聚右旋丙交酯和聚左旋丙交酯乙交酯的制备及其共混物的结晶行为

以辛酸亚锡为催化剂,十八醇为引发剂,分别以右旋丙交酯和左旋丙交酯与乙交酯为原料,在真空条件下经本体熔融开环聚合制备了系列右旋丙交酯聚合物(E)和左旋丙交酯乙交酯共聚物(F),其结构经1H NMR和IR表征。利用DSC研究了E和F共混物(M)的结晶性能,结果表明,E和F能形成具有较高熔点的立构复合物(SC),其形成能力随E分子量的增加而降低,且SC的含量在E和F共混比为49∶51附近出现极大值。     

聚(L-丙交酯)/聚(DL-丙交酯)的结晶性能及相溶性

用共溶液沉淀法制备了聚 (L 丙交酯 ) 聚 (DL 丙交酯 )共混物 (PLLA PDLLA) ,然后用成纤模压法压制成3 2mm的棒材 .用差示扫描量热法研究了共混物的结晶性能和相溶性 .结果表明 ,PLLA组分在共溶液沉淀过程中可生成结晶 ,共混物中PDLLA含量直到 30 %时 ,PLLA组分的结晶熔融温度和结晶度与纯PLLA相同 ,但PDLLA含量为 5 0 %时 ,PLLA组分的结晶熔融温度和结晶度明显下降 .由于加工成型条件的不一致性 ,共混物棒材中的PLLA组分的结晶熔融温度和结晶度呈较大的分散性 .共混物从熔体降温 ,在其后的升温DSC扫描中出现分别相应于PDLLA和PLLA的玻璃化转变 ,表明PDLLA与未结晶的PLLA形成的非晶相是不相溶的     

高分子量聚L-乳酸热降解回收L-丙交酯*

本文综述了高分子量聚L-乳酸(Poly(L-lactide), PLLA)经热降解直接回收L-丙交酯的研究进展。纯PLLA的热降解为无规反应,经添加金属类催化剂后,PLLA则可获得以L-丙交酯为主的热降解产物。本文介绍了聚乳酸热降解的反应机理,详细阐述了添加的金属催化剂的种类,及其催化PLLA热降解生成L-丙交酯及发生消旋化作用的机理。经PLLA热降解直接回收L-丙交酯技术的研究,可缩短PLLA再循环使用周期,既降低生产成本,又充分利用资源,达到促进发展循环经济的目的。     

L-丙交酯中乳酸含量的分析

L-丙交酯;乳酸;乳酸含量;滴定 校正法;乙醇钠     

聚碳酸1,2-丙二酯/聚琥珀酸丁二酯/邻苯二甲酸二烯丙酯共混体系的研究

采用熔融共混的方法制备了聚碳酸1,2-丙二酯(PPC)/聚琥珀酸丁二酯(PBS)共混物和PPC/PBS/DAOP(邻苯二甲酸二烯丙酯)增塑共混物,对共混物的相容性、热性能、结晶性和物理机械性能进行了初步研究.研究结果表明PPC/PBS共混物为不相容体系,PPC对PBS的结晶度影响很小;PBS的加入提高了共混物的起始热分解温度(Td-5%),当共混物中PBS含量从10%增加到90%时,共混物的Td-5%可分别增加15℃到59℃.DAOP对PPC/PBS共混物有增塑作用,当PPC/PBS/DAOP的比例从30/70/0变化到30/70/30时,共混物玻璃化转变温度(Tg)下降了36.9℃.与PPC/PBS共混物相比,组成优化的DAOP增塑共混物PPC/PBS/DAOP(PPC/PBS/DAOP=30/70/5)的断裂伸长率和断裂能最大可提高31倍和34倍,分别达到655.1%和3.4 J/mm2,因此引入DAOP尽管使共混材料的热稳定性有所下降,但拓宽了PPC/PBS共混材料的使用温度窗口.     

吗啉二酮衍生物与L-丙交酯共聚物的体外降解性能

研究了37℃下吗啉二酮衍生物与L-丙交酯的共聚物在磷酸盐缓冲液(PBS)中的降解,并且与聚(L-丙交酯与乙交酯)(PLGA)的降解进行了比较。通过静滴接触角测量、扫描电镜(SEM)、X衍射(XRD)、凝胶色谱仪(GPC)、核磁共振(1H-NMR)和红外光谱(FT-IR)等方法研究了材料的亲水性、表面形貌、结晶结构、失重率、分子量和结构的变化等。结果表明:与PLGA相比,吗啉二酮衍生物与L-丙交酯的共聚物具有更好的亲水性,接触角达到了74°,降解3个月后数均分子量下降80%以上,该共聚物能够实现两组份的同步降解。     

醇铁化合物引发丙交酯开环聚合的研究

分别以乙醇铁、正丙醇铁、异丙醇铁、正丁醇铁为引发剂进行D,L-丙交酯和L-丙交酯的本体开环聚合,研究了在130℃的聚合温度下引发剂用量和聚合时间对聚合反应的影响.结果表明这些醇铁化合物对丙交酯开环聚合都有较好的引发作用;聚合36h,单体转化率可达90%以上.单体转化率在引发剂/单体摩尔比为1/1000时最高,然后随引发剂用量增加和聚合时间延长而降低.乙醇铁表现出最高的引发活性,聚合产物的相对粘均分子量最高可达7·28×104[聚(D,L-丙交酯)]和19·00×104[聚(L-丙交酯)].醇盐配体对聚合产物的分子量和分子量分布影响显著,随醇铁配体体积增大,聚合产物的分子量逐渐降低,分子量分布也逐渐加宽.1H和13C-NMR分析表明醇铁对L-丙交酯的开环聚合没有发生消旋化,对D,L-丙交酯的开环聚合有一定的等规加成选择性.MALDI-TOF MS分析指出D,L-丙交酯在开环聚合过程中发生了分子间的酯交换反应,用13C-NMR评价了各醇铁引发体系在聚合过程中的酯交换程度.但基于谱峰分辨原因,醇铁配体对立构加成选择性和酯交换的影响的规律性不明显.     

锌配合物催化ε-己内酯/L-丙交酯共聚制备环状和线形嵌段共聚酯

以空气稳定的含苯并咪唑基吡啶醇配体的氯化锌配合物为催化剂,与甲基锂相结合,在有无苄醇引发的情况下,分别研究了L-丙交酯(L-LA)的均聚反应以及L-丙交酯和ε-己内酯(ε-CL)的共聚反应.L-丙交酯的均聚反应与ε-己内酯的均聚反应相似,具有较高的聚合活性;聚合物的结构分析结果表明,在聚合体系中有无苄醇存在的情况下,分别得到以线形和环状聚丙交酯(PLA)为主的聚合产物;而加入苄醇后聚合物的分子量降低,分子量分布变窄.在L-丙交酯和ε-己内酯均聚反应的基础上,对2种单体的共聚反应进行了研究.通过顺序加料法,调节ε-CL/L-LA的起始投料比,在有无苄醇存在下,分别制备了一系列不同ε-CL/L-LA比例的线形和环状嵌段共聚物,对均聚物和共聚物的结构和热性能进行了表征.     

二醋酸纤维素接枝丙交酯共聚物的合成与表征

以二醋酸纤维素为接枝骨架,在辛酸亚锡的催化下,通过L-丙交酯的开环接枝聚合反应,合成了二醋酸纤维素和聚丙交酯接枝共聚物(CDA-g-PLA),并采用GPC、FTIR、1H-NMR和DSC对接枝共聚物进行表征.研究了原料质量比、催化剂用量、反应时间、反应温度对单体转化率(C%)、接枝率(G%)的影响.结果表明:反应温度150℃,单体丙交酯与二醋酸纤维素质量比为4:1,反应时间30min,催化剂辛酸亚锡与二醋酸纤维素的质量比为1%时,产物的接枝率较高.     

聚(丙交酯-co-乙交酯)/β-磷酸三钙复合物的电纺研究

对生物可吸收聚(丙交酯-co-乙交酯)(poly(lactide-co-glycolide),PLGA)与β-磷酸三钙(-βTCP)复合物体系进行了电纺.研究了PLGA的浓度,-βTCP与PLGA比例,加料速度,电压,喷头与接收体之间的距离等因素对电纺过程的影响,制备出纳米纤维膜,并用扫描电镜(SEM)等对纤维膜进行表征.结果表明,电纺溶液浓度越高,或者加料速度越快,纳米纤维的直径越粗.力学实验显示,复合物中-βTCP的含量增加使纳米纤维膜的拉伸强度和杨氏模量下降.     

聚乳酸/纳米SiO_2共混物的热性能

以两种含有不同功能团的纳米SiO2对聚左旋乳酸(PLLA)进行了共混改性,从而提高了PLLA的性能。在纳米SiO2的质量分数为0.5~5%范围内,PLLA与之是相容的,其中含有—NH2功能团的RNS型纳米对PLLA的Tg有一定的影响,加入质量分数为5%的RNS型纳米SiO2后,PLLA的Tg降至52℃。由于RNS纳米SiO2中的—NH2与PLLA分子链中的—C=O形成了弱的氢键,因此在相同质量分数下,对PLLA热稳定性的影响要高于含—CH3功能团的DNS纳米SiO2,质量分数为5%的纳米SiO2与PLLA共混后,PLLA/RNS纳米SiO2共混物的热失重起始温度为370℃,而PLLA/RNS纳米SiO2共混物的则为365℃。     

Poly（L—lactide）—Poly（ethylene glycol） Multiblock Copolymers：Synthesis and Properties

Poly (L-lactide)-poly (ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.     

Non-isothermal crystallization of poly(L-lactide) (PLLA) under quiescent and steady shear conditions

<正>The non-isothermal crystallization of poly(L-lactide)(PLLA) under quiescent and steady shear flow conditions was in situ investigated by using polarizing optical microscopy(POM) with a hot shear stage and wide-angle X-ray diffraction(WAXD).The shear rate and the cooling rate both play a significant role in the final crystalline morphology and crystallinity.Under quiescent conditions,the morphology assumes different sized spherulites,and its crystallinity dramatically reduces with increasing the cooling rate.On the other hand,the shear flow increases the onset crystallization temperature,and enhances the final crystallinity.When the shear rate is above 5 s~(-1),cylindrite-like crystals are observed, furthermore,their content depends on the cooling rate.     

PLA大分子单体接枝NVP共聚物的合成与性能

制备了末端为双键的功能化聚乳酸大分子单体(PLA-HEMA),并以此大分子单体与N-乙烯基吡咯烷酮(NVP)进行自由基溶液共聚,合成了具有亲水性PVP-PHEMA主链和疏水性PLA支链的接枝共聚物。用FT-IR1、H-NMR、GPC、DSC、表面接触角测定研究了共聚物的结构与性能。结果表明:共聚物为非晶聚合物;NVP的摩尔投料量对共聚物的性能有显著影响,随NVP投料量增大,共聚物的分子量有所下降,玻璃化转变温度(Tg)增大;由于亲水性PVP和PHEMA链段的引入,共聚物的亲水性优于相应的线型聚乳酸材料。     

Enhancing the Crystallization Performance of Poly(L-lactide) by Intramolecular Hybridizing with Tunable Self-assembly-type Oxalamide Segments

In this work, hydroxyl-terminated oxalamide compounds N~1,N~2-bis(2-hydroxyethyl)oxalamide(OXA1) and N~1,N~(1′)-(ethane-1,2-diyl)bis(N2-(2-hydroxyethyl)oxalamide(OXA2) were synthesized to initiate the ring-opening polymerization of L-lactide for preparation of oxalamide-hybridized poly(L-lactide)(PLA_(OXA)), i.e., PLA_(OXA1) and PLA_(OXA2). The crystallization properties of PLA were improved by the self-assembly of the oxalamide segments in PLA_(OXA) which served as the initial heterogeneous nuclei. The crystal growth kinetics was studied by HoffmanLauritzen theory and it revealed that the nucleation energy barrier of PLA_(OXA1) and PLA_(OXA2) was lower than that of PLA. Consequently, PLA_(OXA) could crystallize much faster than PLA, accompanied with a decrease in spherulite size and half-life crystallization time by 74.8% and 86.5%(T=125 ℃), respectively. In addition, the final crystallinity of PLA_(OXA1) and PLA_(OXA2) was 6 and 8 times higher, respectively, in comparison with that of neat PLA under a controlled cooling rate of 10 ℃/min. The results demonstrate that the hybridization of oxalamide segments in PLA backbone will serve as the self-heteronucleation for promoting the crystallization rate. The higher the content of oxalamide segments(PLA_(OXA2) compared with PLA_(OXA1)) is, the stronger the promotion effect will be. Therefore, this study may provide a universal approach by hybridizing macromolecular structure to facilitate the crystallization of semi-crystalline polymer materials.     

Structural Changes in Drawn Poly(L-lactide)/Clay Hybrid Films

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.     

Mixing of Racemic Poly(L-lactide)/Poly(D-lactide) Blend with Miscible Poly(D,L-lactide):Toward All Stereocomplex-type Polylactide with Strikingly Enhanced SC Crystallizability

Stereocomplex-type polylactide (SC-PLA) consisting of alternatively arranged poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide) (PDLLA) into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability (i.e.,the stability of PLLA/PDLA chain assemblies upon melting) could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt％ PDLLA having weight-average molecular weight of above 1 ×10s g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.     

低分子量结晶性丙交酯/乙交酯与己内酯/乙交酯共聚物热转变温度的组成与分子量依赖性

以1,4-丁二醇为引发剂、辛酸亚锡为催化剂,通过L-丙交酯(LLA)、乙交酯(GA)、ε-己内酯(CL)的开环共聚,制得了低分子量的端羟基结晶性LLA/GA共聚物(PLLGA)和CL/GA共聚物(PCG),分别以FTIR1、H-NMR、GPC、DSC对其微结构和热转变温度进行了表征,重点考察了其热转变温度的组成、分子量依赖性.结果表明,利用辛酸亚锡/二元醇引发开环聚合,通过改变单体配比和单体/引发剂配比,可方便地调控共聚物的组成和分子量;通过改变共聚物的组成和分子量,可在较宽的范围内调节共聚物的热转变温度,并得到了玻璃化温度和熔点与组成、分子量之间定量的经验关系式.     

基于聚丙交酯的多嵌段聚氨酯的形状记忆性能和生物相容性

制备了以聚丙交酯(PLA)为软段, 2,4-甲苯二异氰酸酯(TDI)与乙二醇(EG)反应产物为硬段的多嵌段聚氨酯(PLA-PU), 并对其形状记忆效应和生物相容性进行了研究. 形状压缩50%的样品从起始恢复温度(22~37 ℃)开始, 在10 ℃范围内可以恢复到起始形状, 形变恢复率接近100%, 形变恢复力最大值达到1.5~4 MPa. 细胞培养实验结果初步证明PLA-PU的细胞相容性与PLA相当, 因而有可能用作植入形状记忆医疗器械材料.     

Bio-based and Biodegradable Electrospun Fibers Composed of Poly(L-lactide) and Polyamide 4

Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.