GMA熔融接枝SBS及其对PA6增容研究

采用活性单体甲基丙烯酸缩水甘油酯(GMA)对(苯乙烯／丁二烯／苯乙烯)嵌段共聚物(SBS)进行熔融接枝,制备了GMA接枝SBS(SBS-g-GMA)。用化学滴定方法测定其接枝率,考察了单体GMA和引发剂过氧化二异丙苯的用量对接枝率的影响;测试了尼龙6(PA6)／SBS-g-GMA共混物的拉伸性能和冲击性能,并用扫描电子显微镜观察了PA6／SBS-g-GMA共混物的形态结构。结果表明,用SBS-g-GMA增韧PA6可获得很好的效果。     

接枝共聚物对聚丙烯/尼龙6共混物结构和性能的影响

采用4种接枝共聚物作为增容剂来提高PP/PA6共混物相容性.研究了不同类型接枝共聚物对PP/PA6共混物加工性能的影响,同时也探讨了接枝共聚物对PP/PA6共混物微观结构变化的影响.结果表明PP/PA6共混物为热力学不相容的海-岛型两相结构,接枝共聚物的加入改善了PP与PA6的相容性,使两相分散均匀,对PP/PA6共混物的性能具有一定的改善作用.     

GMA接枝SEBS及其对PA 6的改性及增容

用双螺杆反应挤出法将甲基丙烯酸缩水甘油酯(GMA)接枝到氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)上(即SEBS-g-GMA)，研究引发剂过氧化二异丙苯用量、活性单体GMA用量对接枝率的影响；通过双螺杆挤出、共混，制备聚酰胺(PA)6／SEBS-g-GMA、PA 6／SEBS-g-GMA／SEBS合金，研究SEBS-g-GMA对合金体系的相容性影响及增韧作用，探讨了合金体系的形态结构和力学性能。     

PA6/PP/SEBS-g-MAH共混物的相容性研究

采用马来酸酐接枝(氢化苯乙烯/丁二烯/苯乙烯)共聚物(SEBS-g-MAH)作为增容剂,研究了增容剂用量对尼龙6/聚丙烯(PA6/PP)共混体系相态结构、力学性能的影响,以及在相同增容剂用量下不同PA6、PP配比对体系相形态的影响。结果表明,SEBS-g-MAH中的酸酐基团能与PA6末端的氨基发生化学反应,在PA6和PP的内表面形成PA6-SEBS接枝共聚物,明显改善了两相的界面相容性,并使共混物的力学性能得到显著提高。共混物冲击断面形貌的分析表明,共混物发生了明显的脆韧转变。     

马来酸酐官能化ASA对PA6的增韧研究

采用乳液聚合法制备了一系列马来酸酐（MAH）官能化的丙烯酸丁酯橡胶（PBA）与苯乙烯（St）及丙烯腈（AN）的接枝共聚物（PBA-g-SAN）核壳结构改性剂（ASA-g-MAH）,用于聚酰胺6(PA6)的增韧。Molau实验证实了PA6/ASA-g-MAH共混体系中存在化学反应,考察了MAH含量对共混体系结构和性能的影响。结果表明,随着MAH含量的增加,PA6/ ASA-g-MAH共混物的冲击强度逐渐增大,当MAH含量为4 %（质量分数,下同）时材料冲击强度达到1008 J/m;与PA6/ASA共混物相比,PA6/ASA-g-MAH共混物具有较高的拉伸强度和断裂伸长率;随着MAH含量的增加,ASA- g-MAH在PA6基体中的分散程度越来越好,当MAH含量达到4 %以上时,无聚集现象发生;ASA-g-MAH中橡胶粒子的空洞化和PA6基体的剪切屈服是主要的增韧机理。     

SEBS-g-MA对PS/PA6共混物的相形态和动态流变行为的影响研究

采用马来酸酐接枝氢化苯乙烯-丁二烯嵌段共聚物（SEBS-g-MA）改性聚苯乙烯（PS）/尼龙6（PA6）共混物。SEM观察共混物相态发现,随着SEBS-g-MA加入量的增加,PS/PA6双连续相结构并未改变,而PS和PA6的相畴尺寸逐渐变小,加入量超过10%以后,相畴尺寸出现变大的趋势。动态流变测试表明,PS/PA6共混物熔体的复数粘度、储能模量及损耗模量均随SEBS-g-MA的加入而增加,即SEBS-g-MA同时提高了体系的粘性和弹性,但是体系的粘弹比却出现下降,且随加入量的增多,作用程度更为显著。     

相容剂对PA6/POE力学性能和微观结构影响

转矩流变仪中熔融法制备了苯乙烯(St)和甲基丙烯酸缩水甘油酯(GMA)或甲基丙烯酸羟乙酯(HEMA)分别接枝乙烯-辛烯共聚物(POE),并将接枝物用于聚酰胺6(PA6)增韧改性.结果表明:2种接枝物POE-g-(GMA-co-St)和POE-g-(HEMA-co-St)的最佳反应加工时间分别为8.0 min和10.0 min,二者均能明显改善PA6与POE之间的相容性,但是前者增韧效果更好,其改性共混物力学性能更优.     

SAN—g—GMA的制备及其在PA6／ABS中的应用

采用固相接枝制备苯乙烯/丙烯腈共聚物接枝甲基丙烯酸缩水甘油酯(SAN-g-GMA),研究了过氧化苯甲酰(BPO)和GMA用量对接枝吸光比的影响,以自制的SAN-g-GMA增容尼龙6/丙烯腈-丁二烯-苯乙烯(PA6/ABS)共混物,探讨了SAN-g-GMA对共混物结构与性能的影响.结果表明:SAN-g-GMA能够增容PA6/ABS共混物,改善共混物的力学性能;Molau实验发现,SAN-g-GMA能够促进PA6/ABS两相界面结合,起到相容作用;共混物的SEM照片表明,SAN-g-GMA使ABS在PA6中分散均匀,粒子尺寸减小.     

界面改性PA6/TPE共混物的形态结构与性能

通过控制马来酸酐(MAH)的用量制得不同接枝率的马来酸酐接枝热塑性弹性体(TPE-g-MAH),利用其与尼龙6(PA6)在共混过程中的反应增容作用,实现了与PA6的相容共混,并研究了PA6/TPE共混物的结构与性能。结果表明,TPE-g-MAH可有效地提高PA6/TPE共混物的韧性,且随着其接枝率的增加,共混物的韧性提高;TPE-g-MAH有效地改善了PA6/TPE共混物的界面相容性,并且随着其含量的增加,相界面增容效果变好。     

接枝率对PVC/PA6-g-SMA共混物结构与性能的影响

采用熔融共混方法制备了聚氯乙烯（PVC）与不同接枝率苯乙烯-马来酸酐共聚物(SMA）接枝改性聚酰胺6（PA6-g-SMA）的共混物,研究了PA6-g-SMA接枝率对PVC/PA6-g-SMA共混物力学性能及凝聚态结构的影响。结果表明,接枝率越高,PA6-g-SMA与PVC的相容性越好,在PVC基体中能以更小的相畴均匀分散,对PVC的增韧增强作用越明显;当PA6-g-SMA的接枝率为5.12 %,添加量为15 ％（质量分数,下同）时,共混物的冲击强度为64.7 kJ/m2,拉伸强度为55 MPa。     

Effect of different types of organoclays and compatibilizers on the properties of polystyrene‐based nanocomposites

Polystyrene/organoclay nanocomposites were prepared by melt intercalation in the presence of elastomeric impact modifiers. Three different types of organically modified montmorillonites; Cloisite® 30B, 15A, and 25A, were used as reinforcement, whereas poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS‐g‐MA) and poly(ethylene‐b‐butyl acrylate‐b‐glycidyl methacrylate) (E‐BA‐GMA) elastomeric materials were introduced to act as impact modifier. Owing to its single aliphatic tail on its modifier and absence of hydroxyl groups, Cloisite® 25A displayed the best dispersion in the polystyrene matrix, and mostly delaminated silicate layers were obtained in the presence of SEBS‐g‐MA. This was attributed to the higher viscosity of SEBS‐g‐MA compared with both E‐BA‐GMA and poly(styrene‐co‐vinyloxazolin) (PS). In addition, the compatibility between SEBS‐g‐MA and PS was found to be better in comparison to the compatibility between E‐BA‐GMA and PS owing to the soluble part of SEBS‐g‐MA in PS. The clay particles were observed to be located mostly in the dispersed phase leading to larger elastomeric domains compared with binary PS/elastomer blends. The enlargement of the elastomeric domains resulted in higher impact strength values in the presence of organoclay. Good dispersion of Cloisite® 25A in PS/SEBS‐g‐MA blends enhanced the tensile properties of this nanocomposite produced. It was observed that the change in the strength and stiffness of the ternary nanocomposites mostly depend on the type of the elastomeric material. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and application of MDPE‐g‐GMA as reactive compatibilizer in blends of MDPE/PET and MDPE/PA6

In the present study, glycidyl methacrylate (GMA) grafted medium density polyethylene (MDPE‐g‐GMA) was synthesized in the molten state and applied as a reactive compatibilizer in MDPE/polyamid6 (PA6) and in MDPE/poly(ethylene terephtalate) (PET) blends. Graft copolymerization of GMA onto MDPE was performed in presence and absence of styrene, with different concentrations of dicumyl peroxide (DCP) as a radical initiator. In the presence of styrene, the MDPE‐g‐GMA with 6% GMA was obtained by addition of only 0.1 phr of DCP. Furthermore, the maximum grafting was reached when 0.6 and 0.7 phr concentration of DCP for styrene containing and styrene free samples were used, respectively. Torque‐time measurement showed faster grafting reaction rate in the presence of styrene. Four MDPE‐g‐GMA samples were selected as compatibilizers in the blends. Furthermore, the effects of melt flow index and grafting content of compatibilizers on mechanical properties and morphology of the blends were investigated through tensile tests and SEM analysis. Tensile test results indicated that the presence of compatibilizers in the blends led to 250 and 133% increase in elongation at break for PA6 and PET blends, respectively. Moreover, the best tensile results for blends were obtained using MDPE‐g‐GMA with high flow ability. The average particle size of the dispersed phase decreased by 350% for PA6 and 300% for PET blends compared with nonreactive blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of the molecular structure of impact modifier and compatibilizer on the toughening of PBT/SBS/PS‐GMA blends

This work aims at studying the toughening process of poly(butylene terephthalate) (PBT) through its blends with styrene‐butadiene‐styrene block copolymers (SBS), in the presence of poly(styrene‐ran‐glicydil methacrylate) (PS‐GMA) as reactive compatibilizer. High values of impact strength were attained for PBT/SBS blends without the compatibilizer; however, this improvement is achieved for blends with SBS having similar viscosity compared to PBT, at high SBS content (40 wt %) and for blends prepared under specific processing conditions. The efficiency of the in situ compatibilization of PBT/SBS blends by PS‐GMA was found to be strongly dependent on the SBS and PS‐GMA molecular characteristics. Better compatibilizing results were observed through fine phase morphologies and lower ductile to brittle transition temperatures (DBTT) as the interfacial interaction and stability of the in situ formed compatibilizer are maximized, that is, when the miscibility between SBS and PS‐GMA and reaction degree between PBT and PS‐GMA are maximized. For the PBT/SBS/PS‐GMA blends under study, this was found when it is used the SBS with higher polystyrene content (38 wt %) and with longer PS blocks (M_w = 20,000 g mol^?1) and also the PS‐GMA with moderate GMA contents (4 wt %) and with molecular weight similar to the critical one for PS entanglements (M_c = 35,000 g mol^?1). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5795–5807, 2006     

Investigation on particular morphology of immiscible polyamide 12/polystyrene blends

In this article, a particular phase morphology of immiscible polyamide 12/polystyrene (PA12/PS) blends prepared via in situ anionic ring-opening polymerization of Laurolactam (LL) in the presence of PS was investigated. SEM and FTIR were used to analyze the morphology of the blends. The results showed that PS is dispersed as small droplets in the continuous matrix of PA12 when PS content is less than 5 wt %. When the PS content is higher than 10 wt %, two particular phase morphologies appeared. First, dispersed PS-rich particles with the spherical inclusions of PA12 can be found when PS content is between 10 wt % and 15 wt %. Then, the phase inversion (the phase morphology of the PA12/PS blends changes from the PS dispersed/PA12 matrix to PA12 dispersed/PS matrix system) occurred when PS content is higher than 20 wt %, which is completely different from traditional polymer blends prepared by melt blending. The possible reason for the particular morphology development was illuminated through phase inversion mechanism. Furthermore, the stability of the phase morphologies of the PA12/PS blends was also investigated. SEM showed that the particular morphology is instability, and it will be changed upon annealing at 230°C for 30 min. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PS/PA6/CB共混体系导电性能研究

在哈克流变仪中将炭黑(CB)与聚苯乙烯(PS)、尼龙6(PA6)共混,研究了CB在PS/PA6/CB共混体系中的分散情况及CB含量和PS与PA6的质量比对PS/PA6/CB共混体系导电性能、微观形态的影响。结果表明,CB在PS/PA6/CB共混体系中只分散在PA6中;PS/PA6/CB共混体系的导电性能随着CB含量的增加而增强,CB的体积分数在20%~40%时,PS/PA6/CB共混体系的电导率增幅明显;PS、PA6两相的微观尺寸随CB含量增加而变小;PS/PA6/CB共混体系中PS与PA6质量比约为80/20时,PS/PA6/CB共混体系的导电性能最好。     

Effect of in situ synthesized macroactivator on morphology of PA6/PS blends via successive polymerization

In situ polymerization and in situ compatibilization was adopted for preparation of ternary PA6/PS‐g‐PA6/PS blends by means of successive polymerization of styrene, with TMI and ε‐caprolactam, via free radical copolymerization and anionic ring‐opening polymerization, respectively. Copolymer poly(St‐g‐TMI), the chain of which bears isocyanate (? NCO), acts as a macroactivator to initiate PA6 chain growth from the PS chain and graft copolymer of PS‐g‐PA6 and pure PA6 form, simultaneously. The effect of the macroactivator poly(St‐g‐TMI) on the phase morphology was investigated in detail, using scanning electron microscopy. In case of blends with higher content of PS‐g‐PA6 copolymer, copolymer nanoparticles coexisting with the PS formed the matrix, in which PA6 microspheres were dispersed evenly as minor phase. The content of the compositions (homopolystyrene, homopolyamide 6, and PS‐g‐PA6) of the blends were determined by selective solvent extraction technique. The mechanical properties of PA6/PS‐g‐PA6/PS blends were better than that of PA6/PS blends. Especially for the blends T10 with lower PS‐g‐PA6 copolymer content, both the flexural strength and flexural modulus showed significantly improving because of the improved interfacial adhesion between PS and PA6. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

聚丙烯的官能化及其与尼龙66相容性研究

对聚丙烯（PP）进行官能化，并研究了接枝单体含量，引发剂含量，螺杆转速对接枝率和熔体流动速率的影响。再将不同接枝率的PP与尼龙66共混，研究了接枝率对共混物力学性能及相容性的影响；用扫描电子显微镜观察了共混物的形态，与未增容共混体系相比，增容后共混体系分散相尺寸明显减小，增容共混物的形态依赖于增容剂在共混物中的含量，增容剂的分子量及官能化基团的含量。     

Influence of morphology and ammonium polyphosphate dispersion on the flame retardancy of polystyrene/nylon‐6 blends

The influences of the distribution of ammonium polyphosphate (APP) in polystyrene/nylon‐6 [PS/polyamide‐6 (PA6)] blends and the continuity of the (PA6 + APP) phase on flame retardancy were investigated. The flame retardant properties were evaluated by limiting oxygen index (LOI), vertical flammability test and cone calorimeter tests. The results showed that APP is exclusively dispersed in the PA6 phase, and (PA6 + APP) phase formed a continuous state when the content of PA6 in PS/PA6 blends was higher than 32% (w/w). For blends with a continuous (PA6 + APP) phase, the decrease of PA6 content caused an increase in LOI values from 26% to 33% and a reduction of peak heat release rate. The improvement of flame retardancy was attributed to the increase of APP concentration in the PA6 phase, which benefited the fast formation of a continuous intumescent charred layer. The transformation of (PA6 + APP) phase morphology from a continuous state to a discontinuous state at a PA6 content of below 32% (w/w) caused a decrease in LOI. Results of thermo‐gravimetric and cone calorimeter tests indicated that the discontinuous intumescent charred layer thus formed could be responsible for the deterioration of flame retardant properties, which was also confirmed by scanning electron microscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

Co-continuous and encapsulated three phase morphologies in uncompatibilized and reactively compatibilized polyamide 6/polypropylene/polystyrene ternary blends using two reactive precursors

Phase morphology development in ternary uncompatibilized and reactively compatibilized blends based on polyamide 6 (PA6), polypropylene (PP) and polystyrene (PS) has been investigated. Reactive compatibilization of the blends has been performed using two reactive precursors; maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride copolymer (SMA) for PA6/PP and PA6/PS pairs, respectively. For comparison purposes, uncompatibilized and reactively compatibilized PA6/PP and PA6/PS binary blends, were first investigated. All the blends were melt-blended using a co-rotating twin-screw extruder. The phase morphology investigated using scanning electron microscope (SEM) and selective solvent extraction tests revealed that PA6/PP/PS blends having a weight percent composition of 70/15/15 is constituted from polyamide 6 matrix in which are dispersed composite droplets of PP core encapsulated by PS phase. Whereas, a co-continuous three-phase morphology was formed in the blends having a composition of 40/30/30. This morphology has been significantly affected by the reactive compatibilization. In the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends, PA6 phase was no more continuous but gets finely dispersed in the PS continuous phase. The DSC measurements confirmed the dispersed character of the PA6 phase. Indeed, in the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends where the PA6 particle size was smaller than 1 μm, the bulk crystallization temperature of PA6 (188 °C) was completely suppressed and a new crystallization peak emerges at a lower temperature of 93 °C as a result of homogeneous nucleation of PA6.     

Morphology and properties of PBT/nylon 6/EVA‐g‐MAH ternary blends prepared by reactive extrusion

Morphology and properties of poly(butylene terephthalate) (PBT)/nylon 6 (PA6)/EVA‐g‐MAH ternary blends were investigated. The blends were prepared in a corotating, intermeshing, twin‐screw extruder. The incorporation of maleic anhyride (MAH) grafted onto ethylene‐vinyl acetate copolymer (EVA) (EVA‐g‐MAH) in the PBT/PA6 binary blends decreased the tensile and flexural strength but increased the impact strength, while the mechanical properties of the PBT/PA6 blends were decreased with increasing PA6 content regardless of the presence or absence of the EVA‐g‐MAH. The morphology studies of the ternary blends showed gross phase separation. The rheological properties of the ternary blends suggested that excessively high reactivity between amine end groups of PA6 and MAH grafted onto EVA makes the compatibility between PBT and PA6 worse, although EVA‐g‐MAH was expected to work as a compatibilizer for PBT/PA6 blends. The degree of reactivity between functional groups in PBT, PA6, and EVA‐g‐MAH was also examined by investigating the effect of blending sequence on the properties of the ternary blends.