聚对苯二甲酸二甲酯/聚2,5-呋喃二甲酸二甲酯嵌段聚酯的合成与表征

以生物基单体2,5-呋喃二甲酸、乙二醇为原料合成聚2,5-呋喃二甲酸乙二醇酯(PEF)。采用熔融酯交换法以PEF聚酯部分取代聚对苯二甲酸乙二醇酯(PET),制备了系列PET-b-PEF嵌段共聚酯。通过核磁共振仪(NMR)、差示扫描量热仪(DSC)、热失重仪(TGA)、X射线衍射仪(XRD)等技术手段表征了共聚酯的结构和性能。结果表明,该系列共聚酯的玻璃化转变温度(Tg)在75.8~80.3℃之间,且随着PEF链段质量分数的增加,PET-b-PEF嵌段共聚酯的Tg先降低后升高,结晶度和熔融温度逐渐降低。当PEF链段含量高于15%时,共聚酯没有结晶峰。该系列共聚酯具有良好的热稳定性,起始分解温度在392.2~407.9℃之间,与所制备的PET起始分解温度403.3℃接近。且当共聚酯中PEF链段含量低于15%时,起始分解温度均在407℃左右,优于PET的热稳定性。     

聚L-乳酸/4,4'-二羟基二苯硫醚共混物的分子间相互作用及结晶和熔融行为

利用红外吸收光谱(FTIR)研究了聚乳酸(PLLA)/4,4'-二羟基二苯硫醚(TDP)熔融共混物的分子间相互作用,结果表明,PLLA的羰基与TDP的羟基之间形成了分子间氢键.通过差示扫描量热(DSC)研究了共混物的玻璃化转变行为及非等温结晶和熔融行为.结果表明,样品的玻璃化转变温度(Tg)随TDP含量的增加呈线性下降.共混物的熔融结晶温度(Tc)、结晶焓(ΔHc)、熔融温度(Tm)及熔融焓(ΔHm)均随TDP含量的增加呈下降趋势,而冷结晶温度的变化趋势则相反.当TDP达到40%(质量分数)时,共混物的DSC曲线既未出现结晶峰,也未出现熔融峰,表明该样品已完全成为非晶态物质.广角X射线衍射(WAXD)分析结果表明,TDP的加入未改变PLLA的晶型,但导致其晶面间距变大,晶体结构变得松散.因此共混物熔点的下降归因于分子间氢键的形成降低了PLLA分子链的运动能力及晶体的紧密程度而非晶型的改变.     

对羟基苯甲酸(PHB)聚对苯二甲酸乙二酯(PET)液晶共聚酯和聚对苯二甲酸乙二酯共混物的酯交换表征

在温度280℃附近对含有液晶共聚酯P-Hydroxy Benzoic Acid/Poly(-Ethylene Terephthalate-)PHB/PET和Poly(-Ethylene Terephthalate-)PET的共混样品进行热处理时,发现共混物的熔点随热处理的时间增加而不断降低,热处理温度越高,相同时间内共混物熔点下降程度越大;而具有相同热历史的纯PET样品熔点几乎保持不变.通过NMR方法证实了PHB/PET-TET共混物熔点随热处理时间下降是由于PHB/PET和PET之间发生了酯交换反应.所以可根据共混物的宏观热性质和PHB/PET序列结构变化表征PHB/PET和PET共混物之间的酯交换程度.     

热释电研究聚碳酸酯掺杂染料体系的玻璃化转变

采用热刺激电流 /松弛谱图分析法 (TSC/RMA)研究了聚碳酸酯掺杂染料体系 (TDAA/PC)的玻璃化转变 ,发现染料含量增加 ,体系的玻璃化转变温度 (Tg)随之降低 ,玻璃化转变的温度范围变宽 .在TDAA掺杂质量比达到 4wt%时 ,其玻璃化转变 (协同松弛 )延伸至 95℃ ,温度范围增加到 3 5℃ .在较大的温度范围内存在协同松弛 ,说明在低于Tg 数十度的温度时 ,染料发色体的极化松弛仍然主要受聚合物玻璃化转变的控制 .     

sPS/PET/SsPS-H共混体系的研究

以自制间规聚苯乙烯(sPS)功能化合成的磺化间规聚苯乙烯（SsPS-H)作相容剂,研究其对sPS/PET共混物微相结构与性能的影响,发现SsPS-H能够有效地改善二者的相容性,当sPS/PET/SsPS-H为85／15／2（重量比）时,冲击强度达到11．4kJ/m^2,为纯sPS的3倍,此时材料的弯曲强度为39．1MPa,下降约8％;DMA结果表明,随SsPS-H用量的增加,共混物的Tg逐渐提高;DSC分析结果表明,共混体系中sPS的熔点不受SsPS-H含量的影响,而PET的熔点在加入6份SpPS-H时明显降低。sPS在达到最大结晶速率的温度均随SsPS-H用量的增加先提而后下降。SEM观察到加入SsPS-H后,PET分散相的尺寸减小,且均匀程度增加,共混物室温下冲击断裂显著地由脆性转变为韧性,当加入6份SsPS-H后,冲击断裂又出现脆性。     

玻璃态PET的有序结构与解偏振光的记忆效应

聚合物的非晶态结构究竟是完全无序的 ,还是局部有序的 ,目前存在两种对立的学说 ,即 Flory的无规线团模型和 Yeh的两相球粒模型 [1] .Siegmann等 [2 ]在研究低于玻璃化转变温度 (Tg≈ 3 4 3 K)下的退火对 PET热谱 (DSC)中玻璃化转变的影响时发现 ,未经退火后的 PET在 Tg范围内仅表现出一个拐折 ,而在 3 2 7K退火时 ,随时间的增加 ,出现了类似于吸热峰的转变过程 ,并认为是由玻璃态中有序程度的增加所致 .本文通过解偏振光方法 (DLI)的研究发现 ,在玻璃态的 PET中确实存在着一定的有序结构 ,与晶态 PET中的有序结构不同的是 ,玻璃…     

由特殊相互作用导致的高分子间的络合Ⅷ.聚(苯乙烯-co-4-乙烯基苯酚)/聚甲基丙烯酸乙酯在本体中的相容-络合行为

采用结合物理老化技术的示差扫描量热法(DSC)以及非辐射能量转移荧光光谱法(NRET)研究了聚(苯乙烯-co-4-乙烯基苯酚(STVPh)与聚甲基丙烯酸乙酯(PEMA)共混体系的相容与络合行为.对STVPh/PEMA共混体系,当STVPh中的OH基团含量仅为1mol%时,即可实现相容.随OH基含量继续增加,共混体系的Tg值上升并逐渐接近和高于Fox方程计算值,玻璃化转变区域逐渐变窄,NRET能量转移效率远高于普通的相容体系,共混体系形成络合.此外,还讨论了浇膜溶剂对相容与络合的影响.     

聚酰亚胺对多官能团环氧树脂的增韧作用

本文选择不同比例的聚酰亚胺(PEI)与多官能团的环氧树脂(MY0510)和 NovoIak 树脂(DEN431)共混,以3,3′—二氨基二苯亚砜(DDS)为固化剂,制备一系列的共混物样品。通过三点弯曲试验、扫描电镜和动态力学热分析分别测定共混物的应力强度因子(K_(1c))和临界应变能松驰速率(G_(1c))、形态结构和玻璃化转变温度。当加入 PEI 时,共混物的 K_(1C)和 G_(1C)都有显著的提高,即增加了环氧树脂的韧性。虽然所有共混物只有一个Tg 峰,但电镜的观察结果说明为两相结构。当 PEI 的含量为10%时,PEI 开始从分散相转变为连续相。后固化作用使 Tg 提高了6—20℃,同时也有利于 K_(1C)和 G_(1C)。     

聚乳酸与聚丙撑碳酸酯共混体系的性能

采用熔融共混的方法制备了聚乳酸(PLA)/聚丙撑碳酸酯(PPC)共混物。DSC测试结果表明,纯PLA和PPC的玻璃化转变温度分别为54和37℃,不同组成的PLA/PPC共混物有2个明显的玻璃化转变温度,且与纯PLA和PPC的玻璃化转变温度相对应,说明二者是不相容体系。力学测试结果表明,当PPC质量分数超过20%时,可以看到明显的屈服点。共混物在拉伸过程中也有明显的颈缩、应力发白现象,表明随着PPC含量增加,PLA/PPC共混物由典型的脆性断裂向韧性转变。随着PPC含量的增加,共混物模量降低,断裂伸长率增加,当PPC质量分数为50%时,共混物的断裂伸长率达到最大值62%。共混物的粘度可在很宽的范围内予以调控,以满足不同加工的需要。     

苯酰化聚苯醚—聚苯乙烯共混物相容性研究

采用DSC方法研究了聚苯乙烯和苯甲酰化聚苯醚共混体系的相容性。相容共混体系Gordon-TayIov方程K参数随苯甲酰化程度(取代度)增加而变小,其玻璃化转变区随取代度增加而变宽,取代度大于76mol％时,共混物呈现双玻璃化转变。A~(49)ppo/pS_(19)共混体系热诱导相图同时存在高和低临界共溶温度,且此相行为是可逆的。     

用DSC测量葡萄糖溶液部分玻璃化转变温度的新方法

用差示扫描量热仪, 采用经过退火处理的连续扫描法, 以不同浓度(20%、45%)的葡萄糖溶液为研究对象, 研究了退火温度对Tgf(部分结晶的玻璃化转变温度)的影响, 给出了确定Tg′(部分玻璃化转变温度)的新方法. 研究发现, 不同退火温度下的Tgf不同. 在−50 ℃以上退火, Tgf随着退火温度的增大而减小; 在−50 ℃以下退火, Tgf随着退火温度的增大而增大, 都有很好的线性关系. 不同浓度的溶液具有相似的规律. 提出从Tgf确定Tg′的方法: Tgf在−50 ℃上下随退火温度变化线的交点所对应的部分结晶玻璃化转变温度即为Tg′. 使用该方法测得葡萄糖的Tg′为−55 ℃.     

尼龙1010结晶与熔融行为的研究

用DSC研究了降温速率R对尼龙10 10结晶与熔融的影响,以及室温(RT)和液氮(LN)骤冷退火样品的熔融.降温时结晶温度随R增大线性降低;T_g以上可完成结晶时结晶度相同;结晶起始温度>181℃生成的晶体有三个熔融峰,对应于环状和放射状球晶的转化与熔融;在181℃和T_g间结晶,无放射球晶转化峰;T_g下有结晶放热峰样品加热时有冷结晶发生.RT未退火样品三个熔融峰,退火温度T_α≥180℃样品两个峰,结晶度C∝T_a;LN未退火样品单一熔融峰,T_a>160℃双峰,T_a≤160℃三峰,低温峰温与C均∝T.     

The effect of annealing on the subsequent cold crystallization of amorphous poly(ethylene terephthalate)

Amorphous poly(ethylene terephthalate) was annealed at temperatures around the glass transition temperature and then heated up in differential scanning calorimeter at 20 °C min⁻¹. It was found that the annealing favored the subsequent cold crystallization and this effect became stronger with increasing annealing temperature. The experimental results were explained by considering the structural change during the annealing.     

Crystallization and melting of the system isotactic polystyrene + poly(2,6-dimethyl phenylene oxide)

From glass transition T_g measurements on isotactic polystyrene (IPS)–poly(2,6-dimethyl phenylene oxide) (PPO) blends, it was concluded that thoroughly annealed, freeze-dried samples, or samples evaporated from solution at high temperature, are homogeneous. Without annealing, the freeze-dried blends show two to three T_g's characteristic of the presence of different phases. The overall crystallization rate of these samples is much higher than that observed with annealed samples. The presence of dissolved PPO in annealed samples reduces the overall crystallization rate and the spherulitic growth rate, compared to IPS. The melting behavior of the blends is influenced by the extent of mixing of both polymers. Without annealing, isothermally crystallized, freeze-dried blends show the same melting behavior as IPS (i.e., multiple melting). In homogeneous annealed samples the rate of reorganization is strongly reduced and multiple melting only occurs at low scanning rate (e.g., 1°C/min). This behavior is influenced by the crystallization temperature and by the composition of the blends. The addition of PPO has no influence on the relation between melting point and crystallization temperature and the same equilibrium melting point is found by extrapolation.     

Plasticization and Crystallization of Poly(ethylene Terephthalate) Induced by Water

Commercial poly(ethylene terephthalate) (PET) was treated at R. H.>80% and room temperature for a set time. The glass transition temperature (Tg) decreases with the time of exposure to high humidity. The decrease in Tg is a result of plasticization. Our data indicate that the Tg of dry PET of 76-78°C may decrease to as low a temperature as 65-67°C when it is wet. Induced crystallization of PET in the presence of water reduces the cold crystallization temperature (Tc). The structure of water-induced crystals is imperfect and can be improved in perfection by annealing. This revised version was published online in July 2006 with corrections to the Cover Date.     

Enhancing chain segments mobility to improve the fracture toughness of polypropylene

As a part of a serial work about the annealing inducing improvement of fracture toughness of polypropylene (PP) articles, in this work, a highly efficient mobilizer was introduced into PP and the injection-molded samples were annealed at different temperatures. The mobility of chain segments of PP was investigated by measuring the glass transition temperature. Differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD) were used to characterize the variation of crystalline structure of PP during the annealing process. The fracture behaviors including notched Izod impact fracture and universal tensile fracture were investigated to detect the mechanical properties in response to the variations of both chain segments mobility and crystalline structures. It was found that the mobilizer greatly improved the chain segments mobility. Further results showed that the mobilizer also induced apparent changes of the glass transition temperature and the degree of crystallinity of PP during the annealing process. Consequently, the annealed PP samples containing a few amount of mobilizer exhibited largely increased fracture toughness.     

聚对苯二甲酸乙二酯中正电子湮没寿命参数温度效应的研究

对聚对苯二甲酸乙二酯的非晶、低温热处理(54℃)、高温热处理(180℃)以及双轴拉伸等四种不同试样,测量了室温到180℃范围内不同温度在的正电子湮没寿命谱.根据最小二乘曲线拟合解谱结果,可知最长寿命成份的湮没参数τ和I的温度曲线分别灵敏地反映了聚对苯二甲酸乙二酯的玻璃转变过程和结晶过程.据此讨论了正电子湮没寿命参数与PET转变的关联以及PET玻璃转变的有关性质.     

Studies on partial compatibility of PP and PS

<正>Blends of polystyrene(PS) and polypropylene(PP) were prepared through melt compounding.With an increase of PS content up to 30 wt%,the tensile strength of PP/PS blends increased from 37.4 MPa to 42.2 MPa,although the blends were widely regarded as immiscible.The DSC results showed that there's slight decrease in melting temperature of PP, showing insufficient evidence for partial compatibility between PP and PS.Almost no variation of distinct characterization peaks were observed in FTIR spectra of PS/PP blends compared with those of neat PP and PS,indicating there is no chemical interactions between PP and PS.Since the morphology investigation showed a droplet structure as PS content was up to 30 wt%,the improvement of tensile strength could be simply considered as due to the reinforcing effect of dispersed rigid PS particles on the PP,combining with partial compatibility between them as evaluated by change of C_p at glass transition for both PS and PP.More interestingly,DSC and DMA results showed that the blending of PS and PP could lead to a substantial decrease of the glass transition temperature(T_g) of PP,and increase of T_g of PS.The annealing experiment was carried out to understand the change of T_g in PP/PS blends.It is believed that the compressive stress generated by the contracting PP should be the dominant mechanism for the T_g elevation of PS.On the other hand,the T_g decrease of PP is likely owing to the creation of a large amount free interface of PP and the dilatation of the PP phase resulting from the corresponding tension exerted by PS during cooling.     

冻干保护剂溶液低温退火特性的研究

利用差示扫描量热仪(DSC)研究了10%叔丁醇/10%蔗糖/水溶液的冻结特性, 退火温度及退火时间, 分析了溶液的退火行为. 实验结果表明, 溶液降温时, 蔗糖的存在阻碍了叔丁醇析出, 最大冻结浓缩溶液玻璃化转变温度Tg′由－32.5 ℃降低到－42.0 ℃, 升温时在－30 ℃叔丁醇发生反玻璃化. 在反玻璃化峰附近的温度进行退火可使叔丁醇充分析出, Tg′由－42.0 ℃上升到－34.9 ℃. 所需的退火时间与退火温度有关, 退火温度越接近Tg′, 所需的退火时间越长. 在－37 ℃时, 退火20 min可完全消除反玻璃化.     

Influence of ZnSt2 on structure of acrylate-based ionomers with different lanthanide (La(III)) ion and acid contents

A series of acrylate processing aid（ACR）-based ionomers with different lanthanide（La（Ⅲ）） ion and acid contents were synthesized,and the interaction between ionomer and zinc stearate（ZnSt₂） was investigated immediately after thermally annealing the ionomer/ZnSt₂（3/1 in weight） mixtures at 180℃.The results revealed that the ion groups in ionomer have a strong interaction with ZnSt₂.The annealed mixtures contained hot alcohol extractable and unextractable ZnSt₂.The melting of ZnSt₂ and the thermal behavior of the ionomer in the annealed mixtures were seriously influenced by the contents of La（Ⅲ） and acid in the ionomers.The ionomer containing 0.25 mmol/g acid and 0.37 mmol/g La（Ⅲ） has a detectable cluster phase.Annealing its ZnSt₂ mixture could break down the cluster phase and lower glass transition temperature of the ionomer matrix.However,washing away the extractable ZnSt₂ led to the reappearance of the cluster transition temperature and return of the glass transition temperature of matrix to the original position.