PBS-PPS生物降解聚酯的合成与降解性能EI北大核心CSCD

以癸二酸1,3-丙二醇酯(PPS)预聚物为软段,丁二酸丁二醇酯(PBS)预聚物为硬段,通过直接缩聚方式,合成了一系列聚(丁二酸丁二醇酯癸二酸1,3-丙二醇酯)嵌段共聚物(PBS-PPS)。通过红外光谱(IR)、核磁共振(1H-NMR)、差示扫描量热(DSC)、凝胶色谱(GPC)和扫描电镜(SEM)对产物进行了表征,研究了物料配比对共聚物的结晶性、热性能和降解性的影响。结果表明,合成产物为典型的聚酯结构,随着PPS链段的增加,共聚物的结晶度下降,PBS为68.00%,而PBS-PPS10∶3仅为35.50%;质量损失率增加,PBS在酶解液中10周内质量损失率为27%,而PBS-PPS10∶3为71%;相对分子质量降低程度增大,PBS下降了35%,而PBS-PPS10∶3为81%;共聚物表面形态的破坏程度和酯键的水解程度也有显著提高。     

一种新型可降解共聚物薄膜的制备与性能研究

在氩气环境下,以丁二酸、己二酸、1,4-丁二醇和尿素为原料,通过高温熔融缩聚和扩链反应合成了一种新型可降解丁二酸/己二酸-1,4-丁二醇-尿素聚酯酰脲共聚物,并用压延成膜法制备了共聚物薄膜.采用红外光谱、热重分析、差示量热扫描及万能拉力机对共聚物薄膜的结构与性能进行了表征.结果表明,随着己二酸含量的增加,聚合物薄膜的熔点、结晶度和结晶温度均明显下降.当n（SA）∶n（AA）=1∶1时,共聚物大部分为无定形区域,结晶性能大大降低,水解速率最快,薄膜的降解性能最好.通过调节丁二酸与己二酸添加的物质的量之比,可使聚酯酰脲薄膜在热学性能、力学性能和降解性能之间达到一定程度的可控性.     

聚乙二醇-聚丁二酸丁二醇酯-聚乙二醇嵌段共聚物的合成与表征EI北大核心CSCD

以1,4-丁二酸(SA)和过量的1,4-丁二醇(BD)为反应物,通过熔融缩聚制备了羟基封端聚丁二酸丁二醇酯齐聚物(OH-PBS-OH),以甲氧基聚乙二醇(Me OPEG)与丁二酸酐进行半酯化得到含端羧基的预聚物,再用二氯亚砜对预聚物进行活化,得到含酰氯端基的预聚物(Me OPEG-COCl);以Me OPEG-COCl与OH-PBS-OH为反应物,通过溶液法合成聚乙二醇-聚丁二酸丁二醇酯-聚乙二醇(Me OPEG-PBS-PEGOMe)嵌段共聚物。利用红外光谱、核磁共振、差示扫描量热、广角X射线衍射、偏光显微镜等手段对共聚物的结构、结晶性能和酶降解性能进行研究。结果表明,Me OPEG-PBS-PEGOMe嵌段共聚物中,聚乙二醇(PEG)链段的引入未改变聚丁二酸丁二醇酯(PBS)链段的晶体结构,但结晶形态由球晶转变为麦穗状晶体;同PBS比较,Me OPEG-PBS-PEGOMe嵌段共聚物的结晶速率降低,酶降解速率加快。     

聚乙二醇-聚丁二酸丁二醇酯-聚乙二醇嵌段共聚物的合成与表征

以1,4-丁二酸(SA)和过量的1,4-丁二醇(BD)为反应物,通过熔融缩聚制备了羟基封端聚丁二酸丁二醇酯齐聚物(OH-PBS-OH),以甲氧基聚乙二醇(Me OPEG)与丁二酸酐进行半酯化得到含端羧基的预聚物,再用二氯亚砜对预聚物进行活化,得到含酰氯端基的预聚物(Me OPEG-COCl);以Me OPEG-COCl与OH-PBS-OH为反应物,通过溶液法合成聚乙二醇-聚丁二酸丁二醇酯-聚乙二醇(Me OPEG-PBS-PEGOMe)嵌段共聚物。利用红外光谱、核磁共振、差示扫描量热、广角X射线衍射、偏光显微镜等手段对共聚物的结构、结晶性能和酶降解性能进行研究。结果表明,Me OPEG-PBS-PEGOMe嵌段共聚物中,聚乙二醇(PEG)链段的引入未改变聚丁二酸丁二醇酯(PBS)链段的晶体结构,但结晶形态由球晶转变为麦穗状晶体;同PBS比较,Me OPEG-PBS-PEGOMe嵌段共聚物的结晶速率降低,酶降解速率加快。     

聚(丁二酸丁二醇酯丁二酸环己烷二甲醇酯)的合成与表征

用熔融缩聚法合成了一系列聚(丁二酸丁二醇酯丁二酸环己烷二甲醇酯)的无规共聚物。用FT-IR,1H-NMR,DSC,TGA,XRD及水降解测试等方法表征了材料的结构与性能。通过DSC和TGA分析得到产物的熔点虽然较聚丁二酸丁二醇酯(PBS)有所降低,但是热分解温度却得到了提高;XRD测试结果表明,共聚物的晶体结构并没有发生改变;水降解测试结果表明,共聚物较PBS的降解速率有所提高。     

新型可降解丁二酸-1,4-丁二醇-1,3-丙二醇-尿素共聚物的合成与表征

以丁二酸、1,4-丁二醇、1,3-丙二醇和尿素为原料,采用熔融缩聚法制备低分子量的聚酯酰胺预聚体,以甲苯二异氰酸酯(TDI)作为扩链剂对聚酯酰胺预聚体进行扩链,得到了一系列Mw为1.0×105~1.7×105的新型可降解丁二酸-1,4-丁二醇-1,3丙二醇-尿素共聚物(聚酯酰胺),并采用流延法制备了聚酯酰胺薄膜。考察了尿素含量对聚酯酰胺热性能、结晶性能、力学性能和降解性能的影响。采用FT-IR、1H NMR、GPC、TG、DSC和XRD等对聚酯酰胺进行了表征。结果表明,随着尿素含量的增加,聚酯酰胺的熔点和热稳定性下降。尿素的加入未改变聚酯酰胺中聚酯相的晶型,但破坏了聚酯链段的规整性,使其结晶度降低。随着尿素的加入,聚酯酰胺薄膜的力学性能和降解性能不断提高。     

发展环境友好型生物基材料

<正>一、我国生物基材料产业发展现状与问题在几个五年计划和八六三计划支持下,我国生物基材料包括聚羟基脂肪酸酯(PHA)、聚乳酸(PLA)、丁二酸丁二醇共聚物(PBS)、二氧化碳共聚物(PPC)、对苯二甲酸1,3-丙二醇共     

可降解聚酯酰胺共聚物的合成及其性能研究

以丁二酸、丁二醇、1,6-己二胺为原料,二丁基二月桂酸锡为催化剂,甲苯二异氰酸酯(TDI)为扩链剂,通过熔融共聚,合成了Mw为40~65 k的聚丁二酸-丁二醇-1,6-己二胺共聚物,并采用压延成膜法制得聚酯酰胺薄膜。研究了1,6-己二胺含量对聚酯酰胺的热性能、结晶性能、降解性能和流变性能的影响。结果表明,合成了聚酯酰胺,其熔点达到100.97℃,热分解温度为317.85℃;随着1,6-己二胺添加量增加,聚酯酰胺的拉伸强度不断变大,断裂伸长率略有下降;1,6-己二胺的加入并未改变聚酯酰胺的晶型,但降低了其结晶度;1,6-己二胺的加入提高了聚酯酰胺降解性能,而且改善了其流变性能,这有利于聚酯酰胺的成型加工和应用。     

癸二酸改性丁二酸丁二醇基聚酯材料的结晶性能和降解性能

以癸二酸、丁二酸为二元酸,丁二醇为二元醇,通过熔融共聚的方式合成了聚(癸二酸丁二醇酯丁二酸丁二醇酯)无规共聚物(SE10)和聚丁二酸丁二醇(PBS),并通过酶解实验研究了相对分子质量、结构、表面形态的变化。通过红外光谱、差示量热扫描仪、偏光显微镜、凝胶色谱和扫描电镜对二者降解前后性能进行了研究,相比PBS,SE10晶体直径较小,晶体结构形态变模糊,结晶度由68.0%下降为45.7%,熔点由115.23℃下降为92.40℃。90d后SE薄膜的质量损失率达到63%,珚Mw由34700降为11500,而PBS质量损失率为27%,珚Mw由49000降为33000。表明癸二酸的引入降低了PBS的结晶性能,提高了其降解性能。     

生物可降解聚丁二酸丁二醇酯的合成及两亲性改性研究

脂肪族聚酯由于其生物降解性和经济性，已成为国内外降解材料研究的重点。以丁二酸和丁二醇为原料，通过熔融缩聚法合成聚丁二酸丁二醇酯（PBS），并通过与己内酯、聚乙二醇共聚，改善其降解性能。利用FT-IR、^1H-NMR、DSC、粘度法测定分子量等方法对共聚物组成、热学性能及亲水性能进行了研究。实验结果表明，改性后的聚酯高分子链有更好的柔韧性和亲水性，可以加快降解速率。     

Enhanced wear performance of ultra high molecular weight polyethylene crosslinked by organosilane

Ultra high molecular weight polyethylene (UHMWPE) crosslinked by organosilane was thermal compression molded. The organosilane used was the tri-ethyloxyl vinyl silane. Its gelation, melting behavior, crystallinity, mechanical and wear-resisting properties were systematically investigated. The results showed that the gel ratio of UHMWPE increases with the incorporation of organosilane. At a low content of organosilane, the melting point and crystallinity of the crosslinked UHMWPE increase, and hence the mechanical and wear-resisting properties are improved. However, at a high content of organosilane, these performances of the crosslinked UHMWPE become worse. At 0.4 phr silane, the wear resistance of crosslinked UHMWPE reaches its optimum value.     

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征（Ⅰ）

本文采用直接熔融缩聚法合成了含４，４＇－二烃基二苯酮、对苯二甲酸、对羟基苯甲酸和一缩二乙二醇的四元共聚酯。利用差动扫描量热计（ＤＳＣ）、偏光显微镜、Ｘ射线衍射等手段对该共聚酯进行了表征。结果表明，聚合物具有向列型热致液晶特性。本文还对不同温度和剪切取向下的液晶态织构以及不同条件处理的试样的结晶行为进行了初步的探讨。     

阳离子染料可染共聚酯的结构及性能

采用动态力学分析法(DMA)、热重法(TGA)及X射线衍射法对常规PET、CDP及醚型ECDP的结构及性能进行了研究。结果表明,CDP的Tg高于PET,但其Tα′及Tm均低于PET。ECDP的Tg、Tα′及Tm均低于PET和CDP,并且随PEG含量及分子量的增加而降低;热解活化能(ΔEd)随着SIPE与PEG含量的增加而降低,即热稳定性降低;另外,与常规PET相比,CDP及ECDP的衍射峰位置基本没有改变,改性共聚酯的组分并未砌入晶格,而是存在于无定型区。     

Synthesis and characterization of a novel multiblock copolyester containing poly(ethylene succinate) and poly(butylene succinate)

Multiblock copolyester (PBS-b-PES) containing poly(butylene succinate) (PBS) and poly(ethylene succinate) (PES) was successfully synthesized by chain-extension of dihydroxyl terminated PBS (HO-PBS-OH) and PES (HO-PES-OH) using 1,6-hexmethylene diisocyanate (HDI) as a chain extender. The chemical structures, molecular weights, crystallization behaviors, thermal and mechanical properties of the copolyesters were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), wide-angle X-ray diffraction (WAXD), tensile testing and hydrolytic degradation. High-molecular-weight copolyesters with M_w more than 2.0 × 10⁵ g mol⁻¹ were easily obtained through chain-extension. The copolyesters showed a single glass transition temperature (T_g) which increased with PES content. The melting point temperature (T_m) and relative degree of crystallinity (X_c) of the copolyesters decreased first and then increased with PES content. The copolyesters manifested excellent mechanical properties, for example, PBS₅-b-PES₅ had fracture stress of 61.8 MPa and fracture strain of 1173%. The chain-extension reaction provided a very effective way to produce high molecular weight multiblock copolyesters.     

纳米ATO/PVB隔热透明原位复合材料的制备及性能

利用超声波将经表面预处理的纳米氧化锡锑(ATO)粒子均匀分散到聚乙烯醇(PVA)水溶液中,与正丁醛缩合反应,原位法制备了一系列纳米ATO/聚乙烯醇缩丁醛(PVB)复合材料。采用FTIR、UV/VIS/NIR、TG、TEM及AFM等对所制备的原位纳米ATO/PVB复合材料的结构、微观形貌及性能进行了研究。结果表明: 在合成PVB树脂的阶段添加少量纳米ATO粒子,能更均匀地分散在PVB基质中,所制备的复合材料薄膜的紫外线及近红外光透过率大幅度下降,而可见光透过率降低幅度较小,且随纳米ATO用量增加,紫外屏蔽及隔热性能不断提高。在纳米ATO用量(与PVB质量比为2.76%)较低时,纳米ATO/PVB复合材料的力学性能尤其韧性得到明显提高,断裂伸长率达到纯PVB的7.3倍; 在ATO与PVB质量比为1.74%时,可见光透过率高于70%,紫外光透过率低于10%,近红外光热辐射透过率低于28%,导热系数为0.23 W(m·K)^-1,与纯PVB相比,用纳米ATO/PVB复合材料胶膜所制盖板的隔热空腔内温度下降5.5℃,具有良好的透明度、紫外屏蔽及隔热性能。     

Surface Tensions and Thermal Conductivities of Aqueous LiBr-Based Solutions Containing n-Octanol and 2-Ethyl-1-Hexanol: Application to an Absorption Heat Pump

Surface tensions and thermal conductivities were measured for LiBr+1,3-propanediol+water and LiBr+LiI+1,3-propanediol+water. These two mixtures were chosen as one of the potential candidates for working fluids for absorption heat pumps. Surface tensions and thermal conductivities were measured by the capillary rise method equipped with a cathetometer and the transient hot wire method with a coated tantalum wire, respectively. The measured surface tension and thermal conductivity data were well correlated with a simple polynomial function of temperature and absorbent concentration. In addition, the surface tensions of LiBr+1,3-propanediol+water containing a small amount of alcohol-based surfactants, n-octanol and 2-ethyl-1-hexanol, were also measured at 298.15 K by the ring method. An increase in the surfactant concentration up to about 500 ppm leads to a gradual decrease in the mixture surface tensions.     

Synthesis of waterborne polyurethane using snow as dispersant: Structures and properties controlled by polyols utilization

Waterborne polyurethane (WPU) dispersions have gained attention towards environmentally-friendly synthesis. In this article, a series of waterborne polyurethane emulsions was successfully synthesized and extensively characterized in terms of thermal, mechanical properties, hydrophilic behavior and morphology. Snow was chosen as dispersant instead of commonly used water. Preparation parameters such as intrinsic properties and molecular weight of polyols were discussed systematically. A chain structure was confirmed by Fourier transform infrared (FT-IR) spectroscopy. When comparing the nature of the polyols (PPG, PEG and PNA, 2000 g/mol) of this study, as-synthesized polyether waterborne polyurethane provided higher solid content, viscosity and water-resistance. However, polyester waterborne polyurethane performed differently and it exhibited higher thermal stability and crystallinity. When comparing the samples (WPU-N210, WPU-N220, WPU-N230 and WPU-N240) with different molecular weight of the same polyol (PPG) used as soft segment, the emulsion WPU-N220 with molecular weight of 2000 g/mol PPG provided the highest solid content and lowest viscosity. It was observed that particle size was uniform and highly dispersed for all samples from TEM images. Thermogravimetric, differential scanning calorimetry (DSC) and X-ray diffraction results demonstrated that the emulsion WPU-N230 with molecular weight of 3000 g/mol PPG possessed higher thermal stability and crystallinity than the other samples. The reason was that the T_g and thermal stability were increased with increasing molecular weight. When molecular weight increased, the arrangement of soft segment became more regular and so did the regularity of the molecular chains. This work demonstrated that different polyols as soft segment applied could lead to great differences in the structure and property of the resulting WPU.     

魔芋葡甘聚糖基缓释膜材料的结构表征

以魔芋葡甘聚糖和大豆油为原料通过碱催化制备魔芋葡甘聚糖脂肪酸酯疏水膜(F-KGM);采用紫外-可见分光光度计、傅立叶变换红外光谱仪、十八角静态激光光散射仪、X射线衍射仪、热分析仪和扫描电子显微镜对其进行结构表征。结果表明,F-KGM的重均分子量(-Mw)为3.653×106g/mol,明显高于KGM的1.619×106g/mol,魔芋葡苷聚糖与脂肪酸分子形成酯键,KGM经酯化后,改变了原有的晶体结构,结晶度降低,具有更高的热稳定性,分子乳化融合流延成膜过程中发生分子自组装行为,形成性质稳定且具有良好疏水性能的缓释膜材料。     

疏水性增透聚酯薄膜的制备及应用

以聚苯乙烯为大分子引发剂,丙烯酸聚硅氧烷酯为单体,通过原子转移自由基聚合制备苯乙烯-丙烯酸聚二甲基硅氧烷酯共聚物。将所得聚合物旋涂于聚对苯二甲酸乙二醇酯(PET)薄膜表面,研究共聚物中不同硅氧烷含量对聚酯薄膜性能的影响。通过核磁共振和红外光谱表征了丙烯酸聚硅氧烷酯单体及与苯乙烯共聚产物的结构,结果表明实验成功制备出了苯乙烯共聚物;凝胶渗透色谱结果表明聚合物的相对分子质量与设计相对分子质量相接近,并且相对分子质量分布系数均小于1.4,说明反应具有一定可控性;紫外-可见光分光光度计结果表明聚合物的折射率随着嵌段聚合物中硅氧烷含量的降低而增加;通过场发射扫描电镜(FE-SEM)对改性前后的聚酯薄膜进行观察,结果显示聚酯薄膜表面形成了蜂窝状多孔结构,从而有效改善了薄膜的透光性。总体研究结果表明,随着共聚物中硅氧烷含量的增加,聚酯薄膜的水接触角和透光率均呈先增后减的趋势。当共聚物中硅氧烷含量为19.6%时,PS-PDMS嵌段共聚物折射率为1.38,涂覆在PET表面后薄膜透光率达到92.6%,水接触角为120°。     

天然抗氧化羟丙基甲基纤维素水溶性包装薄膜

将竹叶抗氧化剂(AOB)添加到羟丙基甲基纤维素(HPMC)制膜液中,采用流延法制得具有抗氧化性能的AOB/HPMC复合水溶性包装薄膜。并通过红外吸收光谱、X射线衍射、热重分析等对复合薄膜的官能团变化、结晶情况等进行了表征,测定了样品薄膜的透光率和雾度,利用DPPH自由基清除实验分析了薄膜的抗氧化性能。研究了AOB的添加量对复合包装薄膜的抗氧化性能、水溶性、力学性能和光学性能的影响。实验结果表明:AOB的添加没有破坏HPMC本身的基团,仅扰乱了分子链的排列,导致AOB/HPMC复合薄膜的结晶度下降,热分解温度提高,热稳定性能加强,具有抗氧化性的功能特性;且随着AOB添加量的不断增加,复合水溶性包装薄膜的水溶性不断提高,力学性能和光学性能有所下降,但下降幅度不大,抗氧化性能先增大后降低,当AOB的添加质量分数为0.03%时,复合薄膜对DPPH自由基的清除率达最大值,为89.34%。