聚乳酸基离聚物的合成与表征

聚乳酸是一种绿色环保高分子材料。以丙交酯为单体,辛酸亚锡为催化剂,N-甲基二乙醇胺为引发剂通过丙交酯的开环聚合法制备了聚合物分子链中含有氨基官能团的双端羟基聚乳酸,然后以异佛尔酮二异氰酸酯作为扩链剂进行溶液扩链反应制备了聚乳酸基聚氨酯,然后再与冰醋酸、碘甲烷、溴乙烷反应,制备了以聚乳酸基聚氨酯为基体的离聚物。并采用特性粘数测定、GPC、差示扫描量热法、热重分析法、X射线衍射等方法对聚合物进行了表征。结果表明,聚乳酸基聚氨酯离聚物的特性粘数高于聚乳酸基聚氨酯,离聚物的热稳定性优于聚乳酸及聚乳酸基聚氨酯。     

聚乙二醇改性聚乳酸类材料的合成及应用

介绍了丙交酯与环氧乙烷开环共聚合、丙交酯与聚乙二醇(PEG)开环共聚合，以及在其基础上的扩链3种主要的聚乙二醇改性聚乳酸(PELA)合成方法，并概括了各种PELA合成材料的性能与应用。为了得到功能化和亲水性理想的聚乳酸类生物降解高分子，聚乳酸树脂的PEG改性合成T作越来越引人注目。以PEG、乳酸等为原料，通过简单易行的直接聚合法合成PELA类材料，降低PELA类材料的成本，是未来研究的重要方向。     

原位法合成聚乳酸接枝淀粉共聚物的研究与应用

首次采用阴离子开环聚合的方法,在淀粉上一步法原位接枝聚合得到聚乳酸和淀粉的接枝共聚物。采用强极性溶剂二甲基亚砜（DMSO）将淀粉溶解,然后以叔丁醇钾为引发剂,引发L-丙交酯接枝聚合,提纯后的接枝产物通过红外光谱、核磁共振、XRD等测试方法进行表征。结果表明,在聚合温度为75 ℃,时间为4 h,原料摩尔比为淀粉/丙交酯/叔丁醇钾为10/75/3条件下,接枝产物的接枝率可达83 %。将该接枝产物添加到淀粉和聚乳酸共混体系中,与未添加接枝物的共混体系相比,添加接枝物的共混体系中淀粉的分布更加均匀,性能更加均一。     

聚乳酸的合成研究

聚乳酸是一种脂肪族聚酯类可生物降解高分子材料,己成为生物降解医用材料领域中最受重视的材料之一。本文以D,L-乳酸（两种光学异构体）为原料,通过二步开环聚合法实验,探讨了乳酸合成D,L-丙交酯,以及丙交酯经重结晶提纯并充分干燥后,作为聚合单体进行聚合反应的反应历程中各种反应参数包括温度、反应时间、溶剂、催化剂种类等对丙交酯的产率和聚合产物的分子量的影响。     

可生物降解聚乳酸的扩链研究进展

依据聚乳酸(PLA)分子的端羟基和端羧基结构特点,主要综述了近年来以有机小分子扩链改性PLA的方法、机理与应用,分别介绍了端羟基缩聚扩链剂、端羧基缩聚扩链剂以及其他扩链剂在改性PLA中的应用.其中端羟基缩聚扩链剂主要有多异氰酸酯、双环羧酸酐、二酰氯;端羧基缩聚扩链剂主要有二噁唑啉、双环氧化物、二元胺、二元醇.并且简要介绍了其他低聚物如聚乙二醇(PEG)、聚乙醇酸(PGA)、聚己二酸丁二醇酯(PBA)、聚丁二酸丁二醇酯(PBS)、聚占-己内酯(PCL)与PLA共聚提高其摩尔质量及改性方面的研究进展,最后对PLA的改性研究与应用做了进一步的展望.     

聚乳酸共聚改性及应用研究进展

综述了聚乳酸共聚增韧改性的研究进展,详细介绍了直接缩聚法、开环聚合法、扩链剂法等聚乳酸的共聚改性方法,其中直接缩聚法得到的聚合物的相对分子质量较低,开环聚合法得到的聚合物的相对分子质量较高,扩链剂可以与其他2种方法配合使用。最后,综述了聚乳酸共聚物在医学领域及包装领域的应用研究进展。     

原子转移自由基聚合制备两亲性聚乳酸嵌段共聚物

以双端羟基聚乳酸和2-溴丙酰溴为原料,制备了溴端基的聚乳酸;再以此作为大分子引发剂,溴化亚铜／2,2’-联吡啶为催化体系,实现了N-乙烯基吡咯烷酮的原子转移自由基聚合,制得了两亲性聚乳酸嵌段共聚物。用IR、^1H-NMR、GPC和接触角测定仪对聚合物的结构和亲水性进行了表征,并用TEM研究了聚合物在水溶液中的聚集状态。结果表明,聚乙烯基吡咯烷酮链段的引人,大大提高了聚乳酸共聚物的亲水性,且共聚物在水相中可形成一壳多核球状胶束。     

聚乳酸合成及改性研究进展

综述了近年来国内外聚乳酸直接合成法和丙交酯开环聚合法的研究进展,对聚乳酸改性方法进行了深入的总结和评述,并揭示了聚乳酸材料的研究开发前景。     

聚乳酸改性糯玉米淀粉的制备及表征

以糯玉米淀粉为原料、异辛酸亚锡为催化剂,在丙交酯熔融体系中制备了聚乳酸改性糯玉米淀粉。建立了聚乳酸改性糯玉米淀粉取代度的1HNMR测试方法,以取代度为响应值,反应时间、反应温度、丙交酯添加量为考察因素,通过单因素和响应面实验优化了聚乳酸改性糯玉米淀粉的合成工艺,得到最优工艺为：反应时间12.46 h,反应温度111.75℃,丙交酯添加量为淀粉质量的258%,预测最大取代度为0.0253,通过实际操作条件调整后实际取代度为0.0238。对最优条件下制备的聚乳酸改性淀粉进行了系列表征,证实聚乳酸改性糯玉米淀粉的颗粒结构没有被完全破坏,晶型、相对分子质量等性能优于溶剂法传统技术制备的聚乳酸改性糯玉米淀粉。     

端羟基聚异戊二烯及其共聚物的合成与表征

以仲丁基锂为引发剂,引发异戊二烯本体负离子聚合,再用环氧丙烷甲醇终止法合成了端羟基聚异戊二烯;然后利用端羟基聚异戊二烯的活性端羟基,引发丙交酯的开环聚合制备了聚乳酸一聚异戊二烯共聚物,并采用IR、^1H—NMR、TG等测试手段对产品进行了表征。结果表明,通过改变仲丁基锂及环氧丙烷的用量,可合成相对分子质量及羟基含量可控的且1,4-结构质量分数超过87．5％的端羟基聚异戊二烯。     

乳酸合成丙交酯反应底物的水解处理

聚乳酸是可自然降解的新型环保材料,具有广阔的应用前景。间接法是合成高相对分子质量聚乳酸的主要途径,该法由乳酸经中间体丙交酯开环聚合生成聚乳酸。在合成丙交酯的过程中,会产生约占总量40％的副反应产物（反应底物）,对丙交酯反应底物的合理处置,是聚乳酸产业化面临的诸多难题之一。在试验基础上,根据反应底物的特点,从物料比、温度和压力等方面讨论了反应底物水解处理的最适宜条件,以及水解产物循环利用所必须的预处理措施,开发出反应底物的水解工艺。反应底物可以循环利用,有效降低了聚乳酸的原料成本。     

L-乳酸低聚物的异氰酸酯扩链反应工艺研究

采用直接熔融缩聚法制备L-乳酸低聚物。在氮气氛围下,使用六亚甲基二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)作扩链剂,研究了反应时间、温度、反应官能团配比、低聚物粘均相对分子质量(Mη)等对扩链反应的影响,对扩链产物进行了红外光谱表征及差示扫描量热分析。结果表明:HDI和MDI对L-乳酸低聚物均有较好的扩链效果,扩链反应规律基本相同;HDI的扩链效果优于MDI,扩链反应速率快,扩链时间短,扩链产物Mη高、熔点高、热性能好;较佳扩链反应工艺参数:nNOC∶nOH为1:1,反应温度165℃,HDI扩链时间20 min、MDI扩链时间30 min,L-乳酸低聚物M越高,扩链产物M越高。     

亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究

将聚氨基环氧基硅氧烷（PSQ）以及亚磷酸酯功能化的聚氨基环氧基硅氧烷（PPSQ）与聚乳酸（PLA）通过熔融共混制备了扩链PLA。研究了亚磷酸酯基团的引入对PSQ在PLA中的扩链和阻燃性能的影响,探究PPSQ在PLA中的阻燃机理。结果表明,相比于PSQ,PPSQ可以明显提高PLA的分子量和复合黏度,具有更好的扩链作用;PPSQ的引入可以明显改善PLA的阻燃性能,使得PLA?PPSQ的极限氧指数提高至25.4 %,比纯PLA提升了31.6 %,且使得PLA的热释放速率峰值和总热释放量分别下降了18.1 %和16.6 %。分析可知,由于亚磷酸酯基团的引入,促使PLA?PPSQ中的硅元素在燃烧过程中向炭层表面迁移形成更多富含碳化硅和氧化硅的致密炭层,起到隔热隔氧的作用,进而发挥优异的阻燃性能。     

分子筛改性可降解材料聚乳酸的研究

将吸附有聚乳酸齐聚物的分子筛同工业级聚乳酸在双螺杆挤出机中造粒,制备了分子筛改性聚乳酸材料。研究了分子筛对聚乳酸力学性能的影响,添加量在7%~9%左右时可以起到最好的增强效果;复合材料可以在土壤中自然降解,增加分子筛添加量可以加快复合材料的降解。     

Synthesis,characterization and biocompatibility of novel biodegradable poly[((R)‐3‐hydroxybutyrate)‐block‐(D,L‐lactide)‐block‐(ε‐caprolactone)] triblock copolymers

BACKGROUND: Biodegradable block copolymers have attracted particular attention in both fundamental and applied research because of their unique chain architecture, biodegradability and biocompatibility. Hence, biodegradable poly[((R )‐3 ‐hydroxybutyrate)‐block‐(D ,L ‐lactide)‐block‐(ε‐caprolactone)] (PHB‐PLA‐PCL) triblock copolymers were synthesized, characterized and evaluated for their biocompatibility. RESULTS: The results from nuclear magnetic resonance spectroscopy, gel permeation chromatography and thermogravimetric analysis showed that the novel triblock copolymers were successfully synthesized. Differential scanning calorimetry and wide‐angle X‐ray diffraction showed that the crystallinity of PHB in the copolymers decreased compared with methyl‐PHB (LMPHB) oligomer precursor. Blood compatibility experiments showed that the blood coagulation time became longer accompanied by a reduced number of platelets adhering to films of the copolymers with decreasing PHB content in the triblocks. Murine osteoblast MC3T3‐E1 cells cultured on the triblock copolymer films spread and proliferated significantly better compared with their growth on homopolymers of PHB, PLA and PCL, respectively. CONCLUSION: For the first time, PHB‐PLA‐PCL triblock copolymers were synthesized using low molecular weight LMPHB oligomer as the macroinitiator through ring‐opening polymerization with D ,L ‐lactide and ε‐caprolactone. The triblock copolymers exhibited flexible properties with good biocompatibility; they could be developed into promising biomedical materials for in vivo applications. Copyright © 2008 Society of Chemical Industry     

Synthesis of biodegradable and flexible,polylactic acid based,thermoplastic polyurethane with high gas barrier properties

Polylactic acid (PLA) has the beneficial properties of good mechanical strength, biodegradability and biocompatibility, and these properties make it suitable for use as an environmentally friendly packaging material. However, its use has been limited by its brittleness and poor stability. In this work, we successfully developed an efficient synthesis scheme to improve the mechanical properties, flexibility and gas barrier properties of PLA‐based polymers. Four different PLA‐based thermoplastic polyurethane (PLAPU) polymers were synthesized through the reaction of PLA diol with hexamethylene diisocyanate, followed by chain extension with polycaprolactone (PCL) diol. The relative compositions of the hard PLA and the soft PCL diols in the PLAPU polymers were controlled systematically to optimize the physical properties of the polymers. For example, increasing the content of PCL resulted in higher molecular weight PLAPU polymers that had increased tensile strengths and elongations at break, but their moduli were decreased. At the optimized PLA:PCL ratio of 1:3, the PLAPU polymer had an excellent elongation at break of 1053% with a relatively high Young's modulus of 51.8 MPa. In addition, the gas barrier properties of the PLAPUs were significantly enhanced depending on the molecular weight and PCL content of the polymers. To demonstrate the feasibility of using PLAPU polymers for biodegradable packaging materials, hydrolytic degradation tests were performed in phosphate buffer solution, and the PLAPU polymers were degraded gradually at rates that depended on the content of PCL in the polymers. This optimized PLAPU polymer exhibited excellent flexibility and gas barrier property, as well as high elongation, demonstrating its potential utility as packaging materials. © 2013 Society of Chemical Industry     

Synthesis and characterization of poly(lactic acid) and aliphatic polycarbonate copolymers

BACKGROUND: Poly(lactic acid) (PLA) has received much attention as a biodegradable polymer. But the physical properties of PLA, such as brittleness, limit its wider applicability. Copolymerization polymers ing soft blocks provides a useful method to improve the mechanical properties of PLA. RESULTS: Poly(lactic acid)‐block‐(polycarbonate diol) (PLA‐PCD) copolymers were synthesized using a two‐step process with polycondensation and chain extension reactions. The effect of polycarbonate diol content on the prepolymer properties was studied. The chain‐extended products were characterized using ¹H NMR, F and. The effect of the NCO/OH ratio on the properties of the chain‐extended products, including the mechanical properties and thermal properties, was studied. eight‐average molecular weight of the product can reach 210 000 g mol^?1 when the molar ratio of ? NCO to ? OH is 3:1. CONCLUSION: The PLA‐PCD copolymers obtained can crystallize, and the crystallinity decreases with chain‐extension reaction. The products exhibit superior mechanical properties with elongation at break above 230%, which is much higher than that of PLA chain‐extended products. The products have a good potential for packaging applications. Copyright © 2009 Society of Chemical Industry     

生物降解材料聚乳酸的合成

系统地介绍了包括丙交酯二步法、乳酸溶液聚合法和乳酸熔融聚合法在内的各种聚乳酸合成方法；并从安全和经济的观点出发，对聚乳酸的合成研究方向进行了展望，指出使用安全无毒的催化剂进行乳酸直接熔融聚合生产聚乳酸尤其值得大力开发。     

丙交酯与聚乳酸的合成

以D,L-乳酸为单体,氧化锌为催化剂,将乳酸合成D,L丙交酯;再以辛酸亚锡为催化剂,使丙交酯单体开环聚合制备聚乳酸。结果表明,乳酸在130℃、氧化锌质量分数为1.1%时,其粗产品产率大于60%;丙交酯聚合时,辛酸亚锡用量为0.02 mL时,聚合温度为160℃,常压聚合5 h即可得到粘均分子质量为6.0×104的聚乳酸;测试结果表明丙交酯在辛酸亚锡作用下发生了开环反应。