几种典型固体聚合物体系的~（13）C自旋－晶格弛豫特性

用固体高分辨ＮＭＲ系统地研究了几种典型的均聚物，共聚物，聚合物共混物以及用接枝共聚物增容的不相容聚合物共混体系的１３Ｃ自旋－晶格弛豫特性。研究结果表明：１３Ｃ自旋－晶格弛豫时间（Ｔ１（Ｃ））是表征固体聚合物体系的很有用参数，它能提供有关本体聚合物微观形态结构的信息，并可望建立聚合物的微观结构与宏观性能的关系，它不仅能准确无误地反映共混体系中可能存在的各种相互作用，而且能定性地给出相互作用的大小和准确地指明相互作用产生的位置，因而为揭示共混体系的相容机理提供了最直接的证据，另外Ｔ１（Ｃ）还能给出增容剂对不相容共混体系的增容作用和增容机制的直接实验证据     

聚乳酸/聚苯乙烯共混物的热氧稳定性研究

通过溶液浇铸法制备了聚乳酸/聚苯乙烯共混物,以差热-热重分析研究了共混物的热氧稳定性,结果表明聚乳酸中引入聚苯乙烯,可以增强聚乳酸/聚苯乙烯共混物的热氧稳定性.采用红外光谱分析了共混物不同结构的分子链间相互作用,证实聚乳酸大分子链羰基的未共用电子对和聚苯乙烯大分子链侧基苯环的π电子形成了n-π键.     

动态流变学对PVDF/PTW共混物流体相容性研究

采用熔融共混法制备了聚偏氟乙烯/乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PVDF/PTW)共混物,利用流变仪考察了PVDF/PTW共混物的相互作用及两者的相容性.观察共混物在200℃下的流变曲线,发现在低频区,共混物中PTW含量越大,共混物的流变曲线越偏离经典流变理论,这个结果与cole-cole图相一致.通过时温叠加原理(时温等效主曲线、Han曲线和v GP曲线)系统研究了不同组成的PVDF/PTW共混体系在均相区和相分离区的黏弹行为.结果表明,在均相区,不同温度下,共混体系的动态模量利用时温叠加原理,通过水平位移就可以很好地叠加在一起,无论是储能模量还是损耗模量,在低频末端均近似地符合经典低频末端标度关系;在相分离区,动态模量偏离了经典的低频末端标度关系,其中储能模量的偏离尤为明显,从而导致了时温叠加原理的"失效",相应的Han图、v GP图也表现出不同于均相体系的特征,这些特征的响应可以用来表征共混体系的相容性,表明在研究的一系列配比(PVDF/PTW 100/0、90/10、70/30、50/50、30/70、10/90、0/100,W/W)中,当PVDF/PTW=90/10(W/W)时,两者的相容性较好.SEM也证实了这个结论.     

EAA增容LLDPE/PEO共混物及其增容机理

以乙烯-丙烯酸共聚物(EAA)为增容剂, 研究了它在线性低密度聚乙烯(LLDPE)/聚环氧乙烷(PEO)共混物中的增容作用及其增容机理。采用电子显微镜(SEM)、动态力学分析(DMA)、DSC和红外光谱(IR)对共混物形态及其微观结构进行了表征。结果表明, EAA对LLDPE/PEO共混物有一定的增容作用; 其增容机理为: EAA和LLDPE两者的非晶区部分相容, 而EAA分子中的羧基与PEO分子中的醚氧基相互作用形成了分子间氢键。     

PTW对PA1010/PP共混物的增容作用

为了增加聚酰胺1010/聚丙烯(PA1010/PP)共混物的相容性,提高共混物的力学性能,采用一种新型的反应型增容剂乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PTW)进行增容,通过扫描电镜(SEM)、力学性能、傅里叶变换红外光谱(FTIR)和差示扫描量热(DSC)测试,研究了PTW对PA1010/PP共混物的增容作用.结果表明,随着PTW的加入,共混物的相区尺寸明显变小,当PA1010/PP/PTW质量比为70∶30∶7时,分散相尺寸细小而均匀,表明PTW有较好的增容作用.FTIR结果表明,PTW上的环氧基团和PA1010在熔融共混中发生了化学反应.DSC研究结果表明,PA1010的结晶温度随PTW的加入而降低,说明PTW对PA1010结晶有抑制作用.另外,PTW的加入使PP的结晶温度下降,当PTW质量分数为5%时出现2个结晶峰,即出现异相成核结晶和均相成核结晶,PP均相成核结晶的出现从另一个方面说明,在PA1010基体中分散相PP尺寸非常细小.当PTW质量分数为7%时共混物的力学性能最佳,干态冲击强度达到13.93kJ/m2,是未加增容剂时的2倍,拉伸和弯曲性能基本不变.PTW的增容机理在于其分子链中的甲基丙烯酸缩水甘油酯能与PA1010发生化学反应,而乙烯链段与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

POE-g-PMAH反应性增容PA1010/PP共混物的性能研究

乙烯-辛烯共聚物-g-聚马来酸酐(POE-g-PMAH)作为反应性增容剂,采用熔体共混的方法制备了PA1010/PP共混物,通过扫描电镜(SEM)、力学性能、傅立叶变换红外光谱(FTIR)和示差扫描量热(DSC)测试,研究了POE-g-PMAH对PA1010/PP共混物的增容作用.结果表明,POE-g-PMAH的加入可以减小共混物的相区尺寸,当PA1010/PP/POE-g-PMAH=70/30/15时,分散相尺寸小而均匀;FTIR结果表明接枝在POE上的马来酸酐基团和PA1010在熔融共混期间发生了化学反应;DSC研究结果表明共混体系中PA1010和PP的结晶温度和结晶度随POE-g-PMAH的加入而降低,表明POE-g-PMAH的增容作用对PA1010和PP的结晶有抑制作用.力学性能测试结果表明随着POE-g-PMAH的增加,共混物的冲击强度逐渐增加,当POE-g-PMAH含量增加到15%时,干态冲击强度达到21.13 kJ/m2,是不加增容剂的3.1倍,而拉伸和弯曲强度可以保持较高水平.POE-g-PMAH的增容机理在于其支链中的马来酸酐能与PA1010中的胺基(NH2—)发生化学反应,而主链POE与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

γ-射线辐照法制备HDPE/PA6阻隔性材料及其性能研究

研究了富氧气氛中高密度聚乙烯(HDPE)的γ-射线辐照氧化及其与尼龙-6(PA6)的共混增容和共混材料的阻隔性能.FT-IR测试结果表明, 经γ-射线辐照的HDPE与PA6发生了化学反应或产生了弱相互作用.SEM照片显示4γHDPE (4h辐照,66Gy/min)与PA6具有良好的相容性,PA6在共混体系中呈层状分布.共混材料的阻隔性能测试结果表明4γHDPE/PA6共混物对二甲苯的阻隔性较HDPE/PA6共混物有明显提高.力学性能测试显示4γHDPE/PA6共混物力学性能优良.     

EAA增容LLDPE／SAN共混物的形态及力学性能

采用SEM及力学性能测试等方法，研究了乙烯－丙烯酸共聚物（EAA）含量对其增容线性低密度聚乙烯（LLDPE）／苯乙烯－丙烯腈共聚物（SAN）共混物形态及性能的影响．发现少量的EAA可使共混物中SAN相的相尺寸减小，共混物模量、拉伸强度及断裂伸长率提高．当EAA的含量增加至11．7％时，它在共混物中两相界而的分布达到饱和，即增容剂饱和浓度Cs=11．7％；此时，共混物形态及性能的变化趋势出现明显转折．明显过量的EAA主要起增韧作用．EAA的增容机理为，它与LLDPE组分的非晶区可部分相容，同时又与SAN相存在着分子间特殊作用.     

酸酐化聚砜对聚砜/液晶聚合物共混物的界面增容作用

首先合成了马来酸酐接枝改性聚砜.改性后聚砜材料的表面张力增大,其中的极性分量增加明显,并以此增容聚砜/液晶聚合物(VectraB950)为原位复合体系,研究了增容前后共混物的加工流变行为和界面性能.结果表明,酸酐化聚砜可增强聚砜与液晶聚合物之间的界面作用,引起共混物加工粘度的上升;漫反射FTIR研究表明,增容后共混体系中的特殊相互作用增大;XPS和PLM的研究表明,在熔融加工过程中改性聚砜与液晶聚合物组分之间存在一定的界面化学反应,并生成了接枝共聚物.共混物相容性的提高应归结于相间化学反应与物理作用共同作用的结果.     

氧化石墨烯增容尼龙6/聚苯乙烯共混体系的研究

氧化石墨烯(GO)亲水性的边缘和疏水性的中间片层使其具有两亲特性.利用GO的这种特性,将其加入尼龙6(PA6)/聚苯乙烯(PS)的共混体系,以提高PA6和PS的相容性.通过两步法制备了PA6/PS/GO共混物,研究了GO对PA6/PS共混材料结构形态与力学性能的影响,并对其增容机理进行了探讨.扫描电镜(SEM)结果表明,添加GO后,共混材料的分散相尺寸明显变小,分散更为均匀,少量的GO即可达到良好的增容效果.动态力学性能(DMA)测试进一步证明了GO对PA6/PS共混物具有一定的增容性.理论计算也表明PS/GO共混物和PA6具有更接近的表面自由能和较低的界面自由能.添加GO后共混物材料的拉伸性能和韧性明显提高.GO添加量为0.1 wt％时,共混材料的断裂伸长率较未添加GO的共混材料提高了170％,断裂能也提高了近240％.     

Phase separation behavior of epoxy resin modified with crosslinked rubber

Low molecular weight liquid rubber (ATBN = amine terminated butadiene acrylonitrile copolymer or CTBN = carboxyl terminated butadiene acrylonitrile copolymer)–DGEBA (diglycidyl ether of bisphenol A) blends indicated upper critical solution temperature (UCST) behavior. The phase separation behavior of the neat and crosslinked rubber (ATBN, CTBN)–epoxy blends was analyzed by a laser light scattering experiment. Lauryl peroxide (LPO) was employed to crosslink the rubber during the initial annealing stage. The onset point of the phase separation in the crosslinked ATBN–epoxy system occurred later than in the case of the neat ATBN–epoxy system. However, the onset point of the phase separation process started earlier in the case of the crosslinked CTBN–epoxy system. The domain correlation length of the crosslinked rubber-added system was smaller than that of the neat rubber-added system.     

Effect of P(MMA-co-MAA) compatibilizer on the miscibility of nylon 6/PVDF blends

With the ultimate objective of enhancing the impact strength and weatherability of nylon 6 engineering plastic, blending with poly(vinylidene fluoride) (PVDF) was studied. In the absence of a compatibilizer the two polymers phase separate, resulting in a deterioration of the properties. Since poly(methyl methacrylate) is known to be miscible with PVDF, we evaluated poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) of low methacrylic acid content as the compatibilizer. The carboxylic acid groups in the MAA units were expected to react with the end amino groups of nylon 6 forming block or graft copolymers, P(MMA-co-MAA)-g-nylon 6, in situ, which will function as the actual compatibilizer. The amount of P(MMA-co-MAA) added, the MMA/MAA composition and heat treatment time were varied to study their effects on the miscibility, morphology, and mechanical properties of nylon 6/PVDF blends. The enhancement of the compatibility of nylon 6 and PVDF by addition of P(MMA-co-MAA) and the partial miscibility of nylon 6 and PVDF has been confirmed through DSC, dynamic mechanical testing, SEM of fracture surfaces, and tensile testing. The decrease in the crystallization temperatures on addition of compatibilizer in DSC experiments suggests that the compatibilizer enhances the interaction between the two components and retards the crystallization. The dynamic mechanical thermal analysis experiments suggest that the compatibility in the amorphous regions of nylon 6 and PVDF in particular has been enhanced. The increase in the heat treatment time in the molten state resulted in further enhancement of the miscibility. The enhancement of compatibility by addition of a reactive compatibilizer and heat treatment resulted in a significant increase in the energy of rupture in tensile testing.     

Thermal properties of compatibilized and filled natural rubber/acrylonitrile butadiene rubber blends

The thermal behaviour of natural rubber/acrylonitrile butadiene rubber (NR/NBR) was studied using thermogravimetry (TG) and differential scanning calorimetry (DSC) in terms of blend ratio, crosslinking systems, fillers and compatibilizer (neoprene) were analyzed. The presence of NBR markedly increases the thermal stability of their blends and it lies in between NR and NBR. DSC studies revealed the thermodynamic immiscibility of the NR/NBR blends by the presence of two distinct glass transition temperatures and the immiscibility was prominent even in the presence of a compatibilizer.     

Enhancing toughness of poly (lactic acid)/Thermoplastic polyurethane blends via increasing interface compatibility by polyurethane elastomer prepolymer and its toughening mechanism

Due to the environmental pollution caused by the petroleum-based polymer, poly (lactic acid) (PLA), a biodegradable and biocompatible polymer that obtained from natural and renewable sources, has attracted widespread attention. However, the brittleness of PLA greatly limits its application. In this study, the super toughened PLA-based blends were obtained by compatibilizing the PLA/thermoplastic polyurethane (TPU) blends with the polyurethane elastomer prepolymer (PUEP) as an active compatibilizer. The mechanical properties, thermal properties and corresponding toughening mechanism of PLA/TPU/PUEP system were studied by tensile test, instrumented impact test, dynamic mechanical analysis (DMA), scanning electronic microscope (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All the results demonstrate that the isocyanate (−NCO) group in PUEP is successfully reacted with the –OH groups at both sides of the PLA and the obtained polyurethane (PU)~PLA copolymer (PU ~ cõ PLA) significantly improves the interfacial compatibility of PLA/TPU blends. The gradually refined dispersed phase size and fuzzy phase interface as displayed in SEM images suggest a good interfacial compatibilization in the PLA/TPU/PUEP blends, probably due to the isocyanate reaction between PLA and PUEP. And the interfacial reaction and compatibilization among the components led to the formation of super toughened PLA/TPU/PUEP blends. And the instrumented impact results indicate that most of the impact toughness is provided by the crack propagation rather than the crack initiation during the entire fracture process.     

Effect of maleic anhydride and liquid natural rubber as compatibilizers on the mechanical properties and impact resistance of the NR‐NBR blend

The degree of compatibilization between natural rubber (NR) and acrylonitrile‐butadiene rubber (NBR) was investigated by two different methods. NBR was chemically modified with maleic anhydride in a screw twin mixer with and without reaction initiator, benzoyl peroxide. Also, the effects of molecular weight of liquid natural rubber (LNR) as a compatibilizer were studied. The degree of compatibilization between NBR and NR is determined indirectly through measurements of mechanical properties and impact resistance. The maleic anhydride and benzoyl peroxide concentrations influence the mechanical properties and impact resistance of the blends. Also, the mechanical properties of the blends showed that the molecular weight of LNR played an important role in determing their performance. Copyright © 2004 John Wiley & Sons, Ltd.     

Modification of epoxy resin using reactive liquid (ATBN) rubber

Epoxy resins are widely utilised as high performance thermosetting resins for many industrial applications but unfortunately some are characterised by a relatively low toughness. In this respect, many efforts have been made to improve the toughness of cured epoxy resins by the introduction of rigid particles, reactive rubbers, interpenetrating polymer networks and engineering thermoplastics within the matrix.In the present work liquid amine-terminated butadiene acrylonitrile (ATBN) copolymers containing 16% acrylonitrile is added at different contents to improve the toughness of diglycidyl ether of bisphenol A epoxy resin using polyaminoimidazoline as a curing agent. The chemical reactions suspected to take place during the modification of the epoxy resin were monitored and evidenced using a Fourier transform infrared. The glass transition temperature (T_g) was measured using a differential scanning calorimeter. The mechanical behaviour of the modified epoxy resin was evaluated in terms of Izod impact strength (IS), critical stress intensity factor, and tensile properties at different modifier contents. A scanning electron microscope (SEM) was used to elucidate the mechanisms of deformation and toughening in addition to other morphological features. Finally, the adhesive properties of the modified epoxy resin were measured in terms of tensile shear strength (TSS).When modifying epoxy resin with liquid rubber (ATBN), all reactivity characteristics (gel time and temperature, cure time and exotherm peak) decreased. The infrared analysis evidenced the occurrence of a chemical reaction between the two components. Addition of ATBN led to a decrease in either the glass transition temperature and stress at break accompanied with an increase in elongation at break and the appearance of some yielding. As expected, the tensile modulus decreased slightly from 1.85 to about 1.34 GPa with increasing ATBN content; whereas a 3-fold increase in Izod IS was obtained by just adding 12.5 phr ATBN compared to the unfilled resin. It is obvious that upon addition of ATBN, the Izod IS increased drastically from 0.85 to 2.86 kJ/m² and from 4.19 to 14.26 kJ/m² for notched and unnotched specimens respectively while K_IC varies from 0.91 to 1.49 MPa m^1/2 (1.5-fold increase). Concerning the adhesive properties, the TSS increased from 9.14 to 15.96 MPa just by adding 5 phr ATBN. Finally SEM analysis results suggest rubber particles cavitation and localised plastic shear yielding induced by the presence of the dispersed rubber particles within the epoxy matrix as the prevailing toughening mechanism.     

Improvement in toughness of poly(l-lactide) (PLLA) through reactive blending with acrylonitrile-butadiene-styrene copolymer (ABS): Morphology and properties

Poly(l-lactide) (PLLA) was melt-blended with acrylonitrile-butadiene-styrene copolymer (ABS) with the aim of enhancing impact strength and elongation at break of PLLA, but not sacrificing its modulus and stiffness significantly. However, PLLA and ABS were found to be thermodynamically immiscible by simply melt blending and the formed blends show deteriorated mechanical properties. The reactive styrene/acrylonitrile/glycidyl methacrylate copolymer (SAN-GMA) by incorporating with ethyltriphenyl phosphonium bromide (ETPB) as the catalyst was used as the in situ compatibilizer for PLLA/ABS blends to improve the compatibility between PLLA and ABS. The reactive process during melt blending was investigated by Fourier transformed infra-red (FTIR). It showed that the epoxide group of SAN-GMA reacted with PLLA end groups under the mixing conditions and that the addition of ETPB accelerated the reaction. Phase structure and physical properties of the compatibilized blends were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), tensile tests and impact property measurements. It was found that the size of ABS domains in PLLA matrix is significantly decreased by addition of the reactive compatibilizer. The dynamic mechanical analysis revealed markedly shifted glass transition temperatures for both PLLA and ABS, indicating the improved compatibility between PLLA and ABS. The mechanical tests showed the compatibilized PLLA/ABS blends had a very nice stiffness-toughness balance, i.e., the improved impact strength and the elongation at break with a slightly loss in the modulus.     

固相法氯化聚乙烯对PVC／LLDPE共混体系性能和形态的影响

采用固相法氯化聚乙烯（ＣＰＥ）对聚氯乙烯／线型低密度聚乙烯（ＰＶＣ／ＬＬＤＰＥ）共混体系进行增容改性。扫描电子显微镜、透射电子显微镜、动态力学分析和力学性能测试结果表明，ＣＰＥ对ＰＶＣ／ＬＬＤＰＥ共混体系具有很好的增容作用。     

Reactive blending of polypropylene/polyamide-6 in the presence of tailor-made succinic anhydride-terminated oligopropene compatibilizers

Various anhydride-terminated isotactic and atactic oligopropenes of number average molecular weights ranging between 1,000 and 10,000 g/mole, prepared by maleinating vinylidene-terminated propene oligomers obtained with isospecific and nonstereospecific metallocene-based Ziegler–Natta catalysts, have been evaluated as blend compatibilizers of polypropylene/polyamide-6 (70 vol%/30 vol%) blends to study the role of blend compatibilizer molecular architecture. When added during processing, as shown by IR spectroscopic analysis, the anhydride-terminated oligopropenes react with the amine-terminated polyamide-6 to yield polypropylene-block-polyamide-6 in situ. Such block copolymers are efficient dispersing agents. While the polyamide dispersion in the polypropylene continuous phase is not affected by blend compatibilizer stereoregularities, both stiffness and yield stress as well as notched Charpy impact strength increase with increasing stereoregularities and molecular weights. With oligopropene molecular weights exceeding 1,150 g/mole, the average size of the dispersed polyamide microphases correlates with the volume fraction of the oligopropene-block-polyamide-6 blend compatibilizer and the dicarboxylic acid anhydride/amine molar ratio.     

聚醚砜与含萘环的聚芳醚酮增容共混物的研究

以双酚S型含萘环的聚芳醚酮为增容剂,研究了对聚醚砜(PES)与对苯二酚型-1,4-萘环的聚芳醚酮(1,4-NA-PAEK)共混体系的相容性及力学性能.结果表明,双酚S型含萘环的聚芳醚酮可显著降低PES/NA-PAEK共混体系中NA-PAEK分散相尺寸,改善两组分间的相容性,并且增容剂的加入使共混体系形成了双连续的互锁结构,提高了共混物的力学性能.