Synthesis of high molecular weight polylactic acid from aqueous lactic acid co-catalyzed by tin（Ⅱ）chloride dihydrate and succinic anhydride

Polylactic acid was synthesized from commercial available cheap aqueous lactic acid （85%-90% w/w） using succinic anhydride and SnCl2·2H2O as catalyst in the absence of organic solvents. As a result, polylactic acid with a molecular weight of 60000 was prepared in 10 h. The new procedure is much simple, cheap and outstanding in that the start material is aqueous lactic acid; the catalytic system is environmentally benign.     

Study of Synthesis of Copoly （lactic acid／glycolic acid） by Direct Melt Polycondensation

A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/ptoluenesulfonic acid. In this way, the direct synthesis of copoly (lactic acid/glycolic acid) without any organic solvent was investigated. The properties and structures of products were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction and so on. The results show that comparatively high molecular weight copolymer of lactic acid and glycolic acid can be prepared by direct processing under appropriate technological conditions.     

聚乳酸-聚扁桃酸共聚物的合成与表征

合成乳酸OCA和扁桃酸OCA单体,用DMAP引发乳酸OCA和扁桃酸OCA开环共聚合成可生物降解的聚乳酸-聚扁桃酸共聚物,通过调节聚合共聚单体的比例,可得到分子量从3 620¹1 800 g/mol不等的共聚物,实现了分子量可控的目的.使用1H NMR、GPC、DSC、TEM、XRD等手段对共聚物进行了表征,所得共聚物的热力学性能、降解性能等均得到改善.并对轮状病毒进行负载制备成载药微球,对其降解行为进行研究,为药物控制释放提供一类新的载体材料.     

反相悬浮聚合法合成超高分子量聚丙烯酸钠

以丙烯酸钠和丙烯酰胺为单体,采用反相悬浮聚合法制备了超高分子量的聚丙烯酸钠(NaPA).研究了引发剂浓度、抗交联剂及其他助剂对合成产物聚丙烯酸钠性能的影响.结果表明,(NH4)2S2O8的最佳用量是0.15%(质量分数);随着CO(NH2)2用量的增加分子量提高明显;在聚合体系中加入甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)可提高分子量但用量应控制在9.4×10-4%～15.6×10-4%之间.同时用抗交联剂防止交联反应,结合使用醋酸钠和异丙醇这两种分子量调节剂不仅能提高分子量而且溶解性也得到改善.最终得到了分子量高达3.0×107的产物,其分子量和溶解性能较前人研究成果有明显提高.     

反相悬浮法合成超高分子量AM/AA/AMPS及盐的共聚物

以丙烯酰胺(AM)、丙烯酸(AA)和2-丙烯酰胺-2-甲基丙磺酸(AMPS)为单体,采用反相悬浮聚合法制备了超高分子量的AM/AA/AMPS及盐的共聚物。本实验固定丙烯酰胺的加入量,研究了中和度、2-丙烯酰胺-2-甲基丙磺酸和丙烯酸用量,引发剂浓度、抗交联剂及其他助剂对合成共聚物分子量的影响。结果表明,本实验的中和度为70%比较适宜。在此中和度下,AMPS的适宜用量范围为AM的75%～16.25%;AA的适宜用量范围44%～55%;(NH₄)₂S₂O₈的适宜用量范围为AM/AA/AMPS总量的0.07%～0.12% ;分子量随CO(NH₂)₂的增加而明显升高;甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)的适宜用量范围为0.06 %～0.10%;使用抗交联剂可以解决产品交联造成的难溶问题,但加入量不宜过多,否则分子量会下降;分子量调节剂醋酸钠的用量在1.24 %～1.54%范围内可以使产品的分子量达最佳值。本实验可以得到分子量达1.9×10⁷的AM/AA/AMPS及盐的共聚产物。     

苯羟乙酸锌(Ⅱ)配合物的合成与光谱表征

在水热条件下,以苯羟乙酸(H2L)与硝酸锌为原料合成了苯羟乙酸锌配位物 [Zn(L)2].通过元素分析、红外光谱、质谱、核磁共振以及紫外和荧光光谱确定了它的组成和性质.     

聚乳酸膜表面氨等离子体改性

为研究氨等离子体对聚乳酸膜表面进行改性以及改性时发生的化学变化，采用接触角和XPS来表征．实验结果表明，氨等离子体能对聚乳酸膜表面进行改性，氨主要以-NH-CO-或C-N和-NH3^ 基团形式接枝在聚乳酸膜表面的链段上，并且随着等离子体处理时间从5min延长到20min，聚乳酸膜表面N元素的含量也从3.2％增加至5.2％(P=80W，而接触角则随聚乳酸膜表面接枝上亲水性极强的-NH3基团含量而变化．     

星形聚L-乳酸-甲基丙烯酸酐接枝聚合物的合成与表征

目的由于PLLA合成分子量低、疏水性强、韧性差、细胞相容性不佳,通过对PLLA改性,进一步改善其亲水性、血液相容性。方法以L-乳酸(L-LA)为单体,季戊四醇为扩链剂,辛酸亚锡为催化剂,在微波辐射作用下通过熔融缩聚开环聚合的方法合成了具有星形结构的聚L-乳酸(s-PL-LA);通过合成的s-PLLA与甲基丙烯酸酐(MAAH)的接枝反应,制备了具有甲基丙烯酸酯基的PLLA聚合物(PLLA-MAAH)。通过凝胶渗透色谱(GPC)、核磁共振(NMR)、傅里叶变换红外光谱(FTIR)、差示扫描量热(DSC)、X射线衍射(XRD)、粉末法动态接触角(DCAT)测试等手段对合成的s-PLLA和PLLA-MAAH的相对分子质量、结构与性能等进行了表征。结果由L-乳酸单体合成的聚合物为星形结构s-PLLA,s-PLLA与MAAH接枝反应后形成一个末端多官能团的聚合物PL-LA-MAAH。结论相比于s-PLLA,PLLA-MAAH相对分子质量增加,亲水性增强。     

苯乙烯－甲基丙烯酸共聚物的合成、结构与性能研究

采用悬浮聚合法合成了苯乙烯－甲基丙烯酸共聚物（ＳＭＡＡ），得率为９２％左右。由Ｋｅｌｅｎ－Ｔｕｄｏｓ法求得苯乙烯（Ｓｔ）与甲基丙烯酸（ＭＡＡ）在８０℃进行共聚反应的竞聚率为γ＿（Ｓｔ）＝０．３０５，γ＿（ＭＡＡ）＝０．６００。通过正交试验，确定了最佳配方。经ＦＴ－ＩＲ、ＤＳＣ、元素分析、化学滴定、ＧＰＣ等表征，证实了所合成的产物为透明的苯乙烯－甲基丙烯酸无规共聚物。研究表明，ＳＭＡＡ的耐热性比ＰＳ好得多，其玻璃化温度随共聚物中ＭＡＡ含量增加而增大，活化能为１６６．３ｋＪ／ｍｏｌ。共聚物的加工性能良好，力学性能比ＰＳ有了明显提高。     

甜菜高分子量核DNA的分离

研究了从甜菜中分离高分子量核DNA的方法．利用离心分离细胞核，经低融点琼脂糖块包埋、蛋白酶K原位裂解，结合低融点琼脂糖脉冲电泳去除淀粉制备高分子量核DNA．结果表明利用幼叶制备高分子量核DNA分子量高，更容易去除其中的淀粉；并且利用该方法得到的高分子量核DNA纯度高，适于部分酶切．     

聚乳酸-聚乙二醇嵌段共聚物及其交联聚氨酯弹性体的性能研究

通过改变聚乙二醇的用量,将丙交酯与聚乙二醇共聚制成嵌预聚体,用二苯基甲烷二异氰酸酯扩链后再用三羟甲基丙烷交联,制得系列聚氨酯型新颖性体。通过对其性能研究表明,随着ＰＥＧ含量的增加,共聚物的特性粘度降低,玻璃化转变温度降低,拉伸强度先升后降;聚氨酯弹性体的玻璃化转变温度降低,拉伸强度降低,而降解速度去加快。     

Synthesis and characterization of amphiphilc block copolymer poly(methyl acrylic acid)-block-polytetrahydrofuran

Under the specially designated condition the polymerization of both tetrahydrofuran (THF) and tert-butyl methacrylate (tBMA) is a living one. The diblock copolymer, poly(tert-butyl methacrylate)-block-polytetrahydrofuran (PtBMA-b-PTHF), was successfully synthesized by means of the coupling reaction of living cationic PTHF+, SbF6- with living anionic PtBMA-, Li+. LiCl, which has a beneficial effect on the molecular weight distribution (MWD) in the anionic polymerization of (meth)acrylates, hinders the coupling reaction of living chains and cannot be used in the preparation of tBMA precursor. The hydrolysis of the aforementioned diblock copolymer under acid condition results in the amphiphilic diblock copolymer, i.e. poly(methyl acrylic acid)-block-polytetra- hydrofuran (PMAA-b-PTHF). The diblock copolymers were characterized with GPC and IR.     

Melt rheology of poly (lactic acid) plasticized by epoxidized soybean oil

This study investigated that epoxidized soybean oil (ESO) was blended as plasticizer with poly (lactic acid) (PLA) and its effects on the melt rheological properties, such as melt flow index, apparent shear viscosity, and melt strength of the blends. PLA was blended by the twin-screw plastic extruder at five mass fractions: 3%, 6%, 9%, 12%, and 15% (based on PLA mass). Melt flow index (MFI) was examined with a melt flow indexer. The results indicate that the blends of PLA/ESO had higher MFI than pure PLA, except for MFI at 9% reaching to the lowest point, even lower than that of pure PLA. Melt rheological properties were studied by a capillary rheometer in a temperature range of 160–180 °C. The blends ends exhibited shear-thinning behavior and the apparent shear viscosity was well described by the power law in this shear rate region. The melt strength of PLA plasticized with 6% ESO reached the maximums. ESO was more effective in increasing the melt strength at the mass fractions less than 6%, which could toughen the blends to some extent. Therefore, the authors suggested the optimum addition level of 6%–9% ESO will get good melt rheological performance balance. Biography: XU Yuqiong (1974–), female, Ph.D., research direction: polymer composites.     

埃洛石纳米管对聚乳酸基材料的改性研究进展

埃洛石纳米管（HNTs）是一种天然的无机纳米管状材料，具有与高岭土相似的化学组成以及与碳纳米管类似的一维结构，因其来源广泛、价格低廉，并且具有较大的长径比、较大的比表面积以及高模量等特点，近年来受到广泛关注并被应用于高分子材料的改性之中。本文在HNTs的结构特点和现有的表面改性方法的基础上，梳理了近年来HNTs用于聚乳酸（PLA）基聚合物复合材料改性的相关研究工作，重点关注了HNTs对材料的热稳定性、相结构、结晶性能、降解性能、机械性能以及生物医学性能方面的影响，展望了HNTs改性PLA复合材料的研究和应用前景。     

CdTe/聚乳酸纳米杂化材料的制备及其荧光性能

以十二烷基胺(DDA)为表面修饰剂,将巯基水相法合成的CdTe纳米晶转移至有机溶剂三氯甲烷中,然后采用“物理共混法”实现了CdTe/聚乳酸(CdTe/PLA)纳米杂化材料及其透明荧光膜的制备.通过紫外-可见光谱仪(UV -vis)、荧光(PL)、紫外透射反射分析仪等表征方法考察相转移前后CdTe纳米晶的光学性能,并系统研究了CdTe/PLA纳米杂化材料的荧光性能.结果表明:相转移后CdTe纳米晶的粒径未发生明显变化,其量子产率却提高了;所制备的CdTe/PLA纳米杂化材料具有优越的荧光性能,CdTe纳米晶在聚合物中仍然保持良好的分散性和较好的量子尺寸效应.     

Synthesis and characterization of amphiphilc block copolymer poly(methyl acrylic acid)-block-polytetrahydrofuran

Under the specially designated condition the polymerization of both tetrahydrofuran (THF) andtert-butyl methacrylate (tBMA) is a living one. The diblock copolymer, poly(tert-butyl methacrylate)-block-polytetrahydrofuran (PtBMA-b-PTHF), was successfully synthesized by means of the coupling reaction of living cationic PTHF⁺, SbF₆ with living anionic PtBMA^-, Li⁺. LiCI, which has a beneficial effect on the molecular weight distribution (MWD) in the anionic polymerization of (meth)acrylates, hinders the coupling reaction of living chains and cannot be used in the preparation of tBMA precursor. The hydrolysis of the aforementioned diblock copolymer under acid condition results in the amphiphilic diblock copolymer, i.e. poly(methy1 acrylic acid)-block-polytetrahydrofuran (PMAA-b-PTHF). The diblock copolymers were characterized with GPC and IR.     

双三(邻氯苄基锡)哌嗪二荒酸酯的合成、表征和晶体结构

合成了双核有机锡化合物双(三邻氯苄基锡)哌嗪二荒酸酯.通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征.用X-射线单晶衍射测定了这两个化合物的晶体结构.化合物晶体为单斜晶系,空间群P21／c,a=1.032(2)nm,b=2.569(5)nm,c=1.033(2)nm,β=115.22(3)°,Z=2,V=2.478(8)nm3,Dc=1.644 g／cm3,μ=1.536 mm-1,F(000)=1 224,R1=0.0453,wR2=0.084 3.在该化合物中,锡原子呈五配位畸变三角双锥构型.     

碱性介质中二羟基二过碘酸合镍(IV)配离子氧化天冬氨酸的反应动力学及机理

在碱性介质中于 ２０－３５℃用分光光度法研究了二羟基二过碘酸合镍（ＩＶ）配离子 （ＤＤＮ）氧化天冬氨酸的动力学。结果表明,反应对［Ｎｉ（ＩＶ）］为一级,对天冬氨酸为正分数级。准 一级速率常数（Ｋｏｂｓ）随［ＯＨ－］增加而减小,１／ｋｏｂｓ对［ｉｏ－４］有线性关系,表明二羟基一过碘酸合镍 （ＩＶ）配离子（ＤＭＮ）是氧化剂的活性物种。无盐效应且未检出自由基的存在。据此提出了包括 ＤＰＮ和ＭＰＮ以及天冬氨酸存在前期平衡的反应机理,并求出相应的活化参数。     

Synthesis and magnetic properties of one-dimensional Mn（Ⅱ） complexes linked by dithiooxalato

Three dithiooxalato (Dto) bridging one-dimensional Mn(Ⅱ) complexes [Mn(L)Dto](L=Phen (1), Bpy (2) and en (3)) were synthesized. All of the complexes have the similar one-dimensional structure through Dto bridge. The measurement of the variable temperature magnetic susceptibility of complex 1 showed that there are weak antiferromagnetic interactions between the Mn(Ⅱ) ions.     

Synthesis and magnetic properties of one-dimensional Mn(II) complexes linked by dithiooxalato

Three dithiooxalato (Dto) bridging one-dimensional Mn(II) complexes [Mn(L)Dto](L = Phen (1), Bpy (2) and en (3)) were synthesized. All of the complexes have the similar one-dimensional structure through Dto bridge. The measurement of the variable temperature magnetic susceptibility of complex 1 showed that there are weak antiferromag-netic interactions between the Mn(II) ions.