PBT/石墨烯纳米复合材料的制备及性能研究进展

概述了石墨烯的功能化修饰研究,对聚对苯二甲酸丁二醇酯(PBT)/石墨烯纳米复合材料的制备方法 (熔融共混法、原位聚合法)和性能(力学性能、热学性能、电性能、流变性能)研究进展进行了综述,并对其研究趋势进行了展望。     

原位聚合制备PBT/nano-ZnO复合材料及其结晶性能研究

以精对苯二甲酸（PTA）和1,4-丁二醇（BDO）为基本原料,在5 L熔融缩聚反应釜中,采用原位聚合工艺,通过加入自制纳米氧化锌（nano-ZnO）,制备得到聚对苯二甲酸丁二醇酯（PBT）/nano-ZnO复合材料。采用差示扫描量热仪对PBT/nano-ZnO复合材料的结晶性能进行测试,并研究了复合材料的非等温结晶行为。结果表明,加入nano-ZnO后,不影响PBT的聚合工艺,nano-ZnO对PBT有异相成核作用;Jeziorny法可以很好地分析PBT及其复合材料的非等温结晶过程。     

氧化石墨烯及PBT复合材料的制备与性能

采用Hummers法制备了氧化石墨烯(GO),再分别采用功能性单体KH-550型硅烷偶联剂和聚乙烯基吡咯烷酮(PVP)对GO进行功能化改性,制备了GO-g-KH550和GO-g-PVP杂化材料。分别以GO,GO-g-KH550和GO-g-PVP为填料,聚对苯二甲酸丁二醇酯(PBT)为基体,通过熔融共混-模压成型法制备了不同填料含量的PBT复合材料。测试结果表明:KH550与PVP成功地接枝到了GO的表面上;随着填料质量分数的增加,PBT复合材料的拉伸性能与冲击性能均呈现先增后降的现象,当GO,GO-g-KH550和GO-g-PVP的添加质量分数分别为0.50%,0.50%,0.25%时,复合材料综合性能最佳;当添加的填料质量分数小于0.50%时,填料能均匀的分散在基体材料中,随着添加量的增加,填料逐渐出现团聚现象;填料的加入使复合材料结晶峰向高温方向移动,但结晶度有所下降。     

连续纤维增强聚环状对苯二甲酸丁二醇酯复合材料的研究进展

介绍了环状对苯二甲酸丁二醇酯(CBT)树脂的合成机理及其开环聚合机理,对比了聚环状对苯二甲酸丁二醇酯(PCBT)与聚对苯二甲酸丁二醇酯(PBT)的性能并介绍了纤维增强聚环状对苯二甲酸丁二醇酯复合材料的力学性能,综述了聚环状对苯二甲酸丁二醇酯(PCBT)基复合材料制备工艺的研究进展。     

PBT/AT纳米复合材料的力学性能和热学性能

研究了熔融共混法制备的聚对苯二甲酸丁二醇酯（PBT）/改性凹凸棒粘土（AT）纳米复合材料的力学性能和热学性能。结果表明：AT含量较低时可以使复合材料力学性能明显改善,而AT含量较高时,拉伸和冲击性能下降 凹凸棒粘土在含量低时起成核剂的作用促进PBT结晶,使结晶度增大,而含量高时使PBT的结晶度变小 凹凸棒粘土的加入使基体的结晶不完整。凹凸棒粘土增强改性PBT的机理为其纳米效应。     

聚酯PTT及PTT/PBT共混体系的结晶形态

选取均聚物聚对苯二甲酸丙二醇酯(PTT)及PTT/聚对苯二甲酸丁二醇酯(PBT)共混物为研究对象,以偏光显微镜(POM)和X射线衍射(XRD)为研究手段探讨了均聚物PTT的结晶形态,以及结晶温度、共混物的组成、等温结晶时间等因素对PTT/PBT共混物结晶形态和性能的影响。结果表明,PTT形成环带球晶的条件是155℃,PTT/PBT共混物的结晶尺寸由于PBT的引入而变小,在PTT质量分数小于60%以后就不能产生环带球晶;PTT/PBT共混物结晶时是两个组分各自结晶,并且相互竞争,使其生成环带球晶的关键是结晶组分的结晶速率要和非结晶组分之扩散速率相匹配。     

低模温玻纤增强PET复合材料的制备与表征

采用差示扫描量热法研究了聚对苯二甲酸丁二醇酯(PBT)、乙烯-醋酸乙烯酯共聚物(EVA)、乙烯-正丁基丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物(PTW)对聚对苯二甲酸乙二酯(PET)冷结晶峰温的影响,发现随着PBT含量的增大,PET的冷结晶峰温;当PBT的添加量为50份时,冷结晶峰基本消失;同时加入20份PBT和15份EVA亦可使冷结晶峰消失;PBT、PTW和EVA在降低冷结晶峰温的同时还有助于提高玻纤增强PET复合材料的冲击强度;在PET/PBT体系中,加入适量的无机填料硫酸钡和滑石粉可使热变形温度达到220℃以上。     

有机硅磷酸酯对PBT/PET酯交换反应的影响

采用两次循环扫描方法研究了有机硅磷酸酯对聚对苯二甲酸丁二醇酯/聚对苯二甲酸乙二醇酯（PBT/PET）酯交换反应的影响,测定了PBT/PET合金的结晶性能、热变形温度、力学性能和相对黏度,并与常规的抑制剂亚磷酸三苯酯进行了比较。结果发现：加入有机硅磷酸酯后PBT/PET合金的结晶温度提高了4.5 ℃,相对黏度提高了0.1 dL/g,热变形温度提高了7.0 ℃。而加入亚磷酸三苯酯后PBT/PET合金的结晶温度降低了1.5 ℃。说明有机硅磷酸酯可有效控制PBT/PET合金中端羟基的含量,从而可有效抑制PBT和PET之间的酯交换反应。亚磷酸三苯酯和有机硅磷酸酯的加入对PBT/PET体系的力学性能影响不大。     

PET与PBT配比对阻燃增强PET/PBT合金表面浮纤的影响

研究了不同聚对苯二甲酸乙二醇酯（PET）和聚对苯二甲酸丁二醇酯（PBT）配比对阻燃增强PET/PBT合金表面浮纤的影响。采用二次元影像测试仪和目测的方式,半定量地表征表面浮纤。结果表明,随着PBT含量的增加,表面浮纤逐渐减弱;当PET和PBT质量比接近1∶1时,材料表面质量最好;进一步提高PBT含量时,表面浮纤现象又逐渐严重;阻燃增强PBT材料的表面浮纤现象比阻燃增强PET材料轻。     

碳纤维增强PBT/ABS-g-MAH复合材料的力学性能和流变行为

利用扫描电子显微镜、电子万能试验机、冲击试验机、旋转流变仪和差示扫描量热仪分别研究了聚对苯二甲酸丁二醇酯（PBT）/马来酸酐接枝丙烯腈丁二烯苯乙烯共聚物（ABS-g-MAH）/短切碳纤维（SCF）复合材料的相形态、力学性能、流变和结晶行为。结果表明,复合材料断面上纤维的分布较为均匀,SCF与PBT之间有较好的界面结合性能;当SCF含量为5 %~10 ％时,复合材料的力学性能得到明显提高;随着SCF含量的增加,复合材料熔体的复数黏度呈现先降低后升高的趋势;在体系中添加适量的SCF可以起到成核剂的作用,由于结晶变得相对容易,从而使结晶温度升高,然而过量的SCF会在一定范围内阻碍PBT的结晶。     

Effects of hybrid nucleating agents on glass fiber‐reinforced polyethylene terephthalate/polybutylene terephthalate alloy crystallization

In this article, the Surlyn® 8920 and AX 8900 were mixed as hybrid nucleating agents for glass fiber (GF)‐reinforced polyethylene terephthalate (PET)/polybutylene terephthalate (PBT) alloy. The crystallization behaviors on GF‐reinforced PET/PBT alloy with compound nucleating agents of Surlyn® 8920 and AX 8900 were studied by differential scanning calorimeter. The Jeziorny method, Mo method, and Kissinger method were used for studying the non‐isothermal crystallization process of the composite alloys. While single AX 8900 cannot further improve the crystallization properties of the alloy and reduced the crystallization rate, the introduction of Surlyn® 8920 can effectively ameliorate the condition. The results demonstrated the hybrid nucleating agents of Surlyn® 8920 and AX 8900 not only can accelerate crystal growth, but also can significantly reduce the energy barrier, and it has a good effect in the alloy to the nucleation. POLYM. COMPOS. 37:1167–1172, 2016. © 2014 Society of Plastics Engineers     

Preparation and characterization of poly (butylene terephthalate)/graphene composites by in-situ polymerization of cyclic butylene terephthalate

The ultra-low viscosity of cyclic butylene terephthalate oligomers has been exploited to perform their in-situ ring-opening polymerization in the presence of graphene, to obtain homogeneously dispersed poly(butylene terephthalate)/graphene (PBT/G) composites containing 0.5 to 1.0 %wt of graphene. The results of gel permeation chromatography show that increasing amounts of graphene causes a decrease in the average molecular weight of PBT if the time of polymerization is kept constant, and morphological investigations performed by electron microscopy and x-rays diffraction show that high levels of dispersion of the G sheets are easily obtained by this method of composites processing. Thermal properties of the composites were studied by differential scanning calorimetry and thermogravimetric analysis; results indicate that increasing amounts of G do not strongly influence the degree of crystallinity and the crystallization temperature of PBT, while its thermal stability is significantly increased by the presence of G. All the PBT/G composites demonstrated to be electrically conductive; we found that the electric field assisted thermal annealing of the PBT/G composites induces an increase in conductivity.     

聚对苯二甲酸丙二醇酯的结晶性能研究

采用热台偏光显微镜和DSC差示扫描量热仪对PET、PTT和PBT的结晶性能进行了研究。实验得到的结果是:PBT具有极强的结晶能力。在相同的△T下,PTT的结晶诱导期和球晶出现的时间比PET短,球晶的生长速率也比PET快;同时,在相同的△T下,PTT的总结晶速率大于PET。PET和PTT在较高的温度下等温结晶时倾向于异相成核,而随着等温结晶温度的降低,开始倾向于均相成核。     

复合成核剂对PBT结晶行为的影响

采用熔融共混法制备了聚对苯二甲酸丁二醇酯(PBT)和成核剂二苄山梨醇(DBS)或苯甲酸钠(SB)的共混物,通过差示扫描量热仪(DSC)、X射线衍射仪(XRD)、偏光显微镜(PLM)分析了各成核剂对PBT的结晶行为的影响,结果表明:添加任何一种成核剂均能明显改善PBT的结晶行为,即加快结晶速度、提高结晶度、细化晶体及完善晶体形态;其中复合成核剂要明显优于单一成核剂,复合成核剂中SB的影响程度要大于DBS。还采用热重分析(TGA)仪对体系的热性能进行了研究,发现成核剂的加入并未降低体系的热性能。     

PBT非等温结晶动力学

用差示扫描量热法研究聚对苯二甲酸丁二酯（PBT）的非等温结晶动力学，并分别用Ozawa,Jeziorny和考虑综合因素法来处理PBT的非等温结晶数据。结果表明，PBT非等温结晶过程与Ozawa动力学方程相吻合，但不符合用Jeziorny方法处理的Avrami动力学方程；综合考虑温度和结晶程度对聚合物结晶速度的影响。PBT非等温结晶过程符合结晶动力学方程。     

PBT/PTT合金的非等温结晶行为

采用差示扫描量热法(DSC)研究了聚对苯二甲酸丁二酯(PBT)/聚对苯二甲酸丙二酯(PTT)合金的非等温结晶动力学.随着降温速率的增大,PBT/PTT合金的结晶峰温均降低,结晶峰均加宽.采用Jeziorny法、莫志深法和Flyn-Wall-Ozawa法分析非等温结晶过程,Jeziorny法能够描述PBT/PTT合金的初期结晶过程,对后期结晶存在一定偏差,各PBT/PTT合金的结晶维数变化不大;莫志深和Flyn-Wall-Ozawa法能很好地描述PBT/PTT合金的非等温结晶过程,随PTT含量增加,由Flyn-Wall-Ozawa法求得PBT/PTT合金的活化能呈增加趋势.相对结晶度为0.5,m(PBT)/m(PTT)分别为90∶10,70∶30,50∶50时,PBT/PTT合金的活化能分别为-201.9,-116,0,-66.6 kJ/mol;相对结晶度为0.5时,m(PBT)/m(PTT)为50∶50的合金活化能比PTT(-77.4 kJ/mol)还高.     

Properties of ternary in situ polycarbonate/polybutylene terephthalate/liquid crystalline polymer composites

Ternary in situ polycarbonate (PC)/polybutylene terephthalate (PBT)/liquid crystalline polymer (LCP) composites were prepared by injection molding. The liquid crystalline polymer used was a versatile Vectra A950. The matrix of composite was composed of PC/PBT 60/40 by weight. A solid epoxy resin (bisphenol type‐A) was used as a compatibilizer for the composites. Dynamic mechanical analysis (DMA) showed that epoxy resin was effective to improve the compatibility between PC and PBT, and between PC/PBT and LCP, respectively. Tensile tests revealed that the stiffness of composites shows little change with the LCP content up to 10 wt %. Above this concentration, the stiffness tended to increase with increasing LCP content. Furthermore, the tensile strengths appeared to increase with increasing LCP content, and their values were close to those predicted from the rule of mixtures. Scanning electron microscopic examination showed that LCP ribbons and short fibrils were developed in the composites containing LCP content ≤10 wt %. However, fine and elongated fibrils were formed in the skin and core sections of the composites when the LCP content reached 25 wt % and above. Thermogravimetric analysis indicated that the thermooxidative stability of the PC/PBT 60/40 blend tended to improve with increasing LCP content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1827–1835, 1999     

改善玻纤增强阻燃聚对苯二甲酸丁二醇酯流动性的研究

为提高玻纤增强阻燃聚对聚二甲酸丁二醇酯（PBT）的流动性能，在体系中分别加入了不同的增塑剂。结果表明，适量加入低粘度PBT，乙烯共聚物A，松香酯A，松香酯B可使体系在保持综合性能较好的前提下，流动性能得到不同程度的改善，加工温度的提高也可改善体系的流动性。     

Isothermal and non‐isothermal crystallization of poly(L‐lactic acid)/poly(butylene terephthalate) blends

Isothermal and non‐isothermal crystallization kinetics of poly(l ‐lactic acid)/poly(butylene terephthalate) (PLLA/PBT) blends containing PLLA as major component is detailed in this contribution. PLLA and PBT are not miscible, but compatibility of the polymer pair is ensured by interactions between the functional groups of the two polyesters, established upon melt mixing. Crystal polymorphism of the two polyesters is not influenced by blending, as probed by wide‐angle X‐ray analysis. The addition of PLLA does not affect the temperature range of crystallization kinetics of PBT, nor the crystallinity level attained when the blends are cooled from the melt at constant rate. Conversely, PBT favors crystallization of the biodegradable polyester. The addition of PBT results in an anticipated onset of crystallization of PLLA during cooling at a fixed rate, with a sizeable enhancement of the crystal fraction. Isothermal crystallization analysis confirmed the faster crystallization rate of PLLA in the presence of PBT. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40372.     

PBT结晶速度方程及其应用

用 DSC法研究聚对苯二甲酸丁二酯 ( PBT)的结晶动力学 ,分别在 468.15 ,471.15 ,473.15 K的等温条件下进行了 PBT等温结晶实验 ,从 PBT等温结晶曲线和等速降温结晶曲线得到在不同温度条件下的结晶动力学数学模型。运用模型对不同 PBT试样进行分析 ,能较好地解释不同品质 PBT的结晶行为