PHBV/PEA共混物结晶行为的研究

采用偏光显微镜(POM)和差示扫描量热仪(DSC)深入研究了不同配比的聚己酸戊酸共聚酯/聚己二酸乙二醇酯(PHBV/PEA)共混体系在不同结晶温度下的结晶形貌、结晶热力学以及结晶动力学。结果表明:随着结晶温度的升高,PHBV/PEA共混物中PHBV的球晶尺寸和环带间距均有所增大;随着PEA含量的增加,PHBV球晶尺寸增大,结构更加开放,同时共混物中PEA组分受PHBV组分的影响,由原来的大球晶变成了细小的碎晶。此外,同纯PHBV和纯PEA相比,PHBV/PEA共混体系中两种组分的结晶速率均有所降低。     

聚ε-己内酯及其在共混体系中结晶形态的研究

通过偏光显微镜(POM)研究了不同相对分子质量的聚ε-己内酯(PCL)均聚物的结晶形态及PCL在不同相容共混体系中的结晶形态.分别讨论了相对分子质量对PCL均聚物结晶形态的影响;共混物、共混组成及结晶温度对PCL在相容共混体系中结晶形态的影响.结果表明:PCL的相对分子质量越大,形成的球晶尺寸越小;第二组分的加入有利于...     

PBT/ε-PCL共混物的性能

实验通过熔融共混制备聚对苯二甲酸丁二醇酯(PBT)/聚己内酯(PCL)共混物,共混物中PCL的质量百分比从10%变化到90%,间隔为10%.实验研究PCL树脂质量百分比对共混物相容性、热性能、力学性能、相形态、熔融及结晶行为的影响.DMA和DSC热分析结果表明:PBT和PCL是部分相容体系,相容性随PCL含量的增加而增加,PCL的加入降低了PBT/PCL共混物中PBT相的熔点,改善了PBT的结晶能力.通过SEM对PBT/PCL共混物的相形态研究表明:PBT/PCL共混物具有两相结构,PCL质量含量为50%时发生相反转.力学性能分析结果表明:PCL能够增韧PBT,但效果不明显.     

PHBV/PBS共混物的性能研究

通过熔融共混的方法制备了聚β-羟基丁酸戊酸酯/聚丁二酸丁二醇酯(PHBV/PBS)共混材料。研究了PHBV/PBS共混物的力学性能、相形态、结晶性能、热性能及晶胞结构。结果表明,将PHBV和PBS共混后,PHBV的韧性会有明显改善。当PHBV/PBS/TEC质量比为20/80/5时,PHBV的断裂伸长率由原来的5.7%增至124%、冲击强度由1.7 kJ/m2增加到4.3 kJ/m2,分别为PHBV的21.7倍和2.5倍。DSC研究表明,PBS的加入抑制了PHBV的结晶,但当PHBV/PBS/TEC质量比为20/80/5时,共混物出现了共晶现象。XRD显示PBS的加入在一定程度上影响了PHBV的晶型,复合材料的晶面特征峰发生了明显偏移。     

PHBV共混改性研究进展

介绍了聚(β-羟基丁酸戊酸酯)(PHBV)的现有生产状况、性能特点以及存在的不足。简述了PHBV结晶改性的研究成果,总结了PHBV共混改性的研究进展,包括PHBV与聚乳酸(PLA)、聚己内酯(PCL)、聚己二酸/对苯二甲酸丁二醇酯(PBAT)、二氧化碳共聚物(PPC)、淀粉、纤维素及有机黏土等。     

成核剂对PHBV结晶影响的研究

通过熔融共混的方法,分别将成核剂A、成核剂B、氧化锌(ZnO)、二氧化硅(SiO₂)与聚-3-羟基丁酸/戊酸酯(PHBV)进行共混,研究了它们对PHBV结晶性能的影响。利用差示扫描量热仪研究了复合材料的等温结晶和非等温结晶动力学,利用热台偏光显微镜观察了晶体成核和生长过程。结果表明,这些成核剂均可以改善PHBV结晶不完善的情况,使PHBV的熔融峰从2个变为1个;成核剂A和B可改善PHBV的成核效果,提高PHBV的结晶速率,且球晶尺寸明显细化;加入SiO₂后,形成了同心圆球晶,结晶速率获得改善。     

PHA/PCL复合材料等温结晶行为分析

通过熔融共混制备了聚羟基脂肪酸酯/聚己内酯(PHA/PCL)复合材料,利用差示扫描量热仪(DSC)和偏光显微镜(PLM)研究了PHA/PCL共混体系的等温结晶行为及结晶形貌。结果表明:该共混体系的PHA结晶度均高于纯样,而随着体系中PCL含量的增加,PHA结晶度先增大后减小,且在PHA与PCL的质量比为60:40时达到极大值。PCL的引入可明显提高PHA的结晶能力,但不会对PHA的熔点产生影响。对于PHA/PCL(60/40)共混体系,当等温结晶温度(T_c)为70~130℃时,PHA会出现冷结晶与多重熔融转变,其相对结晶度随着T_c的升高而先增大后减小,且在120℃时达到最大值。     

PCL/PVME共混物的结晶行为

采用溶液共混法制备了聚ε-己内酯(PCL)/ 聚乙烯基甲基醚(PVME)共混物,采用差示扫描量热法（DSC）研究了共混物的相容性,通过广角X射线衍射及偏光显微镜研究了共混物中PVME含量对PCL晶体结构及结晶形态的影响。结果表明,共混物的DSC曲线只出现了一个玻璃化转变温度,说明共混物为相容体系,共混物中PVME 的存在没有改变PCL 的晶体结构。     

增塑剂对PHBV/PBS共混物性能的影响

分别以柠檬酸三乙酯(TEC)、聚乙二醇(PEG)作为聚β-羟基丁酸/戊酸酯(PHBV)和聚丁二酸丁二酯(PBS)共混时的增塑剂,通过熔融加工制得PHBV/PBS共混物。利用熔体流动速率仪、差示扫描量热仪、X射线衍射仪)、万能材料试验仪、扫描电子显微镜等研究PHBV/PBS共混物的熔体流动速率、热性能、晶胞结构、力学性能、相形态等性能。结果表明,随着增塑剂添加量的增加,共混物性能发生显著变化。当PEG和TEC用量均为10份(质量份)时,共混物的熔体流动速率分别增大到纯共混物的约3倍和1.8倍;PEG和TEC均使共混物的拉伸断裂伸长率先增加后降低,其中PEG和TEC的含量分别为2.5份和10份时,共混物有最大断裂伸长率;共混物的结晶(Tc)和熔融温度(Tm),随着两种增塑剂量增加均略有下降。扫描电镜照片表明两种增塑剂对共混物中两相的分散起到促进作用。     

PCL增韧PLA共混材料的制备与性能研究

在聚乳酸(PLA)基体中加入聚己内酯(PCL)、柠檬酸三丁酯(TBC),通过熔融共混制备了PLA/PCL共混材料,并对其相容性、力学性能、热性能等进行了研究。结果表明:PLA/PCL为不相容体系,TBC作为相容剂对体系的韧性和强度影响较大;在TBC的作用下,共混材料两相之间发生了酯交换反应,生成界面相容剂,降低了PCL分散相的尺寸,改善了两相之间的相容性,提高了共混材料的韧性。当PLA与PCL的质量比为80/20、TBC的质量分数占共混材料总质量的8%时,共混材料的断裂伸长率可达125%,冲击强度值可达9.83kJ/m2。同时,共混材料的冷结晶峰消失,结晶趋于完善。     

Miscibility and crystallization behavior of biodegradable blends of two aliphatic polyesters. Poly(3-hydroxybutyrate-co-hydroxyvalerate) and poly(ε-caprolactone)

Biodegradable polymer blends of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(ε-caprolactone) (PCL) blends were prepared with the ratio of PHBV/PCL ranging from 80/20-20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to investigate the miscibility and crystallization of PHBV/PCL blends. Experimental results indicated that PHBV showed no miscibility with PCL for PHBV/PCL blends as evidenced by the existence of unchanged composition independent glass transition temperature and the biphasic melt. Crystallization of PHBV and PCL was studied with DSC and analyzed by the Avrami equation by using two-step crystallization in the PHBV/PCL blends. The crystallization rate of PHBV at 70 °C decreased with the increase of PCL in the blends, while the crystallization mechanism did not change. In the case of the isothermal crystallization of PCL at 42 °C, the crystallization rate increased with the addition of PHBV, and the crystallization mechanism changed, too, indicating that the crystallization of PHBV at 70 °C had an apparent influence on the crystallization of PCL at 42 °C.     

Effects of the energy dissipation rate and surface erosion on the biodegradation of poly(hydroxybutyrate‐co‐hydroxyvalerate) and its blends with synthetic polymers in an aquatic medium

The anaerobic biodegradation of polymers by soil microorganisms was investigated in shaking flask cultures at different rotation speeds or energy dissipation rates. The polymers included poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV), poly(?‐caprolactone) (PCL), polystyrene (PS), two binary PHBV/PCL blends (80/20 and 25/75 w/w), and a triple PHBV/PCL/PS blend (76/5/19 w/w/w). The specific degradation rate of PHBV found from the specimen's residual mass fraction with time was constant after a lag phase and was significantly affected by the agitation strength (<0.5 day^?1 at 60 rpm or lower and >15 day^?1 at 120 rpm or greater). Tiny polymer fragments were formed on the specimen surface and observed with scanning electron microscopy during degradation. The detachment of those fragments under high hydraulic shear stress caused surface erosion and renewal, resulting in the high degradation rate. The hydraulic shear stress (0.6 Pa) at an energy dissipation rate of 0.5 W/kg was a threshold level, above which the external force did not increase the degradation rate very much. PHBV degradation in the binary blends with compatible PCL was retarded, depending on the blend composition. Blending PHBV with noncompatible PS did not affect PHBV degradation, and the overall degradation rate of the triple blend was faster than the rate of PHBV alone because of the surface erosion of both PHBV and nondegradable PS fragments from the specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1036–1045, 2002     

Conductive-filler-filled poly(ϵ-caprolactone)/poly(vinyl butyral) blends. I. Crystallization behavior and morphology

The crystallization behavior and morphology of poly(ϵ-caprolactone) (PCL)/poly(vinyl butyral) (PVB) blends containing carbon black (CB) were studied as functions of PVB and CB content. The presence of CB had no influence on the primary nucleation of PCL crystals or the spherulitic growth rate. They were only influenced by the blend ratio of PVB. The growth rates of spherulites were unchanged throughout the crystallization process, regardless of the CB content. The results indicate that the concentration of PCL at the front of growing spherulite remains constant during crystallization. The distribution of CB in the spherulites was observed using atomic force microscopy to explain these results. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 797–802, 1997     

Advance application of Raman spectroscopy for quantitative analysis of noncrystalline components in thin films of poly(ε-caprolactone)/poly(butadiene) blends

A quantitative analysis method for the distribution of noncrystalline poly(butadiene) component in poly(ε-caprolactone)/poly(butadiene) (PCL/PB) binary blends have been analyzed by advance application of Raman spectroscopy, optical microscopy, and differential scanning calorimetry (DSC) techniques. Thin films of different compositions of PCL/PB binary blends were prepared from solution and isothermally crystallized at a certain temperature. After calibration with real data, quantitative analyses by Raman spectroscopy revealed the amorphous PB are trapped inside the PCL crystals. Polarized optical microscopy and real time atomic force microscopy were used to collect data for the crystal morphology and crystal growth rate. For pure PCL crystals, a morphology of truncated lozenge shape was observed, independent of crystallization temperature and regardless of the blends compositions. For the pure PCL and their blends, almost unique crystal growth rate was found. The miscibility behaviors using DSC were drawn through melting point depression method. The Hoffman-Weeks extrapolations of the blends were found to be linear and identical with those of the neat PCL. The interaction parameter for the blends indicating that the PCL and PB blends have no intermolecular interaction, confirming the blends are immiscible. Despite the immiscibility of the blend, the PCL crystals do not bend during the growth process and do not reduce the growth rate as they do for miscible blend systems.     

Morphology and nonisothermal crystallization of a polyacetal/poly(ε‐caprolactone) reactive blend prepared via a chain‐transfer reaction

A polyacetal (POM)/poly(ε‐caprolactone) (PCL) reactive blend prepared via a chain‐transfer reaction was investigated with respect to its morphology and nonisothermal crystallization, and the results were compared with those of a simple POM/PCL blend. The reactive blend had a microscopically phase‐separated morphology in which the diameter of the PCL microphase was below 100 nm, and it clearly yielded ring‐banded spherulites, whereas between the two blends, there were no significant differences in the diameters and polygonal edges of the spherulites and in the long period of the POM phases. The PCL part of the reactive blend crystallized within the confined microspace with about 10% lower crystallinity than that of the corresponding simple blend. A lower Avrami exponent and crystallization rate parameter of the PCL part were observed in the primary crystallization process of the reactive blend. In contrast, the crystallinity of the POM component and the nonisothermal crystallization kinetic parameters of the POM part showed no noticeable differences between the two blends at any given cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization and melting behavior of partially miscible six‐armed poly(l‐lactic acid)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends

The crystallization kinetics and spherulitic morphology of six‐armed poly(L‐lactic acid) (6a‐PLLA)/poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) crystalline/crystalline partially miscible blends were investigated with differential scanning calorimetry and polarized optical microscopy in this study. Avrami analysis was used to describe the isothermal crystallization process of the neat polymers and their blends. The results suggest that blending had a complex influence on the crystallization rate of the two components during the isothermal crystallization process. Also, the crystallization mechanism of these blends was different from that of the neat polymers. The melting behavior of these blends was also studied after crystallization at various crystallization temperatures. The crystallization of PHBV at 125°C was difficult, so no melting peaks were found. However, it was interesting to find a weak melting peak, which arose from the PHBV component for the 20/80 6a‐PLLA/PHBV blend after crystallization at 125°C, and it is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42548.     

Phase separation and melting behavior in poly(ε‐caprolactone)‐epoxy blends cured by 3,3′‐dimethylmethylene‐di(cyclohexylamine)

The morphology and the melting behavior of poly(ε‐caprolactone)/epoxy blends (PCL/epoxy) have been investigated by SEM and DSC. The mechanism of phase separation varies with the curing temperature and PCL content, which can be deduced from the cured morphology of the blend. Higher temperature leads to lower blend viscosity and a higher curing rate, and the final morphology is determined by the competition of these two factors. The PCL melting behavior of the blend is influenced by the extent of phase separation and crystallization during curing. The dual melting behavior of the PCL blend can be ascribed to the interference of the epoxy, which results in the formation of less perfect PCL crystallites melted at lower temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3107–3114, 2003     

Poly(ϵ-caprolactone)/poly(ethylene oxide) diblock copolymer II. Nonisothermal crystallization and melting behavior

The nonisothermal crystallization behavior and melting process of the poly(ϵ-caprolactone) (PCL)/poly(ethylene oxide) (PEO) diblock copolymer in which the weight fraction of the PCL block is 0.80 has been studied by using differential scanning calorimetry (DSC). Only the PCL block is crystallizable, the PEO block with 0.20 weight fraction cannot crystallize. The kinetics of the PCL/PEO diblock copolymer under nonisothermal crystallization conditions has been analyzed by Ozawa's equation. The experimental data shows no agreement with Ozawa's theoretical predictions in the whole crystallization process, especially in the later stage. A parameter, kinetic crystallinity, is used to characterize the crystallizability of the PCL/PEO diblock copolymer. The amorphous and microphase separating PEO block has a great influence on the crystallization of the PCL block. It bonds chemically with the PCL block, reduces crystallization entropy, and provides nucleating sites for the PCL block crystallization. The existence of the PEO block leads to the occurrence of the two melting peaks of the PCL/PEO diblock copolymer during melting process after nonisothermal crystallization. The comparison of nonisothermal crystallization of the PCL/PEO diblock copolymer, PCL/PEO blend, and PCL and PEO homopolymers has been made. It showed a lower crystallinity of the PCL/PEO diblock copolymer than that of others and a faster crystallization rate of the PCL/PEO diblock copolymer than that of the PCL homopolymer, but a slower crystallization rate than that of the PCL/PEO blend. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1793–1804, 1997     

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)

The crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt‐blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8°C, the melting temperature was depressed by 4°C, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of PHBV formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179°C, respectively. The isothermal crystallization kinetics were also studied. The fold surface free energy of the developing crystals of PHBV isothermally crystallized from the melt decreased; however, a depression in the relative degree of crystallization, a reduction of the linear growth rate of the spherulites, and decreases in the equilibrium melting temperature and crystallization capability of PHBV were detected with the addition of PPC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2514–2521, 2004     

Highly accelerated stereocomplex crystallization by blending star-shaped 4-armed stereo diblock poly(lactide)s with poly(d-lactide) and poly(l-lactide) cores

Star-shaped 4-armed stereo diblock poly(lactide)s with the core/shell types of poly(d-lactide) (PDLA)/poly(l-lactide) (PLLA) and PLLA/PDLA (abbreviated as 4-DL and 4-LD, respectively) and the number-average molecular weights of about 1 × 10⁴ g mol⁻¹ were synthesized and the crystallization behavior of neat 4-DL, 4-LD, and their 50/50 blend (abbreviated as 4-DL/4-LD blend) was investigated. Solely stereocomplex (SC) crystallites as crystalline species were formed in the neat 4-DL, 4-LD, and 4-DL/4-LD blend, irrespective of crystallization temperature (100–160 °C). The overall SC crystallization of 4-DL/4-LD blend was highly accelerated compared with that of neat 4-DL and 4-LD, due to the largely elevated spherulite nuclei number per unit mass in the blend. Such high density of nuclei formation in 4-DL/4-LD blend is attributable to the facile intermolecular interaction and subsequent SC nucleation between the PLLA shell of 4-DL and the PDLA shell of 4-LD. The blending method reported in the present study is applicable for various core/shell types of star-shaped stereo diblock stereocomplexationable polymers to accelerate overall SC crystallization and can counterbalance the lowered crystallization rate caused by the star-shaped architecture. Despite the highly accelerated overall SC crystallization of 4-DL/4-LD blend by blending 4-DL and 4-LD, the spherulite growth rate, induction period for spherulite growth, final crystallinity, crystalline species, growth morphology, and crystallization mechanism were not altered by blending 4-DL and 4-LD.