高韧性PET/PBT合金的制备及性能

甲基丙烯酸环氧丙酯接枝乙烯-辛烯共聚物(POE-g-GMA)用于聚对苯二甲酸乙二醇酯(PET)/聚对苯二甲酸丁二醇酯(PBT)共混物的增韧改性,同时考察了PET、PBT组成变化对共混体系性能的影响。结果表明,加入15%~20%(质量分数,下同)的POE-g-GMA共混体系发生脆韧转变,冲击强度最高可达890 J/m,实现超韧;基体的剪切屈服和橡胶粒子的空洞化是增韧PET/PBT共混物主要形变机理。     

PBT/PC共混体系相容性与力学性能的研究

利用聚对苯二甲酸丁二醇酯(PBT)与聚碳酸酯(PC)之间的酯交换反应,自制了PBT与PC的共聚产物作为PBT/PC共混体系的相容剂,讨论了相容剂对该共混体系综合性能的影响.结果表明,相容剂的加入改善了PBT与PC两相间的相容性,共混体系的强度和韧性得到协调.PBT/PC共混体系中组分PC不仅影响了组分PBT的结晶行为,其分子链还影响PBT分子链的有序排列,阻碍PBT的结晶,降低了PBT的成型收缩率.另一方面,PBT的存在也使得PC的耐溶剂性提高,且PBT的含量越高,体系耐溶剂性越强,同时使PC的流动性得以改善.     

PEN/PBT共混物的结晶行为和热性能

用差示扫描量热量仪(DSC)和热重分析仪(TGA)对聚对萘二甲酸乙二酯(PEN)/聚对苯二甲酸丁二酯(PBT)共混物的相容性、结晶行为和热性能进行了研究。结果表明,PEN/PBT共混物属于热力学相容体系。加入少量PBT会使PEN的冷结晶行为扩大。热稳定性相对较差的PBT的加入会在一定程度上使PEN/PBT共混物的热稳定性下降。     

高强度极性POE弹性体共混物的制备与性能

将聚对苯二甲酸丁二醇酯(PBT)引入到乙烯-辛烯共聚物热塑性弹性体(POE)用于提高其强度,加入甲基丙烯酸环氧丙酯(GMA)接枝的POE(gPOE),提高POE的极性及其与PBT之间的相容性。红外光谱(FT-IR)证实GMA成功接枝到POE分子链上;gPOE提高了共混物的黏度和相容性,PBT在共混体系中均匀分散,粒径细化到0.5μm~1μm;拉伸性能结果表明,PBT为30份,gPOE为35份时,共混物拉伸应变仍可达到近700%,断裂强度可达14MPa左右,是纯POE的2.4倍。     

SEBS-g-MAH增容PS/PC体系的结构与力学性能

研究了不同配比的聚苯乙烯/聚碳酸酯(PS/PC)共混体系的结构与力学性能及彼此之间的关系,讨论了增容剂氢化苯乙烯-丁二烯共聚物接枝马来酸酐(SEBS-g-MAH)对共混物相容性及力学性能的影响。差示扫描量热分析表明,PS/PC表现出2个玻璃化转变温度(Tg),而PS/PC/SEBS-g-MAH则只有1个Tg。扫描电镜的分析结果表明,PS为连续相,PC为分散相,而且SEBS-g-MAH的加入使PS与PC的界面变得模糊。可见增容剂对共混体系具有明显的增容作用。共混物的冲击强度在PC用量大于30 phr时明显提高,拉伸强度和冲击强度在低PC含量时较纯PS有一定程度的下降,但随PC含量增加又逐渐提高;增容共混物的力学性能比未增容的有较大提高;当PC用量约40 phr时共混物具有最好的综合性能。     

采用臭氧化茂金属乙烯-1-辛烯共聚物(POE)对聚碳酸酯进行改性的研究

聚碳酸酯(PC)与经臭氧化处理的POE共混后,其力学性能、低温冲击性能、抗溶剂性能以及冲击性能对壁厚的依赖性显著改善。在PC中加入经120 m in臭氧化处理的POE后,PC/POE(90/10)共混物的冲击强度与PC相比从24.6 kJ/m2提高到72.5 kJ/m2,低温(-20℃)冲击强度从18.8 kJ/m2提高到68.6 kJ/m2。在丙酮中浸泡4 h后,共混物的冲击强度与PC(降至3.2 kJ/m2)相比仅降至43.7 kJ/m2。未经改性处理的PC冲击强度从67.7 kJ/m2(壁厚3.2 mm)迅速下降到11.5 kJ/m2(壁厚6.4 mm);经120m in臭氧化处理,PC/POE(90/10)共混物的冲击强度从75.5 kJ/m2(壁厚3.2 mm)仅下降到58.0 kJ/m2(壁厚6.4 mm)。PC/POE(90/10)共混体系的加工流变性能与PC相比也得到改善。     

核壳结构改性剂对PBT/PC共混物的增韧作用

采用丙烯腈-丁二烯-苯乙烯（ABS）核壳结构改性剂增韧聚对苯二甲酸丁二醇酯（PBT）/聚碳酸酯（PC）共混物。动态力学测试（DMTA）结果表明,PBT与PC为热力学不相容体系,ABS的引入导致PBT、PC玻璃化转变温度相互靠近,相容性提高;差示扫描量热（DSC）研究结果表明,随着ABS的加入,PBT/PC体系中PBT的...     

PBT/(POE/LLDPE)-g-GMA共混物的力学性能与形态结构

采用双螺杆挤出机将甲基丙烯酸缩水甘油酯(GMA)同时接枝到乙烯-辛烯共聚物(POE)和线性低密度聚乙烯LLDPE上,而后将接枝产物与聚对苯二甲酸丁二醇酯(PBT)反应性共混,通过改变POE/LLDPE比例确立了PBT/(POE/LLDPE)-g-GMA共混物分散相的最佳组成。以此为基础考察了GMA加入量对共混物的力学性能、流变行为及相形态的影响,并对共混物的形变机理进行了研究。实验结果表明,POE/LLDPE比例为50/50时冲击强度最大,在此组成下共混物的冲击强度随着GMA加入量的增加而呈现先增大后减小的趋势,并在GMA加入量(GMA/(POE+LLDPE))为5%时达到最大值;体系黏度随GMA加入量的增加而增大,过量的GMA会导致严重的交联,不利于分散相的分散,从而降低了增韧效率;橡胶粒子的空洞化促使基体发生剪切屈服是其主要的形变机理,LLDPE的引入能促进PBT发生进一步形变,从而提高增韧效率。     

核壳粒子特性对其增韧PBT/PC共混物性能的影响

调节叔十二烷基硫醇(TDDM)用量合成了以聚丁二烯(PB)为核,苯乙烯-丙烯腈-甲基丙烯酸环氧丙酯共聚物为壳的核壳粒子ABS-g-GMA。接枝特性测试发现TDDM降低了核壳粒子的接枝率和接枝效率。动态力学热分析结果表明TDDM降低了PB相交联程度,提高了PB空洞化能力。随着TDDM用量增加,ABS-g-GMA屈服应变降低,断裂伸长率提高。透射电镜发现TDDM加入对ABS-g-GMA在聚对苯二甲酸丁二醇酯(PBT)与聚碳酸酯(PC)共混物基体中的分散形态没有不利影响。力学测试表明ABS-g-GMA粒子对PBT/PC共混物具有良好的增韧作用。TDDM对ABS-g-GMA增韧PBT/PC有积极作用,能使共混物冲击韧性和断裂强度得到提高。     

PLA-g-MAH增容改性PLA/PETG共混物的结构与性能

采用熔融法制备聚乳酸接枝马来酸酐(PLA-g-MAH)用于增容改性聚乳酸/聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PLA/PETG)共混物,通过傅里叶转换红外光谱(FT-IR)、扫描电子显微镜(SEM)和力学性能测试,考察了共混物的结构和力学性能。SEM结果显示,加入增容剂PLA-g-MAH后,PLA/PETG共混物两相间的界面明显变得模糊,说明PLA-g-MAH对共混物具有一定的增容作用;增容剂的引入,使共混物的拉伸强度和弯曲模量略有下降,但冲击强度略有提高,断裂伸长率显著提高(PLA的为6.9%,而加入3%增容剂共混物的为21.9%,提高到纯样的3倍左右),表现出良好的性能。     

Fracture toughness and fracture mechanisms of PBT/PC/IM blends: Part V Effect of PBT-PC interfacial strength on the fracture and tensile properties of the PBT/PC blends

To investigate the effect of PBT-PC interfacial strength on the fracture toughness and toughening mechanisms of the PBT/PC system, a series of PBT/PC blends with different content of in situ formed PBT-PC copolymers were made by melt blending. The in situ copolymer was separately prepared via reactive blending of the PBT and PC in the presence of a transesterification catalyst in a twin-screw extruder for a few minutes. The reactive extrudate (RE) was studied using a DSC and the existence of the PBT-PC copolymer in the RE was confirmed. Microstructure characterizations of the PBT/PC/RE blends revealed that the domain sizes of the PBT and PC decrease and the PBT-PC interfacial strength increases with the RE content. Compared with the PBT/PC blend, all the PBT/PC/RE blends have higher yield strength, elongation at break as well as tensile modulus. The quasi-static fracture tests show that fracture toughness of the blends increases with the RE content. Since the highest toughness was obtained with the blend having the highest RE content (7.5%), it is not certain at this stage whether adding more than 7.5% RE will further improve the fracture toughness. The impact toughness of the PBT/PC/RE blends was found to decrease with the increase of the PBT-PC interfacial strength, which confirms the failure mechanisms proposed in the Part-4 of this series.     

聚酯含量对PBT/PET/PA-6三元共混物性能影响

采用ＤＳＣ、ＳＥＭ等方法对ＰＢＴ／ＰＥＴ／ＰＡ６三元共混物中聚酯含量的变化与共混物性能之间的关系进行了研究。实验结果表明,共混物中ＰＥＴ含量的增加有利于提高该三元共混物的热性能和结晶性能;另外,ＰＢＴ含量的增加则大大提高了共混物的抗冲击能力。     

Fracture toughness and fracture mechanisms of polybutylene-terephthalate/polycarbonate/ impact-modifier blends

A series of polybutylene-terephthalate/polycarbonate (PBT/PC) blends with different compositions were prepared using a twin-screw extruder. The morphologies of the blends were revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that a 50/50 PBT/PC blend possessed a bicontinuous structure and the other blends had a dispersed phase of either PBT or PC depending on which was the minor component. A relatively strong interface was observed in the blends with 20%, 40% and 50% PBT; but poor interfacial adhesion was found in the blends with 60% and 80% PBT. The strength of the interfacial boundary was believed to depend on the composition and blending conditions of the individual blend. Fracture experiments showed that the sharp-notch fracture toughness of PC could be significantly increased by mixing with up to 50% PBT without losing its modulus and yield stress. The toughening mechanisms involved in the fracture processes of the blends were studied using both SEM and TEM together with single-edge-double-notched-bend (SEDNB) specimens. It was found that in the toughened blends the growing crazes initiated by the triaxial stress in front of the crack tip were stabilized by the PC domains. The debonding-cavitation mechanism occurred at the PBT/PC interface, which relieved the plane-strain constraint and promoted shear deformation in both PBT and PC. This plastic deformation absorbed a tremendous amount of energy. Crack-interface bridging by the PC domains was clearly verified by the TEM study. Thus, the PC domains not only stabilized the growing crazes they also bridged crack surfaces after the crack has passed by. This effect definitely caused a large plastic-damage zone and hence a high crack resistance. Poor crack resistances of the blends rich in PBT was caused by the poor interfacial adhesion between PBT and PC. In these polymer blends, the growing crazes easily developed into cracks, which subsequently passed through the weak interface of PBT/PC and finally produced fast unstable fracture.     

Mechanical and thermal properties of poly(butylene terephthalate)/poly(ethylene naphthalate), and Nylon66/poly(ethylene naphthalate) blends

The tensile modulus, tensile strength and impact strength of melt blends of (a) poly(ethylene naphthalate) (PEN) and poly(butylene terephalate) (PBT) with 30, 40, 50, 60 and 70 wt% PEN, (b) Nylon66 and PEN with 30, 50 and 70 wt% Nylon66 were measured, and thermal/thermomechanical properties were analysed by differential scanning calorimetry and dynamic mechanical thermal analysis. Scanning electron microscopy was used for examination of the fracture surfaces of the blends.All PBT/PEN blends show two glass transitions corresponding to the presence of two phases: the glass transition temperature, T _g, of the phase with the lower T _g increases with increasing PEN content, and T _g for the phase with higher T _g decreases with increasing PBT content. The implication is that the two polymers are partially miscible, and scanning electron microscopy of fracture surfaces reveals a very small (sub-micron) domain size. Nylon66/PEN blends also show two phases, but the domain size is of the order of m and there is no evidence of partial miscibility.Up to 50 weight proportions PBT does not lower the tensile strength of PBT/PEN blends, and the tensile strength lies between values predicted by the rule of mixtures and a modified rule of mixtures. Incorporation of at least 40% PEN in PBT increases impact strength, but blending with smaller proportions of PEN decreases impact strength. By contrast, blending of Ny66 and PEN results in reduction of tensile strength for all blend compositions.     

PBT／PMMA共混体系的研究

通过PBT/PMMA、PB/PMMA/PC共混物的拉伸行为、动态力学行为和形态,讨论了PC对PBT/PMMA共混体系的性能及形态的影响。指出PC的存在导致共混物中PMMA的粒径变小,使PMMA对PBT显示出增韧效应,但对PBT-PMMA的相容性无明显影响。     

PC-g-PS增容PC/PS共混体系的相容性和性能

研究了不同配比的ＰＣ／ＰＳ共混体系的物理和力学性能及其与相容性的关系,结果表明,ＰＳ含量越高,拉伸强度、冲击强度、密度和吸水率等越低,而表面硬度和耐溶剂开裂能力则提高。通过ＤＳＣ谱、ＳＥＭ等实验结果表明,少量的辐射接枝共聚物ＰＣ－ｇ－ＰＳ加入ＰＣ／ＰＳ共混体系,即能明显改善其相容性。加了共聚物以作为增容剂后,共混物的拉伸强度、冲击强度、密度、表面硬度和耐溶剂开裂能力均要比其相应的简单共混物的值来得高,而吸水率则有所下降。     

Fracture toughness and fracture mechanisms of PBT/PC/IM blends PART IV Impact toughness and failure mechanisms of PBT/PC blends without impact modifier

In this part of the series, the impact behaviour of the PBT and PC blends without impact modifier was studied. Failure mechanism of the blends under various conditions was discussed. It was found that the key toughening process, i.e. interfacial debonding-cavitation, was disabled when the blends were subjected to impact loading. Hence, the fracture of the thick PBT/PC specimens with strong interface occurred under plane-strain condition. Their impact toughness obeys the rule of mixtures and synergistic toughening could not be achieved. When thinner specimens were tested, the fracture took place under non-plane-strain condition. But, the toughness of the blends was much lower than the value predicted by the rule of mixtures. Negative blending effect was obtained. Study on the strain rate effect suggests that under impact loading, the PC domains in the blends are subjected to an additional plastic constraint imposed by the neighboring PBT matrix, which is more rigid at a higher strain rate. Since fracture of the PC is highly sensitive to the plastic constraint at the crack-tip, the PBT imposed high plastic constraint promotes brittle fracture of the PC, leading to a deteriorated impact resistance. Evidences from TEM, SEM and OM studies support the mechanism proposed. Based on this mechanism, some suggestions on the selection of polymer components and design of microstructure for rigid-rigid polymer blends are also given.     

芳基磷酸酯对PC/PBT合金阻燃性能和酯交换反应的影响

在双酚A型聚碳酸酯/聚对苯二甲酸丁二醇酯合金(PC/PBT)中分别采用两种芳基磷酸酯[间苯二酚双(二苯基磷酸酯)(RDP)和双酚A双(二苯基磷酸酯)(BDP)]为阻燃剂,考察了其对PC/PBT合金力学性能、阻燃性能和其在锥形量热仪中的热释放行为影响。并且采用差示扫描量热仪(DSC)研究了芳基磷酸酯对PC/PBT体系的酯交换反应,以解释力学性能变化的原因。结果表明,RDP和BDP在PC/PBT中用量为10%时均达到UL94V-0级别,但加入BDP的体系的力学性能优于加入RDP的体系。热释放行为说明,RDP的阻燃作用同时包括气相与凝聚相作用,而BDP主要为凝聚相阻燃作用。BDP明显地抑制了PC/PBT的酯交换反应,因此有较好的力学性能。