我国苯乙烯的生产消费现状及发展前景

苯乙烯是一种重要的基本有机化工原料，主要用于生产聚苯乙烯树脂（PS）、丙烯腈-丁二烯-苯乙烯三元共聚物（ABS）、苯乙烯-丙烯腈共聚物（SAN）树脂、离子交换树脂、不饱和聚酯以及苯乙烯系热塑性弹性体SBS等。[第一段]     

多壁碳纳米管复合聚碳酸酯/苯乙烯系聚合物复合材料导电性能的研究

采用一步法将聚苯乙烯（PS）、苯乙烯-丙烯腈共聚物（SAN）和甲基丙烯酸甲酯-苯乙烯共聚物（MS）分别与聚碳酸酯（PC）、多壁碳纳米管（MWCNTs）熔融混合,得到PC/PS/MWCNTs、PC/SAN/MWCNTs和PC/MS/MWCNTs三种复合材料。透射电子显微镜和场发射扫描电子显微镜观察表明,MWCNTs选择性分散在PC相中,这与Sumita模型预测的结果完全吻合,且随着PS、SAN或MS含量的增加,体系的体积电阻率-苯乙烯系聚合物含量曲线能够很好地拟合到PC/MWCNTs体系的体积电阻率-MWCNTs有效体积浓度曲线上,体系的体积电阻率变化符合有效浓度的概念。     

ABS装置SAN单元的技术改造

本文通过对树脂合成生产企业的ABS(丙烯腈-丁二烯-苯乙烯)装置中SAN(苯乙烯-丙烯腈)装置的技术和工艺情况调查和研究,对其生产技术和工艺进行了改造,通过这些技术改造,不仅提高了ABS装置的技术水平,还消除了原来装置的安全隐患、质量和消耗问题,对SAN单元生产的发展提供了有效的技术支持。     

苯乙烯生产技术研究

苯乙烯是一种重要的基本有机化工原料,主要用于生产聚苯乙烯树脂（PS）、丙烯腈-丁二烯-苯乙烯三元共聚物（ABS）、苯乙烯一丙烯腈共聚物（SAN）树脂、丁苯橡胶（SBR）和丁苯胶乳（SBR胶乳）、离子交换树脂、不饱和聚酯以及苯乙烯系热塑性弹性体SBS等。此外,还可用于制药、染料、农药以及选矿等行业,用途十分广泛。     

长支链聚丙烯增容聚丙烯共混物的研究

以聚丙烯（PP）为原料,通过熔融接枝法制备长支链聚丙烯（LCBPP）,将LCBPP分别加入到PP／聚苯乙烯（PS）、PP／苯乙烯-丙烯腈嵌段共聚物（SAN）和PP／聚对苯二甲酸乙二醇酯（PET）共混体系里。采用傅里叶变换红外（FTIR）和拉伸流变仪对LCBPP进行表征。采用扫描电子显微镜对共混物的断面进行观察。结果表明,LCBPP对分散相具有一定极性的体系表现出良好的增容效果;在组分比为70/30的PP/SAN 和PP/PET体系中加入５％的LCBPP后,体系分散相尺寸明显细化且分散均匀,但是其增容效果没有枝马来酸酐接聚丙烯（PP-g-MAH）的增容效果明显;LCBPP对于PP/PS体系的相容性有轻微的改善。     

ABS装置节能改造措施应用与效果

本文阐述了大沽化工ABS装置的能源消耗情况,分析了大沽化工ABS装置能耗构成,并采取针对性节能降耗措施,如SAN一期造粒系统改造、优化反应釜程序、热油炉燃烧系统改造、SAN热油炉天然气管线增加节能器、优化生产管理等。2015～2018年四年里,ABS装置能耗由0.199tec/tABS降至0.179tec/tABS,降幅达到10.05%,效果明显。     

燕山乙烯装置蒸汽网络的现状分析与优化方向

介绍了燕山乙烯装置在用蒸汽网络的匹配情况。目前装置消耗蒸汽主要有4种,按蒸汽压力等级划分,分别是10.0 MPa超高压蒸汽（SS）、1.5 MPa中压蒸汽（MS）、0.3 MPa低压蒸汽（LS）和0.25MPa次低压饱和蒸汽（PS）。装置生产运行工况的改变对蒸汽的使用与消耗会产生一定的影响。通过对不同工况条件下相关数据的采集和生产改造等因素的分析,尝试探寻出装置节能运行方向,并从管理、计量、操作等角度为建立更合理、优化、高效的蒸汽网络提出改善建议,以期使燕山乙烯装置蒸汽使用能效水平进一步提高。     

生产装置的优化

英国《１９９８年国际橡胶技术》９９页报道：对现有生产装置进行扩建规划时,反复不断地提出了诸如以下一类问题：装置容量如何和在何处怎样调整,方可获得最高效率及达到将来（产品配方和生产产量）要求等。由于原材料范围广、品种多,现今的原材料储运装置变得越来越复杂。结果用人工方法无法可靠预测将来生产过程何处再会发生瓶颈制约,更不用说某一个装置改造后会受到何等影响。针对这种困境,布勒公司开发成功名为“ＲＵＳＩＭ”的模拟计算机（见图１）。它是分析现有的储运装置和模拟各种改造变型装置在将来生产条件下运行效果的一种…     

悬浮法PEB-g-MAN/SAN共混物的热性能与耐老化性能研究

用悬浮接枝共聚法制备了乙烯-1-丁烯共聚物（PEB）与甲基丙烯酸甲酯和丙烯腈共聚物的接枝共聚物（PEB-g-MAN）,并用其增韧苯乙烯-丙烯腈共聚物（SAN）。用动态力学分析、热重分析、人工气候老化和热氧老化试验等方法研究了PEB-g-MAN/SAN共混物的热性能与耐老化性能。结果表明,PEB-g-MAN/SAN共混物的PEB组分和SAN组分的玻璃化转变温度（Tg）之差明显低于PEB弹性体与SAN树脂的Tg之差,表明PEB-g-MAN与SAN树脂具有良好的相容性;PEB-g-MAN/SAN共混物的热稳定性明显优于SAN树脂,耐气候老化黄变性能和热氧老化后缺口冲击强度保持率明显优于丙烯腈-苯乙烯-丁二烯共聚物（ABS）,而热氧老化后的拉伸、弯曲强度则稍逊于ABS。     

聚苯循环液回收用于生产SAN产品

通过SAN装置废单、原料组成和聚苯循环液组成的对比分析,得出废单和聚苯循环液可用于生产SAN产品。利用聚合产出的废单和聚苯循环液在SAN装置上成功生产出SAN产品,提高了废物的附加值。     

The effects of PC‐PMMA block copolymer on the compatibility and interfacial properties of PC/SAN blends

Block copolymers of polycarbonate (PC) and polymethylmethacrylate (PMMA), PCb‐PMMA, were examined as compatibilizers for blends of PC with styrene‐co‐acrylonitrile (SAN) copolymer. PC‐b‐PMMA was added to blends of PC with SAN containing various amounts of AN. The average diameter of the dispersed particles was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) test and an asymmetric double cantilever beam fracture test. The average particle size and interfacial tension of the PC/SAN blends reached a minimum value when the SAN copolymer contained about 24 wt% AN. A maximum in the adhesion energy was also observed at the same AN content. Interfacial tension and particle size were further reduced by adding PC‐b‐PMMA to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing the interfacial adhesion by the addition of PC‐b‐PMMA. The addition of PC‐b‐PMMA copolymer was more effective at improving the interfacial properties of PC/SAN blends than was varying the AN content of the SAN copolymers. The interfacial properties of the PC/SAN blends were optimized by adding a block copolymer and using an SAN copolymer that had minimum interaction energy with PC.     

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     

The Influence of the compatibilizer Characteristics on the interfacial characteristics and phase morphology of aPA/SAN blends

The main objective of this work is study the influence of the methyl mathacrylate maleic anhydride copolymer (MMA-MA) compatibilizer properties such as molecular weight and maleic anhydride content in the characteristics of amorphous polyamide and styrene acrylonitrile copolymer (aPA/SAN) blends, correlating their interfacial characteristics and phase morphology. The blends aPA/SAN, with and without the compatibilizer, prepared were characterized by transmission electron microscopy (TEM) and small angle X-rays scattering (SAXS). The results show that the maleic anhydride concentration has a more significant effect on the blend properties than the molecular weight of the MMA-MA copolymer. Even though the system aPA/SAN is thermodynamically immiscible, it shows morphology of phases with small particles of SAN. The addition of MMA-MA copolymer with high degrees of MA led to an increase of the SAN phase particle size. With SAXS technique, it was possible to determine the interface thickness and the results shows that the characteristics of the interface do not change with the variation of the compatibilizer characteristics. The results observed in this work indicate that the viscosity ratio is very important factor on the formation of the phase morphology.     

Application of styrene‐acrylonitrile random copolymer–polyarylate block copolymer as reactive compatibilizer for polyamide and acrylonitrile‐butadiene‐styrene blends

Styrene‐acrylonitrile random copolymer (SAN) and polyarylate (PAr) block copolymer were applied as a reactive compatibilizer for polyamide‐6 (PA‐6)/acrylonitrile‐butadiene‐styrene (ABS) copolymer blends. The SAN–PAr block copolymer was found to be effective for compatibilization of PA‐6/ABS blends. With the addition of 3.0–5.0 wt % SAN–PAr block copolymer, the ABS‐rich phase could be reduced to a smaller size than 1.0 μm in the 70/30 and 50/50 PA‐6/ABS blends, although it was several microns in the uncompatibilized blends. As a result, for the blends compatibilized with 3–5 wt % block copolymer the impact energy absorption reached the super toughness region in the 70/30 and 50/50 PA‐6/ABS compositions. The compatibilization mechanism of PA‐6/ABS by the SAN–PAr block copolymer was investigated by tetrahydrofuran extraction of the SAN–PAr block copolymer/PA‐6 blends and the model reactions between the block copolymer and low molecular weight compounds. The results of these experiments indicated that the SAN–PAr block copolymer reacted with the PA‐6 during the melt mixing process via an in situ transreaction between the ester units in the PAr chain and the terminal amine in the PA‐6. As a result, SAN–PAr/PA‐6 block copolymers were generated during the melt mixing process. The SAN–PAr block copolymer was supposed to compatibilize the PA‐6 and ABS blend by anchoring the PAr/PA‐6 and SAN chains to the PA‐6 and ABS phases, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2300–2313, 2002     

Effects of tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) copolymers containing various amounts of acrylonitrile on the interfacial properties of polycarbonate and poly(styrene‐co‐acrylonitrile) blends

Tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) (TMPC‐block‐SAN) block copolymers containing various amounts of acrylonitrile (AN) were examined as compatibilizers for blends of polycarbonate (PC) with poly(styrene‐co‐acrylonitrile) (SAN) copolymers. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fibre retraction technique and an asymmetric double‐cantilever beam fracture test. Reduction in the average diameter of dispersed particles and effective improvement in the interfacial properties was observed by adding TMPC‐block‐SAN copolymers as compatibilizer of PC/SAN blend. TMPC‐block‐SAN copolymer was effective as a compatibilizer when the difference in the AN content of SAN copolymer and that of SAN block in TMPC‐block‐SAN copolymer was less than about 10 wt%. Copyright © 2004 Society of Chemical Industry     

Melting point depression in poly(ɛ-caprolactone) / poly(styrene-co-acrylonitrile) blends

Summary The melting point depression of poly(-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends with changes in acrylonitrile content of SAN and in blend ratio was investigated by differential scanning calorimetry. For the melting points at a constant blend ratio occur a minimum in dependence on the copolymer composition for blends containing about 20 wt% acrylonitrile in SAN. From melting point depression data a negative, binary interaction parameter was obtained for PCL/SAN blends containing a SAN with 19.2 wt% AN. By optical microscopy it can be shown that the shape of the spherulites changes with copolymer composition of SAN and blend ratio.     

Changes in the interfacial properties of PC/SAN blends with compatibilizer

Block copolymers of polycarbonate‐b‐poly(methyl methacrylate) (PC‐b‐PMMA) and tetramethyl poly(carbonate)‐b‐poly(methyl methacrylate) (TMPC‐b‐PMMA) were examined as compatibilizers for blends of polycarbonate (PC) with styrene‐co‐acrylonitrile (SAN) copolymer. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) technique and an asymmetric double cantilever beam fracture test. The average diameter of dispersed particles and interfacial tension of the PC/SAN blends were reduced by adding compatibilizer to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing interfacial adhesion with compatibilizer. TMPC‐b‐PMMA copolymer was more effective than PC‐b‐PMMA copolymer as a compatibilizer for the PC/SAN blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2649–2656, 2003     

Influence of blend composition on the mechanical properties and morphology of PC/ASA/SAN ternary blends

Bisphenol A polycarbonate/acrylonitrile–styrene–acrylic/styrene–acrylonitrile copolymer (PC/ASA/SAN) ternary blends were prepared over a range of compositions via mixing PC, SAN, and ASA copolymer by melt blending. An analysis was made on the mechanical properties and morphology of the blends. Special care was taken to make comparisons of the morphologies and properties of blends with different SAN content. When a small amount SAN was introduced to PC/ASA blends, the dispersion condition of ASA in the matrix was improved and a better integrated mechanical properties was realized. Further increasing the SAN content led to a decrease of impact strength, which was due to the changing of the morphology of the blends and the inherent brittleness of matrix. The study about the effect of ASA content on the properties of PC/ASA/SAN blends showed that the blend with 20 wt% ASA had good mechanical properties.     

Oxazoline‐containing compatibilizers for polyamide/SAN and polyamide/ABS blends

Polyamide (PA) and acrylonitrile/butadiene/styrene copolymer (ABS) may appear as a mixture in the recycled plastic stream. The incompatibility of these blends results in a blend with poor mechanical properties. The aim of this work is to partially convert the nitrile groups of the acrylonitrile/styrene copolymer (SAN) into oxazoline groups by reaction with aminoethanol (AE). Such modified SAN (SAN‐m) can react with the amine or carboxylic acid end groups of PA, and therefore used as compatibilizers for blends of PA with ABS. SAN‐m was found to reduce the SAN‐domain size in the PA/SAN‐blends. The initial acrylonitrile content of SAN‐m had a strong influence on the degree of conversion into oxazoline groups and on the compatibilizing effect. Mechanical properties of SAN‐m compatibilized PA/ABS blends were investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 449–455, 2002     

Effect of the addition of acrylonitrile/ethylene–propylene–diene monomer (EPDM)/styrene graft copolymer on the morphology–properties relationships in poly(styrene‐co‐acrylonitrile)/EPDM rubber blends

Blends of poly(styrene‐co‐acylonitrile) (SAN) with ethylene–propylene–diene monomer (EPDM) rubber were investigated. An improved toughness–stiffness balance of the SAN/EPDM blend was obtained when an appropriate amount of acrylonitrile–EPDM–styrene (AES) graft copolymer was added, prepared by grafting EPDM with styrene–acrylonitrile copolymer, and mixed thoroughly with both of the two components of the blend. Morphological observations indicated a finer dispersion of the EPDM particles in the SAN/EPDM/AES blends, and particle size distribution became narrower with increasing amounts of AES. Meanwhile, it was found that the SAN/EPDM blend having a ratio of 82.5/17.5 by weight was more effective in increasing the impact strength than that of the 90/10 blend. From dynamic mechanic analysis of the blends, the glass‐transition temperature of the EPDM‐rich phase increased from ?53.9 to ?46.2°C, even ?32.0°C, for the ratio of 82.5/17.5 blend of SAN/EPDM, whereas that of the SAN‐rich phase decreased from 109.2 to 108.6 and 107.5°C with the additions of 6 and 10% AES copolymer contents, respectively. It was confirmed that AES graft copolymer is an efficient compatibilizer for SAN/EPDM blend. The compatibilizer plays an important role in connecting two phases and improving the stress transfer in the blends. Certain morphological features such as thin filament connecting and even networking of the dispersed rubber phase may contribute to the overall ductility of the high impact strength of the studied blends. Moreover, its potential to induce a brittle–ductile transition of the glassy SAN matrix is considered to explain the toughening mechanism. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1685–1697, 2004