超临界CO2中聚乳酸的合成及表征

以辛酸亚锡为催化剂用超临界二氧化碳作溶剂成功地实现了L-丙交酯的开环聚合,聚合产物用FT-IR、^1H-NMR、^13C-NMR、DSC和GPC进行了分析表征,结果表明：超临界二氧化碳流体中左旋丙交酯开环聚合不是离子型聚合．可能是配位一插入聚合。所合成的聚乳酸具有很高的光学活性;所得聚合物无论分子量大小,都具有熔点和中等结晶度,且随分子量的增大而升高。     

聚L-丙交酯合成工艺条件研究

在超声波辐射条件下 ,以丙交酯为原料、辛酸亚锡为催化剂 ,通过开环聚合反应制得聚L 丙交酯 (PLLA)。应用红外光谱 (IR)表征聚合物的结构 ,详细讨论了丙交酯纯度、聚合温度、聚合时间和超声辐射对聚合物分子质量的影响。优化聚合条件可获得粘均分子量 >1 80× 1 0 3的聚丙交酯材料 ,聚合结果具有良好的重复性     

生物可吸收材料PDLLA的聚合条件研究

通过乳酸脱水合成出高纯度的D ,L 丙交酯。以辛酸亚锡为引发剂 ,进行丙交酯开环聚合为聚乳酸 (PDLLA)的实验研究。讨论了D ,L 丙交酯开环聚合的影响因素和PDLLA聚合条件     

丙交酯合成条件的研究

丙交酯作为合成聚乳酸的重要中间体,它的制备是影响开环聚合高分子量PLA的关键因素。反应时间和反应温度是制备丙交酯的两个重要的工艺参数,直接影响丙交酯的产率。本文着重就反应时间对丙交酯产率的影响进行了初步研究,并提出了一种制备丙交酯的优化工艺。     

丙交酯的合成与聚合

丙交酯是由乳酸合成聚乳酸的中间体,采用新型La Ti复合氧化物催化乳酸合成丙交酯,粗丙交酯经乙酸乙酯纯化后,差热分析仪测得其熔点为126 4℃,纯化后的丙交酯在一定条件下,经辛酸亚锡引发,开环聚合成聚乳酸,并用红外光谱和差热分析仪对聚乳酸进行了表征。     

环烷氧锡引发L-丙交酯的开环聚合

以环烷氧锡化合物引发L-丙交酯开环聚合制备高分子量聚L-乳酸。考察了单体引发剂配比、聚合温度和聚合时间等聚合条件对聚合产物特性黏度的影响。用1H-NMR、13C-NMR分析聚合产物微观结构表明,环烷氧锡引发L-丙交酯开环聚合是基于酰氧键断裂开环聚合的“配位-插入”机理。DSC、TGA、XRD等测试结果表明,所得聚L-乳酸具有较高的结晶度和立构规整度。     

L-丙交酯和D,L-丙交酯混合制备PLA工艺探讨

以辛酸亚锡为催化剂,采用开环聚合法,对L-丙交酯和D,L-丙交酯混合制备PLA工艺进行探讨,分别考察了D,L-丙交酯含量、催化剂用量、聚合时间、聚合温度和体系真空度对PLA粘均分子量的影响。经过GPC测试,所得PLA的质均分子量达到1.15×105,并采用红外光谱仪和差热-热重分析仪对PLA进行了结构和热性能表征。     

L-丙交酯和聚L-乳酸的制备与性能

从左旋L-乳酸经高温催化反应得到低聚L-乳酸，再经高温裂解减压蒸馏制得单体L-丙交酯（LLA），理论收率高达80%以上。LLA经纯化，再以辛酸亚锡为催化剂开环聚合得到聚L-丙交酯（聚L-乳酸，PLLA），其粘均分子量可达到40万。     

聚乳酸的合成研究

聚乳酸是一种具有良好生物相容性、可降解的高分子材料,被广泛应用于医用领域,受到越来越多的关注。聚乳酸的合成主要有两种方法：乳酸直接缩聚和丙交酯的开环聚合。文中综述了近年来聚乳酸合成研究的最新进展,讨论了直接合成时的反应条件对聚乳酸分子量的影响,似及不同催化剂对丙交酯开环聚合的影响,介绍了聚乳酸聚合的一种高效方法——反应挤出法,并展望了聚乳酸合成研究的前景。     

聚-3-羟基丁酸酯及其共聚物的合成与表征

合成一种环烷氧锡化合物,用氢谱、元素分析和质谱对其结构进行表征确认,并以其作为β-丁内酯开环聚合的引发剂制备聚-3-羟基丁酸酯,考察了单体引发剂配比、聚合时间和聚合温度等聚合条件对聚合产物特性粘度的影响.由丁内酯与丙交酯、己内酯共聚制备聚(丁内酯-丙交酯)和聚(丁内酯-己内酯)共聚物,并用FT-IR、1H-NMR、DSC等手段对聚合物的结构及性能进行了表征.     

A Quantitative Method for Determination of Lactide Composition in Poly(lactide) Using (1)H NMR

A method has been developed to quantitatively determine the composition of d-lactide and meso-lactide stereoisomer impurities in poly(lactide) containing predominantly l-lactide. In this method, the stereosequence information obtained from a few well-resolved resonances in the (1)H NMR spectrum representing RR and R stereogenic defects is used. The d-lactide and meso-lactide as minor components lead to RR and R stereogenic defects, respectively, which influence the isotactic chain length distribution and hence affect the polymer properties. Analytical equations relating the stereosequence probability to the lactide feed composition are not available due the complicated kinetics involved for the melt polymerization; viz. the preference for syndiotactic lactide addition decreases with reducing residual lactide concentration in the batch process. Hence, empirical correlations were determined by least-squares fit to the predictions for the specific stereosequence probabilities provided by Monte Carlo calculations of a number of lactide stereocopolymerizations. The Monte Carlo calculations simulate the kinetics observed for melt polymerization at 180 °C catalyzed by Sn(II) bis(2-ethylhexanoate) (Sn(II) octoate) in a 1:10 000 catalyst/lactide ratio.     

An easy method to monitor lactide polymerization with a boron fluorescent probe

Fluorescence spectroscopy has been widely used to monitor different polymer processes such as polymerization kinetics, chain entanglements, and thermal transitions. The solvent-free controlled ring-opening polymerization (ROP) of lactide is significant both commercially and for research; thus, monitoring this process with a simple fluorescence method can be very useful. Here, a fluorescent dye, difluoroboron 4-methoxydibenzoylmethane (BF(2)dbmOMe) is employed to probe lactide bulk ROP by measuring the emission from solidified reaction aliquots at room temperature. It was found that, through the course of polymerization, the fluorescence of BF(2)dbmOMe in the solid-state aliquots exhibited a systematic shift from yellow to green and then to blue, accompanied by a gradual reduction in the decay lifetime. The fluorescence color change is sensitive to the monomer percent conversion, not the polymer molecular weight. On the basis of these observations and experimental data, we propose that the long-wavelength emission with perceivably longer lifetimes arises from BF(2)dbmOMe dye aggregates (ground and/or excited states), while the dissolved individual dye molecules are responsible for the blue fluorescence with a shorter lifetime. This demonstration of the utility of BF(2)dbmOMe as a fluorescent probe for lactide polymerization could have important practical implications.     

含POSS聚合物的制备与性能研究进展

多面体齐聚倍半硅氧烷(POSS)具有特殊的笼状结构,可从纳米尺度上起到对聚合物的改性作用。通过不同的方法将POSS分子引入到聚合物体系中去,以改善聚合物性能是聚合物改性的重要手段之一。文中从聚合方式上对含POSS聚合物的制备进行介绍,包括传统自由基聚合、活性聚合、缩聚聚合和开环聚合,并对合成的含POSS有机/无机聚合物的性能进行相关介绍。     

含半不稳定边臂配体的钛配合物催化丙交酯聚合

聚乳酸类材料作为可生物降解性材料具有广阔的应用前景。设计、合成了6种含半不稳定边臂的希夫碱配体L1—L6,并与钛酸四异丙酯络合合成相应的6种配合物C1—C6,配合物的结构和化学组成经元素分析、红外测试确定。将其作为催化剂催化丙交酯开环聚合,以催化剂C1为考察对象,系统研究了催化剂用量、温度、时间对聚合反应的影响,发现当单体与催化剂配比为2 000,温度为160℃,反应24h时,聚合产率最高,达90.35%,聚合物分子量达8.41×104。在上述优化条件下,比较了催化剂C1—C6的活性,结果表明催化剂活性按以下顺序递减:C6C4C3C1C2C5,同时,催化剂中心金属钛原子周围位阻相对稍小,配体中含配位能力较弱的半不稳定O边臂均有利于提高催化剂的活性。     

聚乳酸合成研究进展

针对直接法和二步法合成聚乳酸的共性,从单体纯度、催化剂选择到共沸脱水、微波辅助、超临界流体介质,以及到固相聚合、反应挤出、扩链等各个方面,对近年来聚乳酸合成研究的新进展进行了综述,指出各种新方法、新技术的复合应用是提高聚乳酸分子量、降低其成本的关键。     

药物缓释材料聚(乳酸-丙氨酸)的直接法合成与表征

直接以外消旋乳酸(LA)、L-丙氨酸(Ala)为原料[n(LA):n(Ala)=9:1],采用熔融聚合法合成药物缓释材料聚(乳酸-丙氨酸)共聚物[P(LA-co-Ala)],并用特性黏数、FTIR、1H NMR、GPC、DSC、XRD等手段进行系统表征.熔融共聚中采用一次投料并分次预聚,可生成重均相对分子质量(Mw)达3200(分散度Mw/Mn＝1.23)的共聚物,相对分子质量可以达到丙交酯开环共聚法的水平.首次报道了P(LA-co-Ala)]药物缓释材料的DSC与XRD表征结果,其与聚外消旋乳酸(PDLLA)相比,共聚物具有较低的Tg、Tm和结晶度.新方法步骤少、操作简便,且成本更加低廉.     

羟丙基甲壳素接枝聚乳酸的合成和表征

以Sn(OCt)2为催化剂,水溶性的羟丙基甲壳素作主链,通过丙交酯的熔融开环聚合,在其上接枝了聚乳酸支链.利用红外光谱、核磁共振谱对其结构进行了表征.在羟丙基甲壳素与丙交酯的比例分别为5:1,8:1,10:1条件下,反应都能顺利进行.聚乳酸的接枝长度随原料中丙交酯比例增大而增大.1H-NMR谱的结果表明,聚乳酸支链长度最长为5左右.     

原子转移自由基聚合反应改性氧化石墨烯研究进展

原子转移自由基聚合(ATRP)是一种具有潜在应用价值的可控活性自由基聚合方法,通过ATRP反应对氧化石墨烯(GO)进行改性,可以有效控制各种接枝聚合物分子链的长度和接枝密度,赋予GO不同的功能性,如良好的溶剂分散性、环境敏感刺激响应性、生物相容性等。文中分别从GO表面固定引发剂直接引发ATRP反应和GO表面非共价键结合ATRP聚合物分子链2种途径,对ATRP反应改性GO进行综述,总结了ATRP改性反应的过程条件和研究方法,并指出了GO功能化复合材料的功能特性和应用前景。     

Thermosensitive nanocontainers prepared from poly(N-isopropylacrylamide-co-N-(hydroxylmethyl) acrylamide)-g-poly(lactide)

Thermally-responsive graft copolymer of poly(N-isopropylacrylamide-co-N-(hydroxylmethyl)acrylamide)-g-poly(lactide) was synthesized by ring-opening polymerization of D,L-lactide (LA). The polymerization was initiated by the hydroxy group of poly(N-isopropyl acrylamide-co-N-(hydroxylmethyl) acrylamide), using stannous octoate as catalyst. The resulting polymer was temperature-sensitive and the lower critical solution temperature (LCST) was affected by their composition. The chemical structure and physical properties of the grafted copolymers were investigated by various methods. Nanocontainers formed from the self-assembly of poly(N-isopropylacrylamide-co-N-(hydroxylmethyl) acrylamide)-g-poly(lactide) were characterized by transmission electron microscopy (TEM), and a spherical structure was observed. Dynamic light scattering (DLS) results indicate that the particle size increased with the increase of polylactide content in the copolymer. The properties of this polymer are interesting for both industrial application and fundamental research. In particular it will combine a spatial specificity in a passive manner and a temperature-responsive active targeting mechanism for drug delivery system.