Reactive extrusion of recycled poly(ethylene terephthalate) with polycarbonate by addition of chain extender

Poly(ethylene terephthalate) (PET) resin is one of the most widely used engineering plastic with high performance, but the poor impact strength limits its applications for the notch sensitivity. In this research, toughened PET alloy was prepared by blending recycled PET with polycarbonate (PC) and MDI (methylenediphenyl diisocyanate). Intrinsic viscosity and melt viscosity measurements proved increase of the molecular weights of PET via chain‐extending reaction. FTIR and DMA results proved that some PET–PC copolymers were produced and the compatibility of PET phase and PC phase was improved. In addition, the reaction induced by MDI also affected the crystallization behaviors of PET, as observed from DSC results, and the crytallinity of PET decreased with the increase of MDI content. For all of these effects of MDI of increasing of molecular weight, improving of compatibility, and limiting the crystallization behaviors of PET/PC alloy, the notched‐impact strength was greatly improved from 17.3 to 70.5 kJ/m². © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2602–2607, 2007     

酯交换抑制剂对PBT/PC共混体系性能的影响

通过对聚对苯二甲酸丁二酯／聚碳酸酯共混物的力学性能、热性能和微观结构的研究．考察了不同种类的酯交换抑制剂对其性能的影响．并进一步分析了酯交换抑制剂磷酸二氢钠的质量分数[ω（NaH2PO4)]对共混体系性能和结构的影响。结果表明,加入NaH2PO4,可以提高共混体系的简支梁缺口冲击强度、断裂伸长率及热稳定性;当ω（NaH2PO4)为0．75％,共混体系可以获得较好的综合性能。     

Reactive blending of commercial PET and PC with freshly added catalysts

Reactive blending of commercial poly(ethylene terephthalate) (PET) and bisphenol A polycarbonate (PC), with catalysts added in the form of powder dispersed on the polymers just before melt mixing, was performed in a Brabender Plasticord 2000 apparatus at 275°C. Catalytic activity of the catalysts freshly added to polymers was found to be much higher as compared with that of the residues of the same type of catalysts remaining in PET after its synthesis. Furthermore, the catalytic activity appeared to be strongly dependent on the structure of the ligand that influences the catalyst solubility in the polymer melt. N.m.r. spectroscopy, selective degradation of PC fragments, solubility tests in methylene chloride and d.s.c. measurements made it possible to range the catalysts studied according to their catalytic activity.     

PET/PLA共混物相容性和结晶性能的研究

研究了相容剂钛酸四丁酯[Ti(OBu)4]含量、聚乳酸(PLA)含量对聚对苯二甲酸乙二醇酯(PET)/PLA共混物相容性的影响,探讨了共混物的熔融和结晶行为,并对其结晶形貌进行了观察。结果表明,Ti(OBu)4含量为PLA的4%(质量分数,下同)时,PET/PLA共混物的相容性良好,但当PLA含量超过30%时,共混物出现相分离;PLA的加入使PET的结晶峰变窄,结晶速率增加,且结晶峰温度向高温方向移动;PLA的加入使PET的晶粒尺寸大幅减小,晶粒数目大幅增加,结晶更加完善。     

各种扩链剂对PET瓶片反应挤出扩链作用的研究

分别采用甲苯二异氰酸酯、三氧化二锑、邻苯二甲酸酐、均苯四酐、萘四甲酐以及均苯四酐和邻苯二甲酸酐混合物作为聚对苯二甲酸乙二醇酯（PET）瓶片的扩链剂,研究了反应挤出后产物特性黏度的变化。结果表明,甲苯二异氰酸酯、三氧化二锑、邻苯二甲酸酐和萘四甲酐对PET瓶片的扩链效果较弱;均苯四酐可明显提高PET的特性黏度。均苯四酐和邻苯二甲酸酐复配后的扩链效果最为显著;当均苯四甲酸二酐用量为0.3 %、邻苯二甲酸酐用量为0.2 %时,PET的特性黏度达到0.96 dL/g。     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

PC/PET共混合金相容性的研究

采用差示扫描量热仪、扫描电镜等测试手段对聚碳酸酯/聚对苯二甲酸乙二醇酯（PC/PET）共混合金的相容性进行研究。结果表明,未添加相容剂时,随PET含量的增加,共混合金的两个玻璃化转变温度有相互靠近的趋势,说明此体系部分相容。PET的加入可明显改善共混合金的加工流动性。PET含量为65 %左右时改善效果最佳。相容剂的加入使共混合金的拉伸强度和弯曲强度略有下降,但缺口冲击强度得到较大提高,在PC/PET（30/70）中添加3份乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯（PTW）或7份乙烯-丙烯酸乙酯共聚物（EEA）即可使缺口冲击强度由5.5 kJ/m2提高到10 kJ/m2以上。含有甲基丙烯酸缩水甘油酯（GMA）基团的相容剂PTW对两相界面的改善效果最好。     

Nucleation and crystallization of PET droplets dispersed in an amorphous PC matrix

The present work compares the nucleation and crystallization process of poly(ethylene terephthalate) (PET) in bulk and when it is finely dispersed in a polycarbonate (PC) matrix. Two types of 80/20 PC/PET immiscible blends were prepared by twin-screw extrusion at different screw rotation rates in order to produce fine dispersions of PET. The results indicate that the finer the dispersion, the greater the inhibition of the crystallization of the PET droplets. These results are explained by demonstrating (through self-nucleation experiments) that a fractionated crystallization process was developed in the dispersed PET, since the number of PET particles was much greater than the number of heterogeneities originally present in the bulk polymer. The dispersion of PET into droplets also affects its crystallization rate during isothermal crystallization at high temperatures and its reorganization capacity during heating. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1725–1735, 1998     

PET/PTT合金结晶形态的研究

采用XP-201热台偏光显微镜研究了对苯二甲酸乙二醇酯（PET）/对苯二甲酸丙二醇酯（PTT）合金等温结晶时的结晶形态及影响因素。研究结果表明：随着等温结晶温度的升高,PET/PTT(40/60)合金的结晶诱导期变长;在观察的时间范围内各样品的球晶尺寸随着时间的延长而增大;随着PTT含量的增加,样品球晶的线生长速率增大,球晶尺寸增大;对比不同温度下等温结晶的球晶形态,PET/PTT(100/0)样品在190℃结晶时球晶尺寸最大, PET/PTT(40/60)样品和PET/PTT(100/0)样品在180℃结晶时球晶尺寸最大; PET/PTT(0/100)样品等温结晶时呈现出了复杂的条带球晶。     

固相挤出回收PET结晶性能和降解程度的研究

提出一种全新的固相挤出加工方法,即在低温下用双螺杆挤出机挤出加工回收聚对苯二甲酸乙二醇酯(PET)。用WAXD和DSC分别考察PET的结晶形态和结晶性能,通过考察熔体流动速率和特性黏度的变化,评价回收PET树脂的降解程度。研究发现,与传统的熔融挤出法相比,经过固相挤出造粒的回收PET结晶更完善,结晶度提高了10％,晶粒大小分布更窄,而且降解程度有效地减小。     

PET与PTT共聚酯的合成及其性能研究

采用直接酯化法合成了不同比例的PET与PTT共聚酯,研究了所得共聚酯的热性能、力学性能及染色性等与不同组成比之间关系。     

PET/PTT合金非等温结晶行为的研究

采用差示扫描量热仪对熔融共混制备的聚对苯二甲酸乙二醇酯（PET）/聚对苯二甲酸丙二醇酯（PTT）合金的非等温结晶行为进行研究。结果表明,在相同的降温速率时, 随着PTT含量的增加,PET/PTT合金结晶峰温度向低温方向移动,而且当合金中PET与PTT含量接近时,合金样品出现了双重结晶峰;在降温结晶的过程中,随着降温速率的增大,各合金样品结晶峰温度均降低,其结晶峰均宽化;采用Jeziorny法对上述非等温结晶过程进行了分析,分析结果表明,随着降温速率的增大,各合金样品非等温结晶速率常数增加,其Avrami指数在1~5之间,并且逐渐减小。     

Effect of composition and molecular structure on the LC phase of PHB-PEN-PET ternary blend

Poly(p-hydroxybenzoic acid) (PHB)–poly(ethylene terephthalate) (PET) 8/2 thermotropic liquid crystalline copolyester, poly(ethylene 2,6-naphthalate) (PEN), and PET were mechanically blended to pursue the liquid crystalline (LC) phase of ternary blends. The torque values of blends with increasing PHB content abruptly decreased above 40 wt % of PHB content because the melt viscosity of ternary blends dropped. Glass transition temperature and melting temperature of blends increased with increasing PHB content. The tensile strength and initial modulus of blends were low at 10 and 20 wt % PHB. However, the blends containing above 30 wt % PHB were improved with increasing PHB content due to the formation of fibrous structure. The blend of 20 wt % PHB formed irregularly dispersed spherical domains, and the blends of 30–40 wt % PHB showed LCP ellipsoidal domains and fibrils. In the polarized optical photographs, the blends of 40 wt % PHB showed pseudo LC phases. The degree of transesterification and randomness of blends were increased with blending time. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1065–1073, 1998     

PET/PBT共混过程中酯交换反应的~(13)CNMR研究

用13C NM R 考察了添加扩链剂进行反应性共混后PET/PBT 的结构变化。在共混初期,检测不到嵌段共聚物的存在,可能与其含量极少有关。随着共混时间的增加,开始出现酯交换反应,且酯交换度随共混时间和温度而增加。扩链剂的加入能促进酯交换反应,但扩链剂的用量对酯交换的影响并不大     

PTT／PET共混体系结晶行为和形态研究

利用差示扫描量热仪、正交偏光显微镜研究了聚对苯二甲酸丙二醇酯(PTT)、聚对苯二甲酸乙二醇酯(PET)及PTT/PET共混体系(质量比为25∶75)的结晶行为、形态和等温结晶动力学。结果表明,PTT/PET共混物中,少量的PTT部分地起到了成核作用,但在一定程度上阻碍了PET链段规则地进入晶格,影响了结晶速率。偏光显微镜观察到PET、PTT和PTT/PET共混物在120℃下1、20min的溶液滴膜有较清晰的球晶。     

Melt rheological properties of reactive compatibilized HDPE/PET blends

Melt rheological properties of high density polyethylene and poly(ethylene terephthalate) (HDPE/PET) blends compatibilized by an ethylene–butyl acrylate–glycidyl methacrylate terpolymer (EBAGMA) were studied by means of a HAAKE torque rheometer and a capillary rheometer. The phase morphology of the blends was evaluated by a scanning electron microscope (SEM). The results showed that the melts of blends behave pseudoplasticity. The addition of EBAGMA strengthens the interfacial adhesion between HDPE and PET and improves the phase dispersion due to reactive compatibilization. It was observed that the balance torque, melt viscosity, and sensitivity of melt viscosity to shear rate of the melts increase with increasing content of EBAGMA, but the melt flow index and activation energy decrease. At the same time, the plasticizing time is shortened indicating that the processability of the compatibilized blends has been improved. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

含再生材料的PC/PET无卤阻燃合金加工稳定性

通过对再生聚对苯二甲酸乙二酯(PET–R)的多次挤出,研究了扩链对PET–R稳定性的影响。同时,也通过多次挤出和多次注塑的Regrind实验,研究了丙烯腈–苯乙烯塑料接枝甲基丙烯酸缩水甘油酯(AS-g-GMA)加入后再生聚碳酸酯(PC)/PET体系的相容性和稳定性,以及熔体流动速率和冲击强度的变化。通过11个月内的生产数据反映出,经过扩链和稳定化处理后的含再生材料的PC/PET无卤阻燃合金具有很好的加工稳定性。     

PET/TLCP扩链反应性共混物的热性能研究

研究了聚对苯二甲酸乙二酯（PET）和热致性液晶共聚酯60PHB／PET（含60％摩尔对羟基苯甲酸）体系在少量扩链剂双（2－Wu唑啉）（BOZ）存在下的反应性共混条件对共混物的玻璃化转变温度（Tg)、冷结晶温度（Tcc)、熔体结晶温度（Tmc)以及熔点（Tm)等热性能的影响。结果表明,BOZ对酯交换的促进作用使Tg升高;延长共混时间和提高共混温度使Tcc升高,Tmc和Tm下降,并受到BOZ加入量的显著影响。     

复配型结晶成核剂对PET结晶行为的影响

制备了以聚对苯二甲酸乙二醇酯（PET）为基体的复配型PET结晶成核剂母料——Nu-1；利用12SC研究了不同添加量的Nu-1对PET结晶行为的影响；对比了该成核剂与科莱恩公司的101和杜邦公司的Surlyn对PET结晶行为的影响。结果表明：Nu-1的加入可以有效促进PET结晶的成核速率，随着添加量从2％升高到5％，PET的结晶速率明显提高。在添加量相同时，Nu-1对PET结晶的促进作用接近101和Surlyn。     

Effects of mixing time on phase structure and mechanical properties of poly(ethylene terephthalate)/ polycarbonate blends

The effects of interchange reactions on the solid‐state structure and mechanical properties of a 70/30 poly(ethylene terephthalate) (PET)/bisphenol A polycarbonate (PC) blend were studied. Increasing reaction levels were obtained by means of lower screw speeds in the extruder. The progressive production of copolymers with the reaction time increased the amount of each component in the other phase. The concomitant degradation of PET led to a maximum in ductility and tensile and impact strengths whereas the modulus of elasticity and the yield stress were held constant. The maximum in properties took place at a reaction time close to 2.6 min; at longer reaction times the negative effect of degradation began to overcome the positive effect of the interchange reactions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 121–127, 2001