Chain extension of poly(butylene terephthalate) by reactive extrusion

The chain extension reaction in poly(butylene terephthalate) (PBT) melt was studied in detail. A high‐reactivity diepoxy, diglycidyl tetrahydrophthalate, was used as a chain extender that can react with the hydroxyl and carboxyl end groups of PBT at a very fast reaction rate and a relatively high temperature. A Haake mixer 600 was used to record the torque during the chain extension reaction. The data show that this chain extension reaction could be completed within 2 to 3 min at temperatures above 250°C, and the reaction time decreased very fast with an increase in the temperature. Shear rate also had some effects on the reaction rate. The effect of the diepoxy chain extender on the flowability, thermal stability, and mechanical properties of PBT were investigated. The melt flow index (MFI) of the chain‐extended PBT dramatically decreased as the diepoxy was added to PBT. In addition, the notched Izod impact strength and elongation‐at‐break of the chain‐extended PBT also increased. The chain‐extended PBT is more stable thermally. Compared with the conventional solid post‐polycondensation method, this approach is simpler and cheaper to obtain high‐molecular‐weight PBT resins. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1827–1834, 1999     

聚对苯二甲酸甲二酯的热分解行为及其动力学研究

研究了惰性气氛下聚对苯二甲酸甲二酯(PMT)的非等温热分解行为及其动力学,并与聚对苯二甲酸丁二酯 (PBT)进行了对比。研究发现,PMT的热降解过程包括两个主要失重阶段,其热分解反应不是一级反应。第一阶段的起始分解温度较低是由于产物的分子链末端基中含有Br或Cl能催化聚合物的降解反应;第二阶段为分子链主体的热分解过程,由于分子链中苯环的密度较大,分子链的热稳定性比具有较低苯环密度的PBT要高。而PBT的降解失重过程仅为一个阶段,为一级反应。     

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.     

On Toughness and Stiffness of Poly(butylene terephthalate) with Epoxide‐Containing Elastomer by Reactive Extrusion

Summary: To obtain a balance between toughness (as measured by notched impact strength) and elastic stiffness of poly(butylene terephthalate) (PBT), a small amount of tetra‐functional epoxy monomer was incorporated into PBT/[ethylene/methyl acrylate/glycidyl methacrylate terpolymer (E‐MA‐GMA)] blends during the reactive extrusion process. The effectiveness of toughening by E‐MA‐GMA and the effect of the epoxy monomer were investigated. It was found that E‐MA‐GMA was finely dispersed in PBT matrix, whose toughness was significantly enhanced, but the stiffness decreased linearly, with increasing E‐MA‐GMA content. Addition of 0.2 phr epoxy monomer was noted to further improve the dispersion of E‐MA‐GMA particles by increasing the viscosity of the PBT matrix. While use of epoxy monomer had little influence on the notched impact strength of the blends, there was a distinct increase in the elastic stiffness. SEM micrographs of impact‐fracture surfaces indicated that extensive matrix shear yielding was the main impact energy dissipation mechanism in both types of blends, with or without epoxy monomer, and containing 20 wt.‐% or more elastomer.

SEM micrographs of freeze‐fractured surfaces of PBT/E‐MA‐GMA blend illustrating the finer dispersion of E‐MA‐GMA in the presence of epoxy monomer.     

PBT共混改性研究最新进展

综述了最近几年国内外聚对苯二甲酸丁二醇酯(PBT)共混改性的研究进展,分类介绍PBT/聚烯烃、PBT/同系聚酯、PBT/液晶、PBT/弹性体、PBT/聚碳酸酯等不同共混体系,讨论了各体系中的相行为、相容性、热稳定性、力学性能等,并对该类共混物的发展趋势作了简要的分析。     

Fabrication and Properties of Modified Poly(butylene terephthalate) with Two-Step Chain Extension

High-viscosity, low-crosslinked poly(butylene terephthalate) (PBT) from organic chain extenders and inorganic particles are prepared. PBT modification adopted from multifunctional, commercially available chain extension containing nine epoxy groups (ADR9) occurs in the first-step chain extension; hydroxyl addition modified dioxazoline (BOZ) serves as the second step. Anion stratiform inorganic hydrotalcite (HT) is used to adjust the crystallization behavior and damp-heat aging properties of PBT. The reaction between the chain extender and PBT end-groups such as carboxyl (–COOH) and hydroxyl (–OH) enhances the interfacial bonding between the PBT matrix and dispersed HT phases. With a fraction of chain extenders in the PBT matrix, the chain-extended PBT exhibits higher mechanical properties, intrinsic viscosity, average molecular weight, and melt viscosity than those of unmodified PBT. Damp-heat aging resistance measurements show correlation with initial carboxyl content in the resin. Reducing the concentration of carboxyl end-groups in the resin is shown to increase hydrolytic stability. The modified PBT resin can be used in optical fiber communication cable industry for its high level of damp-heat aging resistance as well as good mechanic properties.     

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     

聚丁二酸丁二醇-共-对苯二甲酸丁二酯流变性能研究

采用毛细管流变仪研究了聚丁二酸丁二醇-共-对苯二甲酸丁二酯(PBST)的流变性能。结果表明:PBST熔体为切力变稀型流体,黏流活化能较低,具有较好的成纤性能。同时,讨论了相对分子质量、剪切速率、温度对PBST熔体流动曲线、非牛顿指数、结构黏度指数等的影响,为生物可降解性PBST纤维的生产工艺提供了理论依据。     

ABS-g-GMA增韧聚对苯二甲酸丁二醇酯的研究

用甲基丙烯酸环氧丙酯（（MA）接枝的丙烯腈／丁二烯／苯乙烯（ABs）接枝共聚物（ABS-g-GMA）改善聚对苯二甲酸丁二醇酯（PBT）的缺口冲击韧性。动态力学分析、差示扫描量热分析以及流变性能测试结果表明，GMA引入到ABS中，随GMA含量的增加，PBT与ABS的玻璃化转变温度相互靠近，PBT的熔点降低，共混体系的扭矩、温度提高，这些结果表明GMA提高了PBT与ABS之间的相容性；增容反应导致ABS在PBT基体中均匀、稳定分散，有利于共混物性能的改善；交联反应导致交联聚集网状结构的生成，使共混物性能变差。冲击强度结果表明，1％（质量含量。下同）GMA含量就可以导致PBT／ABS-g-GMA共混物冲击韧性显著改善，当ABS-g-GMA1含量为30％时，共混物冲击强度高达850J／m。     

聚丁二酸丁二酯的结晶动力学研究

采用氯仿溶解聚丁二酸丁二酯（PBS）,然后利用甲醇逐级沉淀分离获得不同相对分子质量及其分布的PBS级分,分别采用差示扫描量热仪、广角X射线衍射仪、偏光显微镜等对不同级分PBS的等温和非等温结晶动力学、晶体形态及结构进行了系统研究。结果表明,随着相对分子质量的增加和相对分子质量分布的变宽,各级分的半结晶时间逐渐降低,结晶半峰宽逐渐变窄,结晶度逐渐增加;但各级分PBS的晶型和晶貌并未发生明显的转变。     

环氧官能化ABS增韧PBT及其共混物

合成了甲基丙烯酸环氧丙酯(GMA)接枝的丙烯腈-丁二烯-苯乙烯(ABS-g-GMA)核壳粒子增韧聚对苯二甲酸丁二醇酯(PBT),加入环氧树脂(Epoxy)为扩链剂进一步提高共混物的性能。红外光谱(FTIR)结果表明:GMA成功接枝到ABS粒子上;研究发现不同GMA含量的ABS-g-GMA粒子在PBT及PBT/Epoxy共混物中均匀分散;ABS-g-GMA对PBT增韧效果较好,Epoxy进一步提高了PBT/ABS-g-GMA共混物的冲击韧性及拉伸强度;ABS-g-GMA增韧PBT的机理是橡胶粒子的空洞化和PBT基体的剪切屈服。     

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。     

Melt characteristics,mechanical, and thermal properties of blown film from modified blends of poly(butylene adipate‐co‐terephthalate) and poly(lactide)

Blown films from poly(butylene adipate‐co‐terephthalate) and poly(lactide) (PLA) blends were investigated. The blends were prepared in a twin‐screw extruder, in the presence of small amounts of dicumyl peroxide (DCP). The influence of DCP concentration on film blowing, rheological, mechanical, and thermal properties of the blends is reported in this article. Rheological results showed a marked increase in polymer melt strength and elasticity with the addition of DCP. As a consequence, the film homogeneity and the stability of the bubble were improved. The modified blend films, compared with the unmodified blend, showed an improvement in tensile strength and modulus with a slight loss in elongation. Fourier transform infrared and gel results revealed that chain scission and branching were more significant than crosslinking when the DCP loadings in the blends were not higher than 0.7%. A reduction in melt temperatures of PLA was observed due to difficulty in chain crystallization. The concentrations of DCP strongly affected the melting temperatures but had an insignificant effect on the decomposition behavior of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚对苯二甲酸丁二醇酯的化学扩链改性研究

以 2 ,2′ -双 ( 2 -唑啉 ) (BOZ)为扩链剂 ,对聚对苯二甲酸丁二醇酯 (PBT)进行扩链改性 ,考察了反应时间、扩链剂用量对扩链效果的影响 ,测试了扩链后PBT的热失重、力学性能和DSC。结果表明 ,BOZ的用量为 0 .44 % ,反应时间 3～ 5min ,PBT的最大扩链效率可达 72 .9% ,PBT的特性粘数从 0 .83dL/g提高到 1.2 1dL/ g ,扩链后PBT热稳定性和力学性能都得到提高。     

Preparation and thermal behavior of random poly(butylene terephthalate/azelate) copolyesters

Poly(butylene terephthalate), poly(butylene azelate), and poly(butylene terephthalate/butylene azelate) random copolymers of various compositions were synthesized in bulk using the well‐known two‐stage polycondensation procedure, and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. As far as the thermal stability is concerned, it was found to be rather similar for all copolymers and homopolymers investigated. All the copolymers were found to be partially crystalline, and the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to pure homopolymers. Flory's equation was found to describe the T_m–composition data and permitted to calculate the melting temperatures (T^°_m ) and the heats of fusion (ΔH_u) of both the completely crystalline homopolymers. Owing to the high crystallization rate, the glass transition was observable only for the copolymers containing from 30 to 70 mol % of the terephthalate units; even though the samples cannot be frozen in a completely amorphous state, the data obtained confirmed that the introduction of the aromatic units gave rise to an increase of T_g, due to a chain stiffening. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2694–2702, 1999     

Further studies of polycarbonate-poly(butylene terephthalate) blends

The mechanical properties (tensile strength, low temperature falling weight impact strength) of XENOY CL-100 (a blend of polycarbonate and polybutylene terephthalate) have been studied. This blend is comprised of tough components and the property combinations that result may be useful for certain applications. The hydrolysis resistance of the blend in deionised water at 40°C has been studied. After 30 weeks it did not lose its tensile strength, but subsequently it did lose 50% of the low temperature (?70°C) falling weight impact strength. If the ?70°C low temperature toughness is an important quality, this should be taken into account. However, the low temperature (?70°C) falling weight impact strength of pure polycarbonate and of pure poly(butylene terephthalate) is very low, whilst XENOY CL-100 is still tough material, even after 30 weeks immersion at 40°C. Further study of the composition of XENOY CL-100 showed that this blend is composed of polycarbonate. poly(butylene terephthalate) and crosslinked acrylic rubber; traces of titanium-catalyst residue for the poly(butylene terephthalate) polymeristaion and black dye have also been found.     

PBS/PBAT共混型全生物降解材料的制备及其性能研究

通过熔融共混法制备了聚丁二酸丁二醇酯（PBS）/聚己二酸对苯二甲酸丁二酯（PBAT）共混物,用熔体流动速率法、扫描量热法、X射线衍射、扫描电镜法及力学性能测试等手段研究了PBS/PBAT共混物的熔体流动性、结晶性能、力学性能以及共混物相容性。结果表明,随着PBAT含量的增加,PBS/PBAT共混体系的拉伸强度先升高后降低,断裂伸长率不断提高,冲击强度先降低后提高;当PBAT含量为20 %（质量分数,下同）时,与纯PBS相比,断裂伸长率提高10倍,冲击强度提高82 %,而拉伸强度仅仅降低6 %。     

Melting behavior and crystallization kinetics of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolyesters

The melting behavior of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolymers was investigated by differential scanning calorimetry after isothermal crystallization from the melt. Multiple endotherms were found for all the samples, and attributed to the melting and recrystallization processes. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the copolymers under investigation were obtained. Two distinct peaks in the crystallization exothermic curve were observed for all the samples. Both of them appeared at higher times than that of PBT, indicating that the introduction of a comonomer decreased the crystallization rate. The observed dependence of this latter on composition was explained on the basis of the content of ether–oxygen atoms in diethylene and triethylene terephthalate units, and of the different sizes of these units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3545–3551, 2001     

Sequence analysis of poly(ethylene terephthalate)/poly(butylene terephthalate) copolymer prepared by ester-interchange reactions

The molecular structure of the copolyester formed through the interchange reaction in poly(ethylene terephthalate)/poly(butylene terephthalate) blends was investigated with ¹³C-NMR spectroscopy. The molar fractions of heterolinkage triads in the copolyesters were lower than the values calculated by Bernoullian statistics; this indicates that the sequence of heterolinkages was far from a random distribution at the initial stage of the interchange reaction. However, the randomness increased and the number-average sequence length decreased with reaction time. The solubility of the blend decreased with increasing sequence length, resulting from the formation of block copolymers with long sequence lengths at the initial stage of the interchange reaction. The solubility of the copolyester formed by a dibutyltin dilaurate (DBTDL)-catalyzed reaction was higher than that of the copolyester formed by a titanium tetrabutoxide-catalyzed reaction; this is related to the fact that alcoholysis prevailed in the DBTDL-catalyzed reaction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 159–168, 2001