Synthesis and characterization of ABS resin using in situ transferring from emulsion to suspension polymerization

A novel approach based on an emulsion in situ suspension polymerization process for synthesizing poly(acrylonitrile–butadiene–styrene) (ABS) resin is reported. Experimental results show that the reaction system can be transformed from an emulsion state to a suspension polymerization state steadily with the content of polybutadiene (PB) in the range 0–15 wt% in ABS resin. When PB is replaced by poly(styrene‐co‐butadiene) with the content of rubber particles being kept below 20 wt%, the emulsion system can be easily transferred to the suspension polymerization state through a process of latex coagulation in the forward direction, which means that the emulsion solution was dripped slowly into the suspension reaction system in the presence of coagulating agent. The dispersion status of the rubber particles in the ABS resin was studied using transmission electron microscopy, which indicated that the rubber particles were in a dispersed state in a continuous matrix of poly(styrene‐co‐acrylonitrile) when the content of rubber particles was below 20 wt%. The mechanical properties of the ABS resins obtained are as follows: elongation at break, 9.4–45.7%; yield tensile strength, 35.1–42.2 MPa; impact strength, 98.2–116.3 J m^?1. Copyright © 2006 Society of Chemical Industry     

Phase separation of some clear polyblends

By using variations of elution and precipitation techniques, a clear ABS resin is found to be a mixture of a styrene–butadiene rubbery copolymer, a methyl methacrylate–styrene–acrylonitrile copolymer, and a graft of the methyl methacrylate–styrene–acrylonitrile copolymer onto the styrene–butadiene rubber. A clear impact acrylic is separated into a methyl methacrylate–styrene–acrylonitrile copolymer and a methyl methacrylate–butadiene rubbery copolymer. Photomicrographs indicate that clarity in the clear ABS and impact acrylic is achieved by matching refractive indices of the continuous and dispersed polymer phases.     

Synthesis of graft copolymer of styrene and acrylonitrile onto poly (butyl acrylate) by using polymeric peroxide

Summary Two-stage seeded emulsion copolymerization of butyl acrylate with tert-butyl 3-isopropenylcumylperoxide (D120) was performed at 70°C . Copolymer latex with 0.2μm of particle size was obtained. Emulsion graft polymerization of styrene and acrylonitrile onto the copolymer of butyl acrylate was initiated by peroxy bonds in the D120 units of the backbone chains at 120°C . Graft copolymers with higher grafting ratio were derived. It was found that the grafting ratio tends to increase with the increasing D120 in feed of copolymerization with butyl acrylate. The graft copolymers were blended with SAN resin, and a kind of AAS resin was obtained. Both elongation at break and Izod impact strength of the AAS resin reached maximum at grafting ratio of 0.25, which were comparable with the values of ABS resin for general purpose. A method to improve the grafting efficiency on the saturated polyacrylate elastomer rubber was developed. Received: 6 March 2002 / Revised version: 8 May 2002 / Accepted: 13 May 2002     

耐候性AAS树脂的制备及对PVC的改性

采用乳液聚合接枝法,以丙烯酸丁酯橡胶为核,以苯乙烯丙烯腈共聚物为壳,制备了AAS树脂。并用AAS树脂对硬质聚氯乙烯(PVC)进行了改性。同时考察了复合稳定剂对PVC加工性能的影响。实验结果发现:当AAS树脂质量分数由10%提高到30%时,材料的冲击强度由200 J/m提高到了1 000 J/m,复合稳定剂的加入明显提高了PVC树脂的挤出性能。     

Mechanical properties and deformation behaviors of acrylonitrile‐butadiene‐styrene under Izod impact test and uniaxial tension at various strain rates

Two polybutadiene‐graft‐acrylonitrile‐styrene copolymer (PBD‐g‐SAN) impact modifiers with different rubber particle size were synthesized by seeded emulsion polymerization. Acrylonitrile‐butadiene‐styrene (ABS) blends with a constant rubber concentration of 15 wt% were prepared by blending those impact modifiers and SAN resin. The major focus was the mechanical properties and deformation mechanisms of ABS blends under Izod impact test and uniaxial tension at various strain rates from 2.564 × 10^?4 S^?1 upto 1.282 × 10^?1 S^?1. By the combination of transmission electron microscope and scanning electron microscope, it was concluded that crazes and cavitation coexisted in ABS blends. The deformation mechanisms of ABS blend containing large rubber particles was rubber particles cavitation and shear yielding in the matrix including crazes, and they do not change with the strain rate. Different from ABS blend with large rubber particles, deformation mechanism of ABS with small rubber particles under tensile condition was only involved in shear yielding in the matrix and no crazes were formed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

ABS树脂湿法挤出工艺及其力学性能的研究

采用湿法挤出工艺,即将乳液聚合合成的丙烯腈-丁二烯-苯乙烯(ABS)接枝共聚物经凝聚和过滤后得到的ABS接枝共聚物湿粉料与苯乙烯-丙烯腈共聚物(SAN)以一定的比例投入湿法挤出机内挤出造粒,直接获得了ABS树脂。考察了ABS接枝共聚物湿粉料含水量、ABS树脂中橡胶含量、抗氧剂含量、挤出机温度及螺杆转速等因素对ABS树脂力学性能的影响。结果表明,挤出温度过高明显引起物料降解,ABS树脂的冲击强度减小,拉伸强度降低;ABS接枝共聚物湿粉料含水量对ABS树脂的性能没有明显影响;透射电子显微镜分析表明,橡胶粒子在SAN基体中分散均匀;湿法挤出的最佳工艺参数为,挤出温度:180℃,螺杆转速:200 r/min,抗氧剂含量:0.154%(质量分数,下同)。     

Analysis of thermal stability of acrylonitrile-acrylic elastomer-styrene terpolymer in injection molding

Acrylonitrile-acrylic elastomer-styrene terpolymer (AAS resin) was developed to improve weatherability of acrylonitrile-butadiene-styrene terpolymer (ABS resin). To compare thermal stability of both resins, test parts of AAS and ABS resins were injection molded at various temperatures and the Izod impact value of the resulting moldings was measured. A study was then made to find the relationship between this value and deterioration of the resins. AAS resin was molded at temperatures from 180°C to 280°C. The impact value of the resulting moldings was almost constant for temperatures up to 260°C, with the first major decrease occurring at 280°C. In contrast, the impact value of conventional ABS resin moldings constantly decreased as the molding temperature was elevated. To explain this phenomenon in both resins, two types of test program steps were undertaken: (1) The cause of the change in characteristics of the AAS resin was determined by obtaining its stress-strain curve in a high-speed flexural strength test; measuring its infrared absorption spectrum; and determining its flow properties with a constant-pressure extrusion type rheometer; (2) the distribution of elastomer in the resin was observed with an electron microscope. It was found that the decrease of impact values of both resins at high temperatures is caused by deterionration of the elastomer. Also, it was found that the different relationships between the impact value and molding temperatures for AAS and ABS resins are due to the difference between the rates of thermal degradation of the acrylic elastomer and butadiene elastomer.     

苯乙烯-异戊二烯-丁二烯三元集成胶乳增韧ABS树脂

采用自由基乳液聚合方法,通过苯乙烯-异戊二烯-丁二烯三元共聚合技术,设计合成了新型三元集成胶乳（SIBL）替代传统成本较高的聚丁二烯胶乳（PBL）,制备丙烯腈-丁二烯-苯乙烯共聚物（ABS树脂）。将高温乳液法制备的SIBL进行附聚,再经过乳液接枝法制备高胶含量的ABS粉料,最后将ABS粉料与本体苯乙烯-丙烯腈共聚物（SAN树脂）掺混、熔融挤出、造粒,制备了低成本新型ABS树脂。考察三种单体配比对SIBL聚合动力学和粒径大小、分布、凝胶含量及玻璃化转变温度（T_g）的影响规律;研究单体配比对SIBL接枝反应和ABS树脂性能影响规律。结果表明: 采用自由基乳液聚合制备三元集成胶乳的方法可行,得到的增韧ABS树脂综合性能优异,其中最具代表ABS树脂韧性的悬臂梁缺口冲击强度得到显著提高,由139J/m提高到233J/m。     

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。     

ABS树脂湿法挤出工艺及产品力学性能的研究

采用湿法挤出工艺,即将乳液聚合合成的经凝聚和过滤的丙烯腈-丁二烯-苯乙烯（ABS）湿粉料与苯乙烯-丙烯腈共聚物（SAN）树脂以一定的比例投入湿法挤出机内挤出造粒,直接获得了ABS树脂。考察了ABS粉料含水量、ABS树脂中橡胶含量、抗氧剂含量、挤出机温度及螺杆转速等因素对ABS树脂力学性能的影响。结果表明,挤出温度过高明显引起物料降解,ABS树脂的冲击强度减小,拉伸强度降低;ABS粉料含水量对ABS树脂的性能没有明显影响;透射电子显微镜分析表明,橡胶粒子在SAN基体中分散均匀;湿法挤出的最佳工艺参数为,挤出温度：180 ℃,螺杆转速：200 r/min,抗氧剂含量：0.154 %（质量分数,下同）。     

连续本体法制备高性能ABS树脂用橡胶的研究

采用不同的橡胶种类和橡胶配比与苯乙烯、丙烯腈进行连续本体法丙烯腈丁二烯苯乙烯共聚物(ABS)中试生产,并对不同条件下的ABS产品进行微观结构和溶胶过程分析。结果表明,使用独山子低顺式聚丁二烯橡胶（50AF）制备的本体ABS产品性能全面优于上海高桥低顺式聚丁二烯橡胶（55AE）、50AF与燕山高顺式聚丁二烯橡胶（BR9004）组成的混合胶; 混合胶中,当50AF与BR9004的混合配比为7∶3时ABS产品性能更好;ABS产品冲击强度均随着胶液含量的增加而增大,熔体流动速率均随着胶液含量的增加而降低。     

Synthesis and properties of styrene–EPDM–vinyl acetate graft polymer

The styrene–EPDM–vinylacetate (SEV) graft polymer, which linked respectively the styrene (St) unit and vinylacetate the (VAc) unit to the ethylene–propylene–diene terpolymer (EPDM) backbone was synthesized by two‐step graft polymerizations: First the graft polymerization of VAc onto EPDM was carried out, and then St was added successively in the prepolymerized solution and further polymerized for a given period to obtain SEV. The effects of concentration of EPDM and an initiator, mole ratio of VAc to St, polymerization time, temperature, and solvent were examined on the graft polymerizations. The synthesized graft polymers (SEVs) that have different contents of St or VAc were identified by Fourier transform IR spectrum. The highest graft ratio has been obtained by 10 wt % of EPDM, 1.0 mole ratio of VAc to St, and 1.0 wt % of BPO in toluene for 48 h at 70°C. The glass transition temperature of SEV is lower than that of poly(vinyl acetate) (PVAc) and polystyrene (PS). The thermal stability of SEV is higher than that of PVAc, PS, and the acrylonitrile–butadiene–styrene (ABS) resin. The tensile strength of SEV was improved as compared with that of EPDM. The light resistance and weatherability of SEV were better than those of ABS. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2296–2304, 2000     

高转化率乳聚丁苯橡胶聚合过程中乳液相对分子质量分布与粒径分布考察

采用中石油吉化分公司乳聚丁苯橡胶高转化率大生产配方,考察了实验室聚合反应釜聚合反应单体转化率随反应时间的变化,采用激光粒度分析仪和凝胶渗透色谱仪测定了聚合反应不同单体转化率的胶乳的粒径分布与分子质量分布,结果表明：胶乳粒径呈正态分布,粒径主要集中分布在0.1μm附近,胶乳的平均粒径随反应时间的延长逐渐增大,但是增加的幅度越来越小;聚合反应时间在11 h前（即转化率小于72%）,胶乳的重均分子质量、Z均分子质量一直增大,而数均分子质量变化无明显规律;而分子质量分布宽度指数随反应的进行变小,表明调整的高转化率配方合成的丁苯橡胶可有效改善聚合生成的胶乳粒径分布。     

橡胶粒子粒径对ABS树脂结构与性能的影响

采用乳液技术在聚丁二烯(PB)和丁苯橡胶(SBR)乳胶粒子上接枝共聚苯乙烯和丙烯腈合成了PB质量分数为60％的ABS接枝粉料,将其与苯乙烯-丙烯腈共聚物(SAN树脂)熔融共混获得了一系列不同组成和结构的丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂),研究了橡胶粒子粒径对ABS树脂的形态结构、力学性能的影响.结果表明,PB和SBR橡胶粒子的粒径分别为0.3μm和0.05 μm左右时,橡胶粒子的粒径对ABS树脂力学性能的影响十分显著.单独采用小拉径SBR橡胶粒子不能有效地增韧SAN树脂,而大粒径PB橡胶粒子对SAN树脂具有良好的增韧效果.     

连续本体法ABS制备工艺进展

综述了连续本体法丙烯腈/丁二烯/苯乙烯(ABS)的制备工艺、接枝和相反转过程的工艺特征、调控粒径及改进性能的方法,指出各种制备工艺的共性和区别,总结出连续本体法ABS制备工艺的关键.     

本体聚合ABS树脂技术进展

综述了国内外主要本体聚合丙烯腈-丁二烯-苯乙烯(ABS)树脂生产工艺,分析了各工艺的技术特点及其成熟度,总结了本体聚合工艺中的关键技术(如ABS树脂性能的影响因素和橡胶粒径的控制方法等)。本体法是最佳的ABS树脂生产工艺,正成为研究重点。本体聚合ABS树脂工艺的研究方向:调整工艺配方、加入第三单体改性、将本体ABS树脂与乳液接枝-掺混法获得的ABS树脂共混制备高性能的ABS树脂新产品。     

The effect of carboxylic monomers on surfactant-free emulsion copolymerization

A study was made of the effect of carboxylic monomers on the surfactant-free emulsion polymerization of styrene and styrene–butadiene. Acid monomers, such as acrylic acid, methacrylic acid, and itaconic acid, were shown to play a critical role in particle formation and particle stabilization in such systems. In the emulsion polymerization of styrene, methacrylic acid forms particles more efficiently than acrylic acid. This difference is attributed to the more hydrophobic nature of the methacrylic monomer which allows it to diffuse more rapidly to the particle surface where it acts to prevent agglomeration. The ability of carboxyl groups to orient at the particle–water interface was studied by acid–base and soap titrations of carboxylated styrene–butadiene latices. The polymerization of itaconic acid onto the particle surface of a styrene–butadiene latex produces a surface carboxyl density much higher than is obtainable with classically adsorbed surfactants. This result is used to explain the greater stability of carboxylated versus noncarboxylated emulsion polymers. During the polymerization of styrene–butadiene latices, carboxyl groups dervied from methacrylic acid are shown to be buried more deeply into the particle as compared to carboxyls derived from the more hydrophilic acrylic acid which orient more at the particle–water interface.     

Impact behavior and fracture morphology of acrylonitrile–butadiene–styrene resins toughened by linear random styrene–isoprene–butadiene rubber

A novel toughening modifier, styrene–isoprene–butadiene rubber (SIBR), was used to improve the impact resistance and toughness of acrylonitrile–butadiene–styrene (ABS) resin via bulk polymerization. For comparison, two kinds of ABS samples were prepared: ABS‐1 was toughened by a conventional modifier (a low‐cis polybutadiene rubber/styrene–butadiene block copolymer), and ABS‐2 was toughened by SIBR. The mechanical properties, microstructures of the as‐prepared materials, and fracture surface morphology of the specimens after impact were studied by instrumented notched Izod impact tests and tensile tests, transmission electron microscopy, and scanning electron microscopy, respectively. The mechanical test results show that ABS‐2 had a much higher impact strength and elongation at break than ABS‐1. The microscopic results suggested that fracture resistance of ABS‐1 only depended on voids, shear yielding, and few crazing, which resulted in less ductile fracture behavior. Compared with ABS‐1, ABS toughened by linear random SIBR (ABS‐2) displayed the synergistic toughening effect of crazing and shear yielding, which could absorb and dissipate massive energy, and presented high ductile fracture behavior. These results were also confirmed by instrumented impact tests. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Softening phenomenon by remilling of styrene–butadiene copolymer rubber–general-purpose polystyrene resin blend

The softening phenomenon by remilling of uncured blends of various commercia styrene—butadiene copolymer rubber (styrene content, 23.5 to 48 wt-%, styrene block 0 to 18 wt-%) with general-purpose polystyrene resin was mainly studied by examining the blend ratio dependence of hardness and compression modulus (in logarithmic form), with special attention to the state of dispersion of the polymers. It was found that the blend of styrene—butadiene copolymer rubber with general-purpose polystyrene resin forms a microheterogeneous polymer blend system and that the hardness and the compression modulus change in S-shaped curves versus blend ratio. However, the degree of softening phenomenon by remilling (roll surface temperature, 70°–90°C) was found to be different for the two blend systems, i.e., random styrene—butadiene copolymer rubber and block styrene—butadiene copolymer rubber. The softening phenomenon is more pronounced in random-type rubbers; and in some block-type rubbers, no softening phenomenon was observed. The influence of the styrene content of the polymer is small. Further discussions have shown us that the strong interaction between the polystyrene block of the copolymer and the styrene homopolymer of the general-purpose polystyrene resin controls the state of dispersion of polymers thereby causing this difference in the softening phenomena among the different kinds of styrene—butadiene copolymer rubbers.     

ABS树脂的性能与形态结构设计 ⅠSAN在PB橡胶粒子上接枝率的控制及其对ABS树脂结构和性能的影响

采用种子乳液聚合技术在聚丁二烯乳胶粒上接枝共聚苯乙烯和丙烯腈 ,通过改变共聚单体和聚丁二烯的投料比合成了一系列PB g SAN共聚物 ,将这些共聚物与SAN树脂进行熔融共混制得了ABS树脂。研究了投料比对SAN在PB上的接枝率、SAN的分子量和ABS树脂的形态结构及性能的影响。结果发现 ,随着投料比的增加 ,SAN在PB上的接枝率及SAN的分子量提高 ,接枝率和SAN分子量共同作用影响着ABS树脂的冲击韧性和加工性能。形态结构研究结果表明 ,投料比不仅影响着橡胶粒子在SAN基体中的分散程度 ,而且影响着橡胶粒子的内部结构 ,随着投料比的增加 ,橡胶粒子在基体中的分散程度提高 ,其内部的包容结构增多并导致了橡胶粒子粒径的增大。