PVC/MBS/埃洛石纳米管复合材料的制备及其性能

采用熔融共混法制备了聚氯乙烯(PVC)/甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)/埃洛石纳米管(HNTs)三元复合材料,研究了HNTs对PVC/MBS共混体系力学性能、热性能和微观结构的影响。结果表明:HNTs与MBS可协同增韧PVC,使复合材料的强度和刚性得到改善,当HNTs的填充量为3 phr时,PVC/MBS(100/3)共混体系的冲击强度、拉伸强度、弯曲强度和弯曲模量分别提高了57.7%、12.1%、7.6%和45.9%;其冲击断面呈现韧性断裂特征;TEM观察结果发现,HNTs在PVC/MBS共混体系中具有良好的分散状态;热失重分析显示,HNTs对PVC/MBS共混体系热稳定性的提高能起到一定作用。     

The experimental results and simulation of temperature dependence of brittle‐ductile transition in PVC/CPE blends and PVC/CPE/nano‐CaCO3 composites

The effect of chlorinated polyethylene (CPE) content and test temperature on the notched Izod impact strength and brittle‐ductile transition behaviors for polyvinylchloride (PVC)/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites is studied. The CPE content and the test temperature regions are from 0–50 phr and 243–363 K, respectively. It is found that the optimum nano‐CaCO₃ content is 15 phr for PVC/CPE/nano‐CaCO₃ ternary composites. For both PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites, the impact strength is improved remarkably when the CPE content or test temperature is higher than the critical value, that is, brittle‐ductile transition content (C_BD) or brittle‐ductile transition temperature (T_BD). The T_BD is closely related to the CPE content, the higher the CPE content, the lower the T_BD. The temperature dependence of impact strength for PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites can be well simulated with a logistic fitting model, and the simulation results can be illustrated with the percolation model proposed by Wu and Jiang. DMA results reveal that both PVC and CPE can affect the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. When the CPE content is enough (20 phr), the CPE is more important than PVC for determining the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. Scanning electron microscopy (SEM) observations reveal that the impact fractured mechanism can change from brittle to ductile with increasing test temperature for these PVC systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fracture and impact strength of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene polymer blends

The Izod impact strength of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene(PVC/MBS)polymer blends can be changed significantly with different levels of MBS and/or MBS particle size. The following results were obtained by investigating the fracture of PVC/MBS test specimens: (1) The dependence of the Izod impact strength of PVC/MBS blend on MBS particle size confirms a maximum around a MBS particle size of 2000 Å. When MBS particle size is smaller than 2000 Å, the Izod impact strength increases with MBS particle size, and crazing occurs mainly in this region. When MBS particle size is larger than 2000 Å, then the Izod impact strength, in contrast, decreases with increasing MBS particle size, and both crazing and shear yielding occur, mainly in this region. (2) Tensile experiments of PVC/MBS blends carried out under various conditions showed that the amount of energy absorption increases with decreasing MBS inter-particle distance and with increasing MBS particle size when crazing is the main energy absorbing mode. The MBS inter-particle distance dominates the energy absorption when shear yielding is the main energy absorbing mode. (3) Therefore, the Izod impact strength of PVC/MBS blends and the maximum around a MBS particle size of 2000 Å can be explained as follows: Below 2000 Å, the energy absorption by crazing dominates the total energy absorption, and the energy absorption by crazing increases with MBS particle size. Above 2000 Å, the energy absorption by shear yielding is dominant, and the energy absorption by shear yielding increases with decreasing inter-particle distance, that is to say, decreasing MBS particle size.     

乳化剂对合成MBS树脂和PVC/MBS合金力学性能的影响

通过调节乳化剂十二烷基苯磺酸钠（SDBS）的用量合成MBS树脂，并将其与聚氯乙烯（PVC）树脂进行共混，测试PVC／MBS合金的力学性能。测试结果表明：乳化剂的用量越多，MBS树脂相的相对分子质量越低，PVC／MBS合金的拉伸强度变化不明显，其冲击强度先增大后减小。     

苯乙烯在MBS中的结合方式对PVC/MBS性能的影响

以乳液聚合法合成了化学组成恒定的具有核-壳结构的(甲基丙烯酸甲酯/丁二烯/苯乙烯)共聚物(MBS),通过改变原料及其配比,使苯乙烯(St)在MBS中以共聚或接枝方式结合,用动态力学热分析仪研究了MBS内耗与温度的关系。将MBS与聚氯乙烯(PVC)共混,研究了St结合方式对共混物冲击韧性及增韧机理的影响,结果表明,随着MBS核中St含量的增加,PVC/MBS共混物的脆-韧转变向高温移动;当St仅以接枝的方式结合时,橡胶粒子的空洞化及剪切屈服是主要的增韧机理,当St仅以共聚方式结合时,剪切屈服是主要的增韧机理。     

A Study of the Viscoelastic and Rheological Properties of PVC/CPE Blends Modified by Using Polylauryllactam

Abstract

Polylauryllactam was used to improve the impact strength of polyvinylchloride (PVC)/chlorinated polyethylene (CPE) blends without sacrificing their tensile properties. The enhancement of the impact strength increased with the increase of the CPE content in the PVC/CPE blends due to the formation of intermolecular hydrogen bonds among PVC, polylauryllactam and CPE macromolecules. A doubled impact strength of the PVC/CPE blend with 20 weight percent of CPE was obtained after the addition of 1.5 phr polylauryllactam. The PVC/CPE blends with polylauryllactam have a better dimensional stability compared with the PVC/CPE blends without the additive, according to their viscoelastic characteristics. Polylauryllactam shortened the processing time to reach a minimum melt viscosity in the processing of the PVC/CPE blends.     

超支化聚（酰胺-酯）／ABS／聚氯乙烯共混体系相容性研究

研究了超支化聚(酰胺-酯)(HBP)对ABS/聚氯乙烯(ABS/PVC)共混体系的增容作用。讨论了HBP用量对ABS/PVC(80/20)和相同量HBP对不同比例ABS/PVC力学性能的影响。实验结果表明ABS/PVC共混物中加入HBP,可以有效改善共混体系的相容性;加入2份HBP时,ABS/PVC(80/20)共混物拉伸强度达到最大值,继续增加HBP,共混物拉伸强度快速下降,而共混物冲击强度单调下降;不同比例ABS/PVC中加入2份HBP共混物拉伸强度比未加入HBP共混物拉伸强度增加,但共混物冲击强度减小。扫描电子显微镜研究结果证明了HBP增强了ABS/PVC的界面黏结作用,减小了共混体系的相分离程度。     

PVC/SBS/MBS三元共混体系的力学性能及光学透明性研究

采用冲击实验、拉伸实验、超景深三维显微镜、扫描电镜和分光光度计等手段，对PVC／SBS／MBS三元共混体系的冲击强度、拉伸强度、形态结构以及光学透明性等进行了研究。实验结果表明，MBS能有效改善PVC／SBS共混体系的界面相容性。当SBS和MBS的总量不变时，随着MBS相对含量的增加，共混体系的缺口冲击强度逐渐增加，透光率在m（MBS）／m（SBS）=28／80时达到最大值，光学透明性能最好。     

PP-g-（DMC-co-St）增容PP／PVC共混体系的研究

利用合成的多单体接枝物[PP-g-（DMC-co-St）]增容PP／PVC共混体系,研究了其用量对共混物力学性能以及流变性能的影响,并通过扫描电镜（SEM）分析了共混物的亚微观相结构。结果表明：①在试验条件下,共混物熔体具有典型的假塑性流体特征,在PP-g-（DMC-co-St）用量为6份时,熔体的表观黏流活化能和非牛顿指数最大;②PP-g-（DMC-co-St）对PP／PVC共混体系有较好的增容效果,增容后在PP-g-（DMC-co-St）用量为6份时,试样的拉伸强度、缺口冲击强度出现最大值,与扫描电镜照片的分析结果一致。     

Miscibility and thermal and mechanical properties of melt‐mixed poly(lactic acid)/poly(trimethylene terephthalate)/(methyl methacrylate)‐butadiene‐styrene copolymer blends

This study examined the miscibility and mechanical properties of melt‐mixed poly(lactic acid) (PLA), poly (trimethylene terephthalate) (PTT), and PLA/PTT blend with 5–10 phr of methyl methacrylate‐butadiene‐styrene copolymer (MBS). The isothermal crystallization kinetics of the PTT blends were analyzed by using the Avrami equation. The Differential Scanning Calorimetry (DSC) and scanning electron microscope results indicated that the miscibility of the PLA/PTT blends was improved by adding 5–10 phr of MBS. Although PLA, with the addition of 10 phr of MBS, had lower tensile strength at yield and higher breaking elongation and impact strength than pure PLA, no improvement in these mechanical properties could be observed in PLA/PTT blends. This result is explained by assuming that the crystallization of PTT at the interface favors the disentanglement of MBS from the PTT domain. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

PP/PVC/PP-HBP共混体系研究

研究了聚丙烯接枝超支化聚(酰胺-酯)(PP-HBP)对聚丙烯／聚氯乙烯(PP／PVC)共混体系力学性能的影响。结果表明，在PP／PVC(质量比为70／30)共混体系中加入5份PP-HBP时，共混物拉伸强度和冲击强度均出现最大值。扫描电子显微镜（SEM)研究结果证明，PP-HBP增强了PP／PVC的界面粘结作用，减小了共混体系的相分离程度。     

乙烯-甲基丙烯酸甲酯共聚物增容回收聚乙烯／聚氯乙烯共混体系的研究

采用乙烯-甲基丙烯酸甲酯共聚物（EMMA）作为增容剂制备了回收聚乙烯／聚氯乙烯（RPE／PVC）共混材料。通过差示扫描量热仪（DSC）研究了共混材料两相之间的相容性;通过微控电子万能实验机、电子冲击实验机研究了EMMA和RPE对共混材料性能的影响。DSC试验结果表明,EMMA能显著改善PVC与RPE之间的相容性,使共混材料中PVC的玻璃化转变峰变宽且变得模糊;力学性能试验结果表明,加入3份EMMA时,RPE／PVC（10／100）共混材料的冲击强度、拉伸强度、弯曲强度和弯曲模量分别提高了270％、74％、60．9％和9．1％;随着RPE含量的增加RPE／PVC共混材料的力学性能下降,当EMMA含量为3份、RPE含量为10份时,共混材料的综合性能较佳。     

PVC/Elvaloy741/MBS及PVC/Elvaloy741/MBS/CaCO_3共混填充体系的研究

研究了 PVC/Elvaloy74 1 /MBS及 PVC/Elvaloy74 1 /MBS/Ca CO3共混填充新体系 ,并对其物理机械性能的测试结果进行了讨论。结果表明 :当 PVC为 1 0 0份、Elvaloy74 1为 6份、MBS用量为 2 5.5份时 ,体系冲击强度达到 4 6.3 k J/m2 ,且综合性能良好 ;该三元共混体系在填充大量 Ca CO3(1 0 0份 )时 ,仍能保持较高的缺口冲击强度 (1 7k J/m2 ) ,显示出良好的填充性     

PVC／Elvaloy741／MBS及PVC／Elvaloy741／MBS／CaCO3共混填充体系的研究

研究了PVC／Elvaloy741/MBS及PVC／Elvaloy741/MBS/CaCO3共混填充新体系,对其物理机械性能的测试结果进行了讨论。结果表明：当PVC为100份、Elvaloy741为6份、MBS用量为25.5份时,体系冲击强度达到46.3kJ/m^2,且综合性能良好;该三元共混体系的填充大量CaCO3(100份）时,仍能保持较高的缺口冲击强度（17kJ/m^2）,显示出良好的填充性。     

Fracture behavior of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene polymer blends

The fracture mode of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene (PVC/MBS) polymer blends can change from ductile to brittle in accordance with the changes in shape of the test specimen or test conditions. Therefore, the mechanisms of impact energy absorption and the main cause of stress whitening are complicated. The following results on PVC/MBS blends were obtained by carrying out fracture experiments at different test speeds and temperatures:

• (1) The ductile/brittle fracture mode of the PVC and PVC/MBS blends can be explained by σ (the craze initiation stress)/σ_y (the shear yield initiation stress), which depends on the strain rates and temperature.
• (2) The fracture behavior of the PVC/MBS blends can be classified into the following types from the standpoints of fracture mode and whitening degree: Fracture I: ductile fracture without whitening; Fracture II: ductile fracture with whitening; and Fracture III: brittle fracture without whitening.
• (3) The following concepts can be estimated from the measurements of yield stress, specific gravity and SEM, TEM and visual observations. In Fracture I, shear yield occurs mainly. In Fracture II, both shear yield and crazing occur. In Fracture III, deformation of the rubber and local crazing occur.
• (4) The main cause of stress whitening in PVC/MBS blends is light scattering by cavities in the rubber particles.
• (5) In Fracture II, at first, crazes with cavities in the rubber particles occur. Then, shear yield occurs. Finally, crazes are healed by the heat, and only the cavities in the rubber remain.

     

Phase morphology and dynamic mechanical behavior for MIS toughened polyvinyl chloride

Graft copolymers of isoprene (Is), styrene (St), and methyl methacrylate (MMA) monomers (MIS) with typical core–shell structure were synthesized by seed emulsion polymerization and used as a toughening agent for preparation of polyvinyl chloride (PVC)/MIS blends. The St and MMA monomers were separately grafted on the cross‐linked poly‐isoprene rubber core. The toughness, sub‐micro‐morphology, and dynamic mechanical behavior of the blends were characterized by impact machine, scanning electron microscopy (SEM), and dynamic mechanical analyzer. The results showed that the impact strength of the blends was optimized when the content of MIS in PVC/MIS blends was kept at a constant value of 8 wt %, while the content of Is in MIS was 70 wt %. SEM morphologies of impact fractured surface showed that the PVC/MIS blends were typical ductile fracture because of the toughness effect of rubber particles, which correlated well with the mechanical properties. Under the same rubber content condition, the curves of the dynamic mechanical behavior of MIS toughened PVC blends appeared a more obvious rubber peak, indicating that the rubber content of MIS was higher than that of methyl methacrylate–butadiene–styrene (MBS), which explained the better toughening effect of MIS compared with MBS. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Processing morphology of PVC/MBS blend

MBS resin, an impact modifier for PVC, plays an important role in PVC processing, the details of which, however, are not well understood. The use of a temperature programmable Brabender Plasticorder and new microscopic techniques have revealed that MBS inhibits the comminution of PVC grain in the initial stage of processing, and PVC breakdown occurs after the MBS melts. Dynamic melting of MBS is observed as a Brabender torque peak. These characteristics of PVC/MBS blends are quite different from those of PVC/processing aid blends. Processing features of PVC/MBS blends are reported and compared with those of PVC/processing aid blends.     

Influence of impact load‐temperature conformity on toughening of poly(vinyl chloride) by core‐shell rubber particles

The work focused on the elucidation of several key parameters in toughening poly(vinyl chloride) (PVC) by the methyl methacrylate–butadiene–styrene (MBS) core‐shell particles. Accordingly, blends containing various weight percent of the MBS particles were prepared and characterized by dilute solution viscometry, dynamic light scattering, dynamic mechanical thermal analysis, transmission electron microscopy, and temperature variable impact test. The results showed PVC/MBS solution miscibility in almost all compositions with their maximum thermodynamic affinities at about 17 and 67 wt % of MBS in tetrahydrofurane (THF). In addition, MBS weight percent increase in its blend with the PVC above 10 led to severe impact energy raise with eventual leveling at about 17 wt %. Furthermore, blend toughness and its components miscibility in solution increased in parallel up to 20 wt % of MBS particles. On the other hand, blend toughness declined with test temperature decrease toward impact modifier core T_g at about ?30°C even for the sample with 20 wt % of the MBS particles. Finally, the brittle‐ductile transition of the blend containing 20 wt % of the MBS particles comparison with its matrix tan δ‐temperature correlation implied 2500 J/m impact energy equivalence with 90°C sample temperature rise in secondary relaxation activation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

透明硬质聚氯乙烯改性剂的研究

研究了改性剂MBS对透明硬质聚氯乙烯力学性能、塑化性能及透明性的影响,考察了改性剂ACR-201在MBS/PVC体系中的作用。实验结果表明,BTA-712在提高硬质聚氯乙烯冲击强度、断裂伸长率和改善其加工性能方面占优势;QB-31在透明性等方面超过同类进口产品B-31。ACR-201不仅是一种良好的加工助剂,还能进一步提高MBS/PVC的力学性能和透明性。     

3-巯基丁酸酯对MBS树脂相相对分子质量及PVC/MBS力学性能的影响

通过添加3-巯基丁酸酯合成了一系列树脂相相对分子质量变化的甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物(MBS树脂)。并将其与聚氯乙烯(PVC)树脂进行熔融共混,测试了PVC/MBS合金的力学性能。结果表明,链转移剂3-巯基丁酸酯用量越多,MBS树脂相的相对分子质量越低,PVC/MBS合金的熔体流动速率越高、加工流动性越好、冲击强度越低,但对拉伸强度影响不大。这对开发系列MBS树脂具有重要指导意义。