classic crystallization hypotheses or the direct morphological observations.The underlying mechanisms,to some extent,lie in the generation of stereocomplex crystals (SCs) during the cooling/heating which affects the subsequent crystallization dynamics.The huge gap between the melting enthalpies of 100％ crystalline SCs (142 J/g) and homo-crystals (HCs,93 J/g) is most likely responsible for the confusing kinetic parameters acquired from the deduction of Avrami equation,which is based on the integration of enthalpies as a function of crystallization time.This prompts for great care that the classic Avrami equation is not applicable to accurately describe the crystallization kinetics of stereocomplex PLA,given the generation of SCs prior to crystallization and the coexistence of HCs and SCs during crystallization.