聚乳酸/聚丁二酸丁二醇酯共混物的研究

通过熔融共混制备了聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混物,采用扫描电子显微镜、差示扫描量热仪、旋转流变仪对其相容性、热性能和黏度等进行了研究,并研究了PBS的加入对PLA力学性能的影响。结果表明,PLA和PBS之间是部分相容的,PBS的少量添加并不影响PLA的拉伸强度,且其冲击强度随着PBS含量的增加呈先上升后下降的趋势,当PBS含量为10份时,共混物的冲击强度最好;与纯PLA相比,共混物的黏度有所增加,且随着PBS含量的增加,共混物的黏度逐渐增大;PBS的添加起到异相成核作用,促进了PLA的结晶。     

聚乳酸/聚己二酸对苯二甲酸丁二酯合共混体系发泡行为研究

采用多环氧基团增容剂制备了聚乳酸/聚己二酸对苯二甲酸丁二酯(PLA/PBAT)共混物,研究了增容剂含量对于PLA/PBAT共混体系的结晶和流变性能的影响。并采用高压釜发泡的方法进行PLA/PBAT共混物的间歇发泡,研究增容剂对发泡材料泡体结构的影响。结果表明,增容剂加入后会降低其绝对结晶度,以及显著改善PLA/PBAT共混体系的熔体弹性,提高其可发性;增容剂可以有效地改善共混体系的泡体结构,降低共混物发泡密度,提高其发泡倍率。     

Partially Bio-Based Polyester Bead Foams via Extrusion Foaming of Poly(butylene terephthalate)/Poly(butylene furanoate) Blends

The interest in bio-based alternatives to classical polyesters such as poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) is steadily growing to achieve a more sustainable approach to polymer materials. In this study, PBT/poly(butylene furanoate) (PBF) blends are prepared, characterized and extrusion foamed. PBF as a bio-based polyester offers two advantages. The ecological footprint of the material is reduced, and additionally, it can be used in Diels-Alder reactions at the blend surface to support fusion of the foamed beads. The blending behavior of the polyesters is investigated using samples prepared in a microcompounder, particularly focused on the miscibility of the blends and transesterification reactions. The blends are thermodynamically immiscible but show a certain degree of transesterification according to nuclear magnetic resonance (NMR) spectroscopy. The morphology of blend beads produced by an extrusion foaming process is analyzed regarding their cell density, cell size distribution, and open-cell content. It is shown that PBF has a positive effect on the bead foam morphology. The use of a bifunctional linker designed for chemical fusion of the bead surfaces allows to obtaining of molded parts, in contrast to beads containing pure PBT.     

改性碳酸钙用于聚氯乙烯的研究

研究了一种改性碳酸钙的性质及其在聚氯乙烯中的应用情况。研究结果表明,这种改性碳酸钙与普通碳酸钙相比,具有吸油值低、堆积密度大、分散性好、热稳定性高等特点。填充于聚氯乙烯中,不仅能改善物料的加工性能及制品的物理力学性能,而且还具有较高的热稳定性能。     

P3/4HB/PBS共混物的物理性能及微生物降解

将不同比例的聚(3-羟基丁酸-co-4-羟基丁酸)共聚酯(P3/4HB)和聚丁二酸丁二酯(PBS)进行物理共混,通过FTIR、DSC、TG和SEM研究了复合材料的力学性能、亲水性能、热稳定性和结晶性。当PBS的添加量为10%时,复合材料的力学性能较好。与纯P3/4HB相比,拉伸强度增加了154%,达到了18.6 MPa;断裂伸长率增加了82%,为638%;弹性模量约下降94 MPa。复合物水溶解性能较小,只有0.34%,抗水性增强。DSC分析表明,2种聚合物的相容性较好。PBS的添加降低了材料的熔点,增加了结晶性能,同时减缓了材料的结晶速率。TG分析结果表明,复合材料稳定性增强,加工窗口拓宽了32℃。采用Pseudomonas.mendocina DS04-T菌株降解复合材料,当降解时间为120 h时,复合材料降解率为92.5%。     

两亲性超支化聚（胺-酯）对PVC／PP共混体系的增容作用

研究了两亲性超支化聚（胺-酯）（A-HPAE）对PVC／PP共混体系的增容作用，讨论了其用量对PVC／A-HPAE／PP共混体系力学性能和复数黏度的影响。结果表明，在PVC／PP共混物中加入2份（质量份，下同）A-HPAE时，能很好地改善共混体系的相容性，使共混物的拉伸强度和断裂伸长率分别达到26．18mPa和18．72％，比未加的分别提高了107．67％和34．68％；共混体系的绝对复数黏度随着A-HPAE用量的增大而降低；扫描电子显微镜分析表明，A-HPAE增强了PVC和PP之间的界面黏结作用，减小了共混体系中分散相的尺寸。     

聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物的非等温结晶动力学

采用熔融挤出法制备了聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物。利用差示扫描量热仪研究了聚乳酸及其共混体系的非等温结晶过程。用经Jeziorny修正的Avrami方程和Mo法对其非等温结晶动力学进行了分析。结果表明:Avrami方程和Mo法都适用于处理聚乳酸及其共混体系的非等温结晶过程,共混物的结晶速率大于聚乳酸的结晶速率。此外,用Huffman-Lauritzen理论计算了非等温结晶的结晶活化能,发现共混体系的结晶活化能绝对值小于聚乳酸。     

超支化聚（酰胺-酯）／ABS／聚氯乙烯共混体系相容性研究

研究了超支化聚(酰胺-酯)(HBP)对ABS/聚氯乙烯(ABS/PVC)共混体系的增容作用。讨论了HBP用量对ABS/PVC(80/20)和相同量HBP对不同比例ABS/PVC力学性能的影响。实验结果表明ABS/PVC共混物中加入HBP,可以有效改善共混体系的相容性;加入2份HBP时,ABS/PVC(80/20)共混物拉伸强度达到最大值,继续增加HBP,共混物拉伸强度快速下降,而共混物冲击强度单调下降;不同比例ABS/PVC中加入2份HBP共混物拉伸强度比未加入HBP共混物拉伸强度增加,但共混物冲击强度减小。扫描电子显微镜研究结果证明了HBP增强了ABS/PVC的界面黏结作用,减小了共混体系的相分离程度。     

Characterization of Commercial Grades of Poly(Carbonate of Bisphenol A)

This study characterized three different commercial grades of poly(carbonate of bisphenol A) samples (for extrusion, CD, and DVD) by several instrumental analysis methods, such as elemental analysis (EA), inductively coupled plasma mass spectrometry (ICP-MS), Fourier-Transform infrared spectroscopy (FTIR), viscosity measurements, differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). The results of EA and ICP-MS showed that the chemical composition of the samples has no significant differences and the C/H ratio approaches theoretical value. The most abundant metal element in the samples is Fe. FTIR spectra demonstrated they have the same chain structure. Comparing the intrinsic viscosities and viscosity average molecular weights from the results of viscometry analysis, the values fell in the order: extrusion grade > CD grade > DVD grade. Various thermal properties determined by DSC and TG analysis showed the same sequence as the results of viscometry analysis and a close relationship between molecular weight and thermal properties was found.     

Thermal Property and Hydrogen Bonding in Blends of Poly(vinylphenol) and Poly(hydroxylether of Bisphenol A)

The thermal property and hydrogen bonding in polymer blends of poly(vinylphenol) (PVPh) and poly(hydroxylether of bisphenol A) (phenoxy) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (NMR). This PVPh/phenoxy blend shows single composition-dependent glass transition temperature over the entire compositions, indicating that the hydrogen bonding exists between the hydroxyl of PVPh and hydroxyl of phenoxy. The negative T _g deviation of the PVPh/phenoxy blend indicates the strong intermolecular hydrogen-bonding interaction. The inter-association constant for the PVPh/phenoxy blend is significantly higher than self-association constants of PVPh and phenoxy, revealing that the tendency toward hydrogen bonding between PVPh and phenoxy is more favorable than the intra-hydrogen bonding of the PVPh and phenoxy in the blend.     

超支化聚（酰胺-酯）对聚丙烯／聚氯乙烯／苯乙烯-甲基丙烯酸甲酯共聚物接枝聚丙烯共混体系的增容作用

研究了超支化聚(酰胺-酯)(HBP))对聚丙烯/聚氯乙烯/苯乙烯-甲基丙烯酸甲酯共聚物接枝聚丙烯共混体系[PP/PVC/PP-g-(St-co-MMA)]的增容作用。讨论了HBP的用量对PP/PVC(80/20)共混物力学性能的影响；研究了剪切应力、剪切速率和温度对PP/PVC(80/20)共混物熔体黏度的影响。实验结果表明在PP/PVC/PP-g-(St-co-MMA)(80/20/6)共混物中加入1份HBP时，就可以很好改善共混体系的相容性，使共混物拉伸强度达到最大值，同时使熔体表观黏度达到较小值。该共混物熔体属于假塑性流体。扫描电子显微镜(SEM)研究结果证明了HBP增强了PP/PVC/PP-g-(St-co-MMA)的界面粘结作用，减小了共混体系的相分离程度。     

Bio-Based Degradable Poly(ether-ester)s from Melt-Polymerization of Aromatic Ester and Ether Diols

Vanillin, as a promising aromatic aldehyde, possesses worthy structural and bioactive properties useful in the design of novel sustainable polymeric materials. Its versatility and structural similarity to terephthalic acid (TPA) can lead to materials with properties similar to conventional poly(ethylene terephthalate) (PET). In this perspective, a symmetrical dimethylated dialkoxydivanillic diester monomer (DEMV) derived from vanillin was synthesized via a direct-coupling method. Then, a series of poly(ether-ester)s were synthesized via melt-polymerization incorporating mixtures of phenyl/phenyloxy diols (with hydroxyl side-chains in the 1,2-, 1,3- and 1,4-positions) and a cyclic diol, 1,4-cyclohexanedimethanol (CHDM). The polymers obtained had high molecular weights (M_w = 5.3–7.9 × 10⁴ g.mol⁻¹) and polydispersity index (Đ) values of 1.54–2.88. Thermal analysis showed the polymers are semi-crystalline materials with melting temperatures of 204–240 °C, and tunable glass transition temperatures (T_g) of 98–120 °C. Their 5% decomposition temperature (T_d,5%) varied from 430–315 °C, which endows the polymers with a broad processing window, owing to their rigid phenyl rings and trans-CHDM groups. These poly(ether-ester)s displayed remarkable impact strength and satisfactory gas barrier properties, due to the insertion of the cyclic alkyl chain moieties. Ultimately, the synergistic influence of the ester and ether bonds provided better control over the behavior and mechanism of in vitro degradation under passive and enzymatic incubation for 90 days. Regarding the morphology, scanning electron microscopy (SEM) imaging confirmed considerable surface degradation in the polymer matrices of both polymer series, with weight losses reaching up to 35% in enzymatic degradation, which demonstrates the significant influence of ether bonds for biodegradation.     

Extrusion Foaming of Poly (lactic acid)/Soy Protein Concentrate Blends

Poly(lactic acid) (PLA) and soy protein concentrate (SPC) were compounded using poly(2‐ethyl‐2‐oxazoline) as compatibilizer by twin‐screw extrusion, and the resulting blends were foamed by a chemical blowing agent (CBA) using the same extruder. Effects of foaming temperature and CBA content on cell density and foam density were investigated. Polymeric methylene diphenyl diisocyanate (pMDI) as a co‐compatibilizer was added prior to foaming extrusion and its effects on foam morphology and properties were also studied. The results showed that cell density and foam density were greatly influenced by foaming temperature and CBA content. Using the strong interfacial modifier pMDI in PLA/SPC blends resulted in high‐cell density and low‐foam density when CBA concentration was low.

     

基于共混聚醚共聚酰胺的气体分离膜的制备及性能研究

聚合物共混可以制备出兼有几种聚合物特性的共混膜。为了提高气体分离膜的综合性能,以2种不同型号的聚醚共聚酰胺（具有高选择性的Pebax1657和具有高渗透性的Pebax2533）为膜材料制备了气体分离膜,并对分离膜进行结构表征、分离性能和力学性能测试。结果表明,随着Pebax2533含量的增加,聚酰胺段的链间距逐渐增大,自由体积分数增大,玻璃化转变温度降低,断裂伸长率逐渐提高;与纯Pebax1657膜相比,共混膜的CO2和N2渗透系数同时增大,N2渗透系数增加速度较快;选择性逐渐降低;与纯Pebax膜相比,两者共混后的膜的综合性能有所提高。     

Phase Behaviour of Poly(ethylene oxide)/Poly(styrene-co-maleic anhydride) Blends

Thermal behaviour and morphology of blends of poly(ethylene oxide) (PEO) and poly(styrene-co-maleic anhydride) (SMA) prepared by the coprecipitation technique were studied by means of differential scanning calorimetry, optical microscopy and thermogravimetry. SMA containing 25wt% maleic anhydride (MA) was found to be miscible with PEO when the SMA content was greater than 80%. The melting temperature and crystallinity depended on the composition of the blend. SMA appears to segregate interlamellarly during the isothermal crystallization of PEO. The thermal stability of blends was enhanced and was higher than that of pure PEO and SMA. © of SCI.     

New Miscible Poly(ether imide)/Poly(phenyl sulfone) Blends

Summary: Blends of PEI and PPSU were prepared directly during the plasticization step of an injection molding process throughout the full composition range. The molded blends were transparent and showed a single glass transition and no dispersed phase by SEM. These characteristics did not allow the presence of a single miscibilized phase to be inferred unambiguously due to the very similar T_gs and refractive indices of the two components of the blends. Miscibility was inferred after close observation of the position, height and area of the enthalpy relaxation peak of the 50/50 blend. The modulus of elasticity and yield stress changed linearly with composition, leading to polymer materials with intermediate characteristics. The linearity was attributed to the lack of decrease in free volume induced by mixing and to the similar orientation of the components before and after mixing. The PPSU presence only slightly reduced the known tendency towards brittle fracture of PEI under notched impact conditions, but the presence of a single amorphous phase led to an expected ductile behavior of the blends close to that predicted by the single rule of mixtures.

Break stress (?) and break strain (○) of PEI/PPSU blends as a function of composition.     

碳酸钙高填充聚乳酸复合材料的制备及性能

在扩链剂Joncryl和增塑剂乙酰柠檬酸三丁酯存在下,采用微米级碳酸钙对聚乳酸(PLA)基体进行了高填充改性,制备碳酸钙高填充聚乳酸基复合材料,并用电子拉力机、扫描电镜、ARES流变仪等手段对材料的结构与性能等进行测试与表征.结果表明:碳酸钙高含量时可以明显提高材料的拉伸强度、弯曲强度,而材料的冲击强度会有所下降,但质量含量在30％ ～60％时复合材料的冲击强度仍高于纯聚乳酸.随碳酸钙含量的增加,材料的储能模量逐渐增大.碳酸钙的加入可以提高材料的弹性,材料的剪切黏度随剪切速率的增大而逐渐降低.     

HBP/PVC的流变行为

研究了不饱和超支化聚(酰胺－酯)(HBP)／聚氯乙烯(PVC)的流变行为和玻璃化温度的变化。讨论了剪切应力和剪切速度对HBP／PVC熔体表观粘度的影响。结果表明,在研究的HBP添加量范围内,HBP／PVC的熔体表观粘度大于PVC的。当PVC中加入HBP小于7份时,HBP／PVC的熔体表观粘度逐渐增加;当PVC中加入HBP等于7份时,HBP／PVC的熔体表观粘度出现最大值;当PVC中加入HBP大于7份时,HBP／PVC的熔体表观粘度减小。差示扫描量热仪(DSC)研究结果证明了HBP和PVC相容性较好,且与测得的流变行为结果相一致。从化学反应和形成氢键的机理解释了HBP／PVC的相容性。     

Compatibilization of PS and PA6 Blends by Means of Poly(oxyalkylene)amine Modified Styrene-Maleic Anhydride Copolymer

The compatibilization effect of SMA-co-M2070-co-DAP comb-like copolymers, SMMD, on immiscible blends of polystyrene (PS) and polyamide-6 (PA6) is examined in terms of phase structure, thermal behavior, dynamic mechanical analysis, and mechanical properties. A series of SMMD copolymers are synthesized and confirmed by the FT-IR analysis. These compatibilizers have different amphiphilic properties depending on the content of hydrophilic poly(oxyethylene) segments (M2070) and the molar ratio of MA/amine. The morphologies of PS/PA6, affected by the increasing amount of SMMD compatibilizer, show a more regular and finer dispersion. The sizes of dispersed particles have no marked changes over the saturation level of compatibilizer. The glass transition temperatures of the blends are between that of PS and PA6, while the added SMMD copolymer is mainly located at the interface. Using these SMMD copolymers, the compatibilized blends show some improvements in mechanical properties, including Izod impact strength and flexural properties. The graft poly(oxyethylene) and amide functionalities in SMMD structures in forming hydrogen bonding with PA6 and, the polystyrene backbone in π–π interaction with PS facilitate the compatibilizing effect.     

Melt Crystallization Behavior and Spherulitic Morphology of Poly(Trimethylene Terephthalate)/Poly(Propylene Glycol) Copolymers with Different Poly(Propylene Glycol) Molecular Weights

Poly(trimethylene terephthalate)/poly(propylene glycol) (PTT/PPG) copolymers with different PPG molecular weights (400–4,000?g?/mol) were successfully synthesized and characterized. Double melting endotherms during isothermal melt crystallization were observed by differential scanning calorimetry. Middle-temperature melting endotherms in all copolymers were stronger than that in PTT homopolymer and became smaller with the increasing PPG molecular weight. Nonisothermal crystallization kinetics of all samples were analyzed by Ozawa and Mo models. Polarized optical microscopy micrographs revealed that ring-banded spherulitic morphology was relatively easier to be observed in copolymers with higher PPG molecular weight at lower crystallization temperature, and PPG molecular weight nearly had no influence on the band spacing.