PET-PEN共聚酯对PET/PEN共混物的增容作用及其机理

使用聚对苯二甲酸乙二酯(PET)-聚萘二甲酸乙二酯(PEN)无规共聚酯作增容剂,通过双螺杆挤出机熔融共混,制备了不同PET-PEN共聚酯用量的PET/PEN共混物,采用差示扫描量热分析、热重分析、热变形温度测试以及力学实验等方法,研究了该共混物的相容性及其它性能。结果表明,PET-PEN共聚酯对PET/PEN共混物具有明显的增容作用,能有效提高PET/PEN共混物的热稳定性,其用量越高,热稳定性提高越明显,当PET-PEN共聚酯用量为15质量份时,起始失重温度提高了20.3℃。PET-PEN共聚酯增容剂能提高PET/PEN共混物的维卡软化温度、拉伸和弯曲性能以及冲击性能,当PET-PEN共聚酯用量为5质量份时,增容改性的综合效果最好。     

回收PET共混物的非等温结晶和熔融行为

采用双螺杆挤出机制备了聚丙烯(PP)/回收聚对苯二甲酸乙二酯(r-PET)、r-PET/马来酸酐接枝PP(PP-g-MAH)和r-PET/甲基丙烯酸缩水甘油酯接枝PP(PP-g-GMA)共混物,并研究了共混物组成、熔融温度与时间以及降温速率对共混物非等温结晶与熔融行为的影响.结果表明,r-PET与PP共混,结晶温度均提高,这与组分间起到异相成核诱导结晶作用有关.r-PET结晶温度随PP-g-MAH用量增加而降低,但受PP-g-GMA用量影响较小;r-PET可提高PP-g-MAH结晶温度,但降低PP-g-GMA结晶温度.熔融温度提高,共混物中PP结晶温度和熔点均降低,r-PET熔融峰形和熔点取决于共混物的熔融温度及界面相互作用.     

增容剂对PP/r-PET共混物非等温结晶动力学的影响

采用差示扫描量热法研究了增容剂甲基丙烯酸缩水甘油酯接枝聚丙烯(PP-g-GMA)对聚丙烯(PP)/回收聚对苯二甲酸乙二酯(r-PET)共混物的非等温结晶动力学的影响。结果表明:在PP/r-PET共混体系中,r-PET起到异相成核的作用,PP的结晶峰温升高,半结晶时间减少;增容剂PP-g-GMA的加入使PP/r-PET的结晶温度降低,半结晶时间增大,但降低了PP的结晶活化能。     

PET/PEN共混体系的结晶及动态力学性能

通过熔融共混法制备了PET/PEN复合材料,利用差示扫描量热法(DSC)和动态热机械分析(DMA)研究了共混比例对复合材料结晶性能和动态力学性能的影响,结果表明:随PEN含量的增加,PET/PEN复合材料的结晶温度向低温方向移动,结晶能力变差,结晶度减小,当PEN用量大于50份时,共混物为非晶共聚物。PEN的加入可以显著提高PET的储能模量,随PEN含量的增加,复合材料的储能模量逐渐减小。tanδ-温度曲线表明:复合材料存在1个θg和1个冷结晶峰温度。随PEN含量的增加,共混物的θg和冷结晶峰逐渐增强,且冷结晶峰温度逐渐向高温方向移动,冷结晶倾向增强。     

PTT/PP共混物的性能研究

通过熔融共混制备了聚对苯二甲酸丙二酯/聚丙烯(PTT/PP=75/25)及其马来酸酐接枝PP(PP-g-MAH)增容共混物,研究了PTT/PP及其增容共混物的结晶性能、力学性能、流变性能和结晶形态。研究结果表明,PTT与PP共混能提高PP、PTT组分的结晶温度;对于增容共混物,随PP-g-MAH用量的增加,PP和PTT的结晶温度基本不变。加入PP使PTT拉伸强度降低,冲击强度提高;PP-g-MAH增容使共混物的拉伸和冲击强度都提高。增容共混物的熔体粘度明显降低,存在明显的剪切变稀现象,但熔体粘度与PP-g-MAH用量无关。在一定用量范围内,随PP-g-MAH用量的增加,PP分散相的尺寸变小。     

PET/PEA共混物的非等温结晶及晶态结构

采用升、降温DSC和广角X射线衍射等测试手段研究了不同共混比的PET/液晶共聚酯酰胺(PEA)机械共混物、溶液共混物的非等混结晶和晶态结构。结果表明PEA在20％的范围内能起到成核剂的作用,促进PET结晶,并且当PEA的加入量为2.5％时,PET最易结晶;共混物中PET的晶态结构受PEA的影响不大,PEA的引入使共混物各晶面间距增大,共混物的结晶度呈现先上升而后降低之趋势。     

PLA/PBAT/PDEGA共混物的制备北大核心

以聚己二酸二甘酯(PDEGA)为增塑剂,通过双螺杆挤出机制备了聚乳酸(PLA)/聚对苯二甲酸-己二酸-丁二酯(PBAT)/PDEGA共混物,并研究了PLA/PBAT/PDEGA共混物的热性能、结晶行为、力学性能、冲击断面形态、阻隔性能、流变性能和熔体强度。结果表明:加入PDEGA和PBAT,提高了PLA的冷结晶能力,并改善了PLA的柔韧性;PLA/PBAT/PDEGA共混物对水蒸气的阻隔性能受PDEGA和PBAT影响不大;加入PDEGA和PBAT,增强了共混物的流动性。     

PET/聚烯烃共混改性的研究进展

从聚对苯二甲酸乙二酯(PET)/聚烯烃(PO)共混物的形态结构、力学性能、结晶性能、气体渗透性能和加工流变性能、生物降解等方面详细阐述了国内外PET/PO共混改性的最新研究进展,并对PET/PO共混物的发展趋势作了简要分析.     

离聚物增容PET/TLCP共混物的研究及应用

研究了聚对苯二甲酸乙二酯(PET)/热致液晶聚合物(TLCP)原位复合共混物的流变行为、相容性、熔体结晶、耐磨性和微观结构.结果表明,TLCP的加入降低了共混物的扭矩,而增容剂离聚物的加入却提高了扭矩;少量TLCP的加入提高了共混物的结晶速率和结晶度,但是离聚物的加入反而降低了其结晶速率和结晶度;TLCP的加入能提高PET的耐磨性,离聚物的加入使PET/TLCP共混物的耐磨性进一步提高,离聚物的质量分数为5%时,PET/TLCP共混物的耐磨性最佳;TLCP在PET中能原位形成微纤结构,离聚物加入使微纤变小,分布更均匀;利用离聚物增容PET/TLCP所制备的工业丝编织成的造纸网,其使用寿命延长了20%,经济效益显著.     

PTT/mPE共混物的制备和性能研究

研究了聚对苯二甲酸丙二酯(PTT)/茂金属聚乙烯(mPE)共混体系的流变性能、结晶熔融行为、力学性能以及增容剂对共混物相形态的影响。结果表明：PTT/mPE共混物熔体为假塑性流体,熔体表观黏度随PTT含量的增加而迅速降低,PTT含量高于40％时共混物表观黏度迅速下降,PTT含量越多对温度变化的敏感性越强。PTT和mPE可分别结晶,但PTT组分的结晶峰温度Tpc和结晶熔融峰温度Tm均比纯PTT的明显提高,而mPE组分的Tpc和Tm与纯mPE的相近,mPE可以促进PTT熔体结晶,但已经形成的PTT晶体不影响mPE的结晶,mPE的结晶行为主要发生在mPE微相区内。增容剂马来酸酐接枝乙丙橡胶提高了PTT与mPE间的相容性,共混物的冲击强度随着增容剂的增加而提高,mPE和增容剂共同发挥了增韧作用。     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Spherulitic crystallization in blends of poly(ethylene oxide) and poly(methyl methacrylate)

The crystallization kinetics of binary blends of poly(ethylene oxide) and poly(methyl methacrylate) were investigated. The isothermal spherulitic growth rates were measured by means of a polarized light microscope. The temperature and composition dependence on the growth rates have been analysed. The temperature range studied was from 44° to 58°C. The introduction of poly(methyl methacrylate) into poly(ethylene oxide) resulted in a reduction of the spherulitic growth rate as the proportion of poly(methyl methacrylate) was increased from zero to 40% by weight. Results have been analysed using the theoretical equations of Boon and Azcue for the growth rate of polymer-diluent mixtures. The experimental results are in good agreement with this equation. The temperature coefficient is negative as is the case in the crystallization of bulk homopolymers.     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Study of the miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) blends

The miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) (PEO/PVA) blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarizing optical microscopy. Because the glass‐transition temperature of PVA was near the melting point of PEO crystalline, an uncommon DSC procedure was used to determine the glass‐transition temperature of the PVA‐rich phase. From the DSC and DMA results, two glass‐transition temperatures, which corresponded to the PEO‐rich phase and the PVA‐rich phase, were observed. It was an important criterion to indicate that a blend was immiscible. It was also found that the preparation method of samples influenced the morphology and crystallization behaviors of PEO/PVA blends. The domain size of the disperse phase (PVA‐rich) for the solution‐cast blends was much larger than that for the coprecipitated blends. The crystallinity, spherulitic morphology, and isothermal crystallization behavior of PEO in the solution‐cast blends were similar to those of the neat PEO. On the contrary, these properties in the coprecipitated blends were different from those of the neat PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1562–1568, 2004     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-T_m component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-T_m component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

聚丁二酸丁二醇酯/聚乙二醇硬脂酸酯共混物非等温结晶行为

以聚丁二酸丁二醇酯（PBS）和聚乙二醇硬脂酸酯（PEOST）为原料,采用溶液共混法制备了PEOST质量分数分别为10%（POS-10）和30%（POS-30）的两种合金材料。通过差示扫描量热法（DSC）研究了合金材料的非等温结晶行为,用莫志深（Mo）法分析了PBS的非等温结晶动力学,采用Kissinger法和Friedman法计算PBS的结晶活化能,并用红外（FTIR）和偏光显微镜（POM）进行表征。研究结果表明：PBS先结晶形成结晶微区不利于PEOST结晶,而较高含量的PEOST有利于PBS的结晶。受PBS先结晶的影响,POS-10降温DSC曲线没有出现PEOST的结晶峰,而POS-30在低的降温速率情况下出现了PEOST双结晶峰;升温DSC曲线中两试样均出现了PEOST的熔融峰。在相同的冷却速率下,POS-30的PEOST熔融温度（T_m）和熔融焓（△H_m）大于POS-10;POS-30的PBS结晶峰温度（T_p）、结晶焓（△H_c）大于POS-10,而结晶半峰宽（D）值更小;但两者的T_m和△H_m相当。随冷却速率的增加,PBS的D值增大,而PEOST的D值却降低;冷却速率的增加对PBS的T_m值影响不大,但使PEOST的T_m略有减小。Mo法适合用于共混物中PBS的非等温结晶动力学分析。POS-30的PBS绝对值结晶活化能要大于POS-10。POS-30在红外光谱谱图中出现了PEOST结晶的红外响应峰（1109cm^-1和841cm^-1）而POS-10没有。     

High molecular weight poly( -lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly( -lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)等温结晶行为研究

以对苯二甲酸(PTA)、乙二醇(EG)、异山梨醇(ISB)为原料,通过直接熔融缩聚法合成聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)(PEIT)共聚酯。利用差示扫描量热法(DSC)研究了共聚酯的结晶行为,采用Avrami方程分析了共聚酯的等温结晶动力学。结果表明,PEIT共聚酯结晶行为受共聚组成和结晶温度影响。随着ISB用量的增加或结晶温度的降低,共聚酯半结晶周期t1/2增加、结晶速率变慢;ISB摩尔分数超过20%,共聚酯无法结晶。