SAN共聚物中AN含量对PVC/ABS/DOP共混物结构与性能的影响

采用半连续乳液聚合技术将聚苯乙烯(St)和丙烯腈(AN)接枝到聚丁二烯(PB)乳胶粒子上,通过改变共聚单体的投料比(St/AN)合成了一系列不同AN含量的丙烯腈-丁二烯-苯乙烯共聚物(ABS)接枝共聚物,将其与聚氯乙烯(PVC)和增塑剂邻苯二甲酸二辛酯(DOP)熔融共混制得PVC/ABS/DOP(40/40/20)共混物。研究了共混物的热挺型性、微观形态结构和动态力学性能。结果发现,该共混物为双相连续结构,随着接枝SAN共聚物中AN含量的增加,由于DOP小分子与SAN共聚物的相互作用逐渐减弱,导致了SAN相的Tg和共混物的储能模量不断提高,改善了共混物的热挺型性,阐明了PVC/ABS/DOP共混物热挺型性的科学本质。     

悬浮法EPM—g—SAN的合成与表征

以悬浮法实施二元乙丙橡胶（EPM）与单体苯乙烯（St）和丙烯腈（AN）的接枝共聚反应。合成了EPM—g—SAN,用其与SAN树脂共混制备了高抗冲塑料乙丙橡胶与苯乙烯及丙烯腈的三元共聚物（AES）。研究了AN／St—AN和EPM／St-AN的配料比对接枝反应体系的单体转化率、接枝率和接枝效率及AES缺口冲击强度的影响。用FTIR对EPM—g—SAN所含g—SAN（包括接枝链和非接枝共聚物）的组成进行了定量分析。结果表明,当AN质量分数为35％、EPM质量分数为60％,接枝反应体系的单体转化率、接枝率和接枝效率分别为92％、45％和27．6％。在此条件下合成的EPM—g—SAN对SAN树脂的增韧效率最高,用其制备的AES的悬臂梁缺口冲击强度达到53．2kJ／m^2。FTIR定量分析表明,在EPM—g—SAN的g—SAN中AN单元的平均组成比小于AN单体的配料比,而AN单元在接枝链SAN中的组成比小于在非接枝共聚物SAN中的组成比;当g—SAN所含接枝链的组成与非接枝共聚物的组成相等时,其EPM—g—SAN对SAN树脂有更高的增韧效率。     

悬浮法合成EPDM—g—MAN接枝共聚物及其对SAN树脂的增韧作用

用悬浮接枝共聚合法合成了乙烯-丙烯-乙叉降冰片烯三元乙丙橡胶（EPDM）与甲基丙烯酸甲酯-丙烯腈（MMA—AN）共单体的接枝共聚物（EPDM—g—MAN）。将其与苯乙烯-丙烯腈共聚物（SAN树脂）共混制备了耐热氧老化黄变性能优异的高抗冲工程塑料EPDM—g—MAN／SAN共混物（AEMS）。研究了仇（AN）／m（MMA—AN）和m（EPDM）／m（MMA—AN）对5个接枝共聚体系反应行为的影响。结果发现,随着AN比率（fAN）的增加,共单体的转化率（CR）、接枝率（GR）和接枝效率（GE）都有所下降;随着m（EPDM）／m（MMA—AN）的增加,CR先增后降,GE增加,GR下降;随着优（AN）／（MMA—AN）和m（EPDM）／m（MMA—AN）的增加,AEMS的缺口冲击强度先增后降,出现极大值。AEMS在‰为5％,CR为98．9％,GR为68．4％,GE为84．6％时出现极大值,为76．8kJ／m^2。FTIR图谱显示,EPDM确已接枝上了甲基丙烯酸甲酯一丙烯腈（MAN）支链。TEM分析表明,m（EPDM）／m（MMA～AN）为55／45,fAN为10％时合成的EPDM—g—MAN在SAN树脂中以“海-岛”结构存在,相界面模糊,EPDM粒子的粒径范围为0．2～0．5μm,增韧效率高。     

PVC/SAN/ABS共混物的增韧机理

采用以乳液聚合的方法合成丙烯腈-丁二烯-苯乙烯共聚物(ABS)接枝粉料,将其与PVC、苯乙烯/丙烯腈共聚物（SAN）树脂熔融共混制备PVC/SAN/ABS共混物。恒定共混物中ABS含量,改变体系中SAN与PVC的比例从70.5/17.5至18/70。TEM分析表明,当共混物中SAN含量较多时,可以观察到银纹的存在;当共混物中PVC含量较多,可以观察到剪切屈服的发生;SEM分析发现,当共混物中PVC含量较多时,断裂表面出现了大量的空洞并伴随着基体的塑性流动;SAXS分析表明,当共混物中SAN的含量较多时,散射强度的增加是银纹的贡献能力增大的结果。     

AN含量对PVC/SAN共混物相容性的影响

采用乳液聚合技术合成了一系列不同丙烯腈（AN）含量的苯乙烯-丙烯腈（SAN）共聚物,将其与聚氯乙烯（PVC）熔融共混,形成PVC/SAN共混物,并引入增塑剂邻苯二甲酸二辛酯（DOP）。通过动态力学分析仪（DMA）和扫描电子显微镜（SEM）对共混物的玻璃化转变温度和相结构进行表征,考察不同AN含量对PVC/SAN共混物相容性的影响。     

ABS接枝共聚物对PVC树脂的增韧改性

对聚氯乙烯(PVC)/丙烯腈-苯乙烯-丁二烯接枝共聚物(ABS)共混物的脆韧转变、相形态以及动态力学性能进行研究。将不同摩尔质量的PVC与ABS熔融共混制备测试样品。结果表明:低摩尔质量PVC共混物比高摩尔质量PVC共混物的脆韧转变出现时所需的橡胶含量低。在体系中加入增塑剂DOP后,测试结果得到明显改善。通过透射电镜观察发现,高摩尔质量PVC共混物中存在未完全塑化的PVC,其相区尺寸大于PVC初级粒子的尺寸。并得出PVC与SAN部分相容,不影响橡胶粒子在基体中的均匀分散。     

PP-g-(GMA-co-St)增容PVC/PP共混物的研究

制备了一种新型的多单体接枝PP[PP-g-（GMA—co—St）]，研究了其对聚氯乙烯／聚丙烯（PVC／PP）共混体系的增容作用。讨论了接枝PP用量对共混物的界面相互作用、力学性能、耐热变形性能和加工流变性能的影响，并通过扫描电镜（SEM）对共混物的微观相结构进行了观察。结果表明，该接枝PP对PVC／PP共混体系有较好的增容效果，接枝PP的加入使共混物的界面相互作用增强。共混物的力学性能在接枝PP用量为20份时最佳；熔体流动速率在其质量分数为20％后下降缓慢，共混物的耐热变形性能随PP—g-（GMA—co—St）用量的增加而增强。     

在ABS/PVC共混体系中添加α-SAN树脂配方的研究

本文介绍了ABS/PVC共混体系中添加α—SAN树脂,进行三元共混改性的研究,找出了能使共混物综合性能较佳的三元共混物的配方。实验证明,通过添加α—SAN树脂,可改进ABS/PVC共混物的性能,有利于该共混物进一步降低价格,扩大应用。此外,对该共混物中最适宜于PVC改性用的ABS品种和用量,也进行了选择性的探讨。     

EPDM-g-MAN的合成及AEMS的冲击性能研究

用(乙烯/丙烯/二烯)共聚物(EPDM)与甲基丙烯酸甲酯(MMA)、丙烯腈(AN)进行溶液接枝共聚合成了(EPDM/MMA/AN)接枝共聚物(EPDM-g-MAN),并将其与(苯乙烯/丙烯腈)共聚物(SAN)共混制得高抗冲耐老化黄变性能优异的EPDM-g-MAN/SAN共混物(AEMS).研究了AN用量对不同EPDM-g-MAN接枝体系单体转化率(CR)、接枝率(GR)、接枝效率(GE)及AEMS缺口冲击强度的影响.结果发现,随着AN用量的增加,EPDM-g-MAN的CR逐渐下降;GR、GE在AN质量分数为5%时出现最大值;AEMS的缺口冲击强度均在AN质量分数为10%时出现最大值,为61.0 kJ/m2;EPDM相以条状形态构成的近连续相结构存在,径向尺寸较小的EPDM条形结构能诱发SAN基体剪切屈服,径向尺寸较大的EPDM条形结构仅能诱发基体空穴化.     

PB-g-SAN接枝粉料的含胶量对ABS性能的影响

通过种子乳液聚合合成了一系列含胶量不同的聚丁二烯接枝(苯乙烯／丙烯腈)共聚物(PB-g-SAN)接枝粉料。考察了PB—g-SAN接枝粉料的含肢量对其接枝率的影响。将PB-g-SAN接枝粉料与SAN共混制备ABS，控制二者比例使每批ABS含胶量相同，均为15％。研究了PB—g—SAN接枝粉料的含胶量对ABS性能的影响。发现PB—g-SAN接枝粉料的含胶量在60％时，ABS的力学性能最好。     

Toughness,dynamic mechanical property,and morphology of polyvinylchloride/acrylonitrile‐styrene‐butyl acrylate blends

Acrylonitrile‐styrene‐butyl acrylate (ASA) graft copolymers with different acrylonitrile (AN) contents, the core‐shell ratio, and tert‐dodecyl mercaptan (TDDM) amounts were synthesized by seed emulsion polymerization. Polyvinylchloride (PVC)/ASA blends were prepared by melt blending ASA graft copolymers with PVC resin. Then the toughness, dynamic mechanical property, and morphology of the PVC/ASA blends were investigated. The results indicated that the impact strength of the PVC/ASA blends increased and then decreased with the increase of the AN content in poly(styrene‐co‐acrylonitrile (SAN) copolymer, and increased with the increase of the core‐shell ratio of ASA. It was shown that brittle‐ductile transition of PVC/ASA blends was dependent on poly(butyl acrylate) (PBA) rubber content in blends and independent of AN content in SAN copolymer. The introduction of TDDM made the toughness of PVC/ASA blends poor. Dynamic mechanical analysis (DMA) curves exhibited that PVC and SAN copolymers were immiscible over the entire AN composition range. From scanning electron microscopy (SEM), it was found that the dispersion of ASA in PVC/ASA blends was dependent on the AN content in SAN copolymer and TDDM amounts. J. VINYL ADDIT. TECHNOL., 22:43–50, 2016. © 2014 Society of Plastics Engineers     

Effect of the composition of α-MSAN copolymer on the miscibility of PVC/α-MSAN blends

A series of α-methylstyrene, styrene, and acrylonitrile (α-MSAN) copolymers with different acrylonitrile (AN) contents were synthesized by altering α-MSt, St, and AN ratios with emulsion copolymerization method. By melt-blending these copolymers with PVC resin and di-isooctyl phthalate (DOP), PVC/α-MSAN, and PVC/α-MSAN/DOP blends were prepared. The miscibility and morphology of the blends were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy. The PVC is immiscible with SAN by melt-mixing, whereas PVC is miscible with α-MSAN (α-MSt/St = 1/1) if AN weight percent is within the window range of 20–25 wt %, and α-MSAN (not containing St) with 35 wt % AN is miscible with PVC even when they are blended by melt-mixing. Replacement of styrene with α-methylstyrene widens the miscibility window with PVC. The miscibility of PVC/α-MSAN blends is substantially improved with the increasing α-MSt content in α-MSAN copolymer containing identical AN content. When DOP was introduced into the PVC/α-MSAN (α-MSt/St = 1/1) blends, a single tan δ peak over room temperature in DMA detection is found as AN content in α-MSAN copolymer is within the range of 15–25 wt %, and SEM observation also shows that the blends are homogeneous. When the AN content in α-MSAN copolymer is over 35 wt %, the presence of DOP causes the phase domain extended. The phase domain size of the PVC/α-MSAN/DOP blends intensively depends on AN content in α-MSAN copolymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PB橡胶粒径对CPVC/PVC/ABS共混体系结构与性能的影响

采用乳液聚合技术合成了一系列不同PB橡胶粒径的ABS核壳改性剂,将其与CPVC、PVC共混,考察了CPVC/PVC/ABS共混物的结构与性能。动态力学分析表明：CPVC与PVC比例为90/10时,CPVC/PVC共混物部分相容,CPVC/PVC/ABS共混物也是部分相容;扫描电子显微镜分析其形态结构表明：共混物中ABS分散受PB橡胶粒径影响,PB橡胶粒径为113 nm的ABS在CPVC中分散最均匀。力学性能测试表明：随着PB橡胶粒径的增加,共混物的冲击强度先增大后减小,拉伸强度并无明显变化。     

Effect of α-MSt content in α-MSAN copolymer on the miscibility of PVC/α-MSAN blends

A series of α-methylstyrene, styrene and acrylonitrile(α-MSAN) copolymers with different α-methylstyrene (α-MSt) content were synthesized by altering α-MSt and St ratios with emulsion copolymerization method. By melt blending these copolymers with PVC resin and di-isooctyl phthalate (DOP), PVC/α-MSAN and PVC/α-MSAN/DOP blends were prepared. The miscibility and morphology of the blends were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The miscibility of PVC/α-MSAN blends is substantially improved with the increasing α-MSt content in α-MSAN copolymer containing identical AN content and the blends show homogeneous morphology as the α-MSt content in α-MSAN copolymer is up to 22.5wt%. α-MSAN copolymer containing 37.5wt% α-MSt is fully miscible with PVC throughout the whole composition range. When DOP was introduced into the PVC/α-MSAN blends, a single Tanδ peak over room temperature in DMA detection is found as α-MSt content in α-MSAN copolymer is from 15 to 75 wt%, and morphology result also shows that the PVC and α-MSAN copolymer is miscible under the influence of DOP.     

Influence of the tert‐dodecyl mercaptan content in poly(acrylonitrile‐butadiene‐styrene) on properties of chlorinated polyvinyl chloride/poly(acrylonitrile‐butadiene‐styrene) blends

A series of poly(acrylonitrile‐butadiene‐styrene) (ABS) grafting modifiers were synthesized by emulsion grafting poly(acrylonitrile‐styrene) (SAN) copolymer onto polybutadiene (PB) latex rubber particles. The chain transfer reagent tert‐dodecyl mercaptan (TDDM) was used to regulate the grafting degree of ABS and the molecular weight of SAN copolymers. By blending these ABS modifiers with Chlorinated polyvinyl chloride (CPVC) resin, a series of CPVC/ABS blends were obtained. The morphology, compatibility, and the mechanical properties of CPVC/ABS blends were investigated. The scanning electron microscope (SEM) studies showed that the ABS domain all uniformly dispersed in CPVC matrix. Dynamic mechanical analyses (DMA) results showed that the compatibility between CPVC and SAN became enhanced with the TDDM content. From the mechanical properties study of the CPVC/ABS blends, it was revealed that the impact strength first increases and then decreases with the TDDM content, which means that the compatibility between CPVC and the SAN was not the only requirement for maximizing toughness. The decreasing of tensile strength and the elongations might attribute to the lower entanglement between chains of CPVC and SAN. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

乳液接枝聚合的反应控制对ABS树脂性能的影响

采用种子乳液聚合方法合成PB-g-SAN(ABS)接枝共聚物,与苯乙烯丙烯腈共聚物(SAN)熔融共混制备ABS树脂。主要研究了在聚丁二烯橡胶粒子(PB)上接枝苯乙烯(St)和丙烯腈(AN)单体制备ABS接枝共聚物过程中,单体的加料时间和预溶胀过程的控制对单体的接枝效果、ABS橡胶粒子的形态以及最终ABS树脂性能的影响。实验结果表明:与一次投料工艺相比,在接枝过程中连续进料方式有助于提高接枝效率,且单体连续加料时间适当缩短有助于提高ABS树脂的冲击强度;单体预溶胀过程会降低接枝效率,并且容易使St单体进入PB相形成内包容结构,接枝过程中保持预溶胀合适的单体量有助于提高ABS树脂的冲击强度。     

Investigation on the miscibility of the blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The miscibility was investigated in blends of poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt % blends of PMMA with the SAN copolymers containing 5, 35, and 50 wt % of AN were immiscible, while the blend with copolymer containing 25 wt % of AN was miscible. The morphologies of PMMA/SAN blends were characterized by virtue of scanning electron microscopy and transmission electron microscopy. It was found that the miscibility of PMMA/SAN blends were in consistence with the morphologies observed. Moreover, the different morphologies in blends of PMMA and SAN were also observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of matrix SAN in ABS/PMMA blends

The effect of the molecular weight and acrylonitrile (AN) content of the styrene–acrylonitrile copolymer (SAN) on the morphology, mechanical properties, and rheological properties of acrylonitrile–butadiene–styrene terpolymer/poly(methyl methacrylate) (ABS)/PMMA (60/40 by weight) blends were studied. When the AN content of matrix SAN (32%) was close to that of graft SAN (30%) AN, rubber particles existed separately. However, with matrix SAN having 35% AN, rubber particles showed tendency to agglomerate each other. With increasing molecular weight of matrix SAN, impact strength, ultimate elongation, and abrasion resistance of the blend generally increased. Yield strength increased with molecular weight at a constant AN content of matrix SAN, and it decreased with the decrease of AN content in spite of the increasing molecular weight of SAN. Melt properties, rather than the morphological and mechanical properties, were more sensitive to the AN content, rather than the molecular weight of matrix SAN. © 1994 John Wiley & Sons, Inc.     

Effects of addition of acrylic compatibilizer on the morphology and mechanical behavior of amorphous polyamide/SAN blends

Amorphous polyamide (aPA)/acrylonitrile‐styrene copolymer (SAN) blends were prepared using methyl methacrylate‐maleic anhydride copolymer MMA‐MA as compatibilizer. The aPA/SAN blends can be considered as a less complex version of the aPA/ABS (acrylonitrilebutadiene‐styrene) blends, due to the absence of the ABS rubber phase in the SAN material. It is known that acrylic copolymer might be miscible with SAN, whereas the maleic anhydride groups from MMA‐MA can react in situ with the amine end groups of aPA during melt blending. As a result, it is possible the in situ formation of aPA‐g‐MMA‐MA grafted copolymers at the aPA/SAN interface during the melt processing of the blends. In this study, the MA content in the MMA‐MA copolymer and its molecular weight was varied independently and their effects on the blend morphology and stress–strain behavior were evaluated. The morphology of the blends aPA/SAN showed a minimum in the SAN particle size at low amounts of MA in the compatibilizer, however, as the MA content in the MMA‐MA copolymer was increased larger SAN particle sizes were observed in the systems. In addition, higher MA content in the compatibilizer lead to less ductile aPA/SAN blends under tensile testing. The results shown the viscosity ratio also plays a very important role in the morphology formation and consequently on the properties of the aPA/SAN blends studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Blends of imidized acrylic polymers with SAN copolymers and with PVC

A series of imidized acrylic polymers of varying structural composition generated by reaction of methylamine with poly(methyl methacrylate) were blended with a range of styrene/acrylonitrile or SAN copolymers (0–33% AN) and with poly(vinyl chloride). On the basis of glass transition behavior determined by differential scanning calorimetry, some but not all imidized acrylic structures were found to be miscible with PVC and with SAN copolymers within a limited window of AN levels. Acid functionality in the imidized acrylics appears to hinder their miscibility with SAN rather significantly and with PVC to a lesser extent. Miscible SAN blends showed lower critical solution temperature behavior whereas miscible blends with PVC did not up to the highest attainable temperatures. The composition factors that influence the phase behavior are described and interpreted in terms of possible mechanisms.