Synthesis of polystyrene-styrene/butadiene diblock copolymers via reversible addition-fragmentation chain transfer miniemulsion polymerization

Polystyrene-styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization.During the polymerization process,the molecular weight distribution was narrow and the numerical molecular weight of the copolymers increased with increasing conversion of monomers,which was close to the theoretical.FT-IR and ^1H NMR results indicated that the microstructure of the polymer was mainly 1,4-trans-butadiene with small amount of 1,2-units,and composition in the copolymers was obtained.

Thermal Stability Improvement and Structural Change of Oil Gels Formed by Styrene-Butadiene-Styrene Triblock Copolymer Induced by Adding Poly(phenylene ether)

The thermal stability of oil gels formed by styrene-butadiene-styrene triblock copolymer (SBS) was improved by adding a small amount of poly(phenylene ether) (PPE), which has a higher glass transition temperature (Tg). In naphthenic oil which is a good solvent for the butadiene blocks, but a non-solvent for the styrene blocks and PPE, PPE was selectively included into styrene blocks in SBS, and induced the increase of the Tg of these blocks. The melting temperature determined by viscoelastic measurements and softening temperature of the gels were elevated by adding PPE, while no significant change was detected by adding polystyrene. The gel became opaque by adding PPE, and partially separated phases were observed by field emission scanning electron microscopy (FE-SEM). The dependence of the viscoelastic behavior on the PPE concentration can be explained by the structural change observed by FE-SEM.

Synthesis and characterization of miktoarm star copolymer of styrene and butadiene using multifunctional macromolecular initiator

A new kind of multifunctional macromolecular initiator with Sn-C bonds and polydiene arms was synthesized by living anionic polymerization. At first, polydiene-stannum chloride （PD-SnCl3） was prepared by the reaction of n-butyl-Li （n-BuLi）, stannic chloride （SnCl4） and diene. Then PD-SnCl3 was used to react with the dilithium initiator to prepare the multifunctional organic macromolecular initiators. The result suggested that the initiators had a remarkable yield by GPC, nearly 90%. By using these multifunctional macromolecular initiators, styrene and butadiene were effectively polymefized via anionic polymerization, which gave birth to novel miktoarm star copolymers. The relative molecular weight and polydispersity index, microstructure contents, copolymerization components, glass transition temperature （Tg） and morphology of the miktoarm star copolymers were investigated by GPC-UV, ~H NMR, DSC and TEM, respectively. 2009 Xing Ying Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

STUDY ON STYRENE-BUTADIENE BLOCK COPOLYMER FOR THE MODIFICATI0N OF TIRE TREAD

This paper mainly deals with the design and synthesis of a novel styrene-butadieneblock copolymer. When this copolymer is used in the tread portion of tyres, it can improvewet skid resistance and reduce rolling resistance without sacrificing its general physical-mechanical properties. The visco-elastic curve of tire tread using the novel copolymer asits rubber portion was showed. Reactivity ratios for two monomers in the polymerizingsystem were calculated. The diagrams of differelitial, integral and finite difference calculithroughout the whole molecular chain were presented. The influence of the micro- andmacro-structure of the copolymer chain on wet skid resistance and rolling resistance wasdiscussed

Study on the Effect of Carboxyl Terminated Butadiene Acrylonitrile (CTBN) Copolymer Concentration on the Decomposition Kinetics Parameters of Blends of Glycidyl Epoxy and Non-Glycidyl Epoxy Resin

The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo gravimetric analysis (TGA) technique under a nitrogen atmosphere. The blends were prepared by physical mixing and were cured with diamine. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. From this value of reaction order, activation energy (E), and pre-exponential factor (Z) were calculated. It was found that the activation energy increased with the addition of liquid elastomer.

Synthesis and performance of miktoarm star copolymers of styrene and butadiene

A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molecular weight, polydispersity index, microstructure and unit composition of the miktoarm star copolymers were characterized with GPC and 1H-NMR. Performances of the miktoarm star styrene-butadiene rubbers were investigated in comparison with those of the blend rubbers such as the tin-coupled star-shaped random copolymers of styrene-butadiene rubber（S-SBR）/natural rubber （NR） blend rubber and S-SBR/Cis-1, 4-polybutadiene rubber （Cis-BR） blend rubber.

CHARACTERIZATION OF IRON COMPLEXES SUPPORTED ON POLYMER AND THEIR CATALYTIC ACTIVITY IN BUTADIENE POLYMERIZATION

Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.

Performance of CTBN(carboxyl-terminated poly (butadiene-co-acrylonitrile))-EP(diglycidyl ether of bisphenol-A (DGEBA)) Prepolymers and CTBN-EP/polyetheramine (PEA) System

CTBN-EP prepolymers were synthesized from CTBN and epoxy resin under the catalysis of HTMAB. FTIR analyses indicate the formation of ester group between the carboxyl group of CTBN and the oxirane group of epoxy resin. The viscosity of modified prepolymer increases with CTBN content increasing, but the epoxy value of the prepolymer decreases greatly. DSC analyses verify that CTBN affects the curing process of CTBN-EP/PEA system. Mechanical testing presents the improved toughness of CTBN-EP/PEA curings for the decrease of tensile strength, flexural strength and compressive strength, and increase of impact strength and elongation-at-break with the CTBN content increasing. SEM micrographs show the rubber phase with many holes in diameter about 0.5-1.5 μm is formed when CTBN content is lower than 10 phr. However, the pattern of SEM graph shows some stalactite-like strips when CTBN content is higher than 15 phr. Furthermore, the SEM image of 25 phr CTBN sample forms a kind of co-continuous structure.

Studies on Rheological, Thermal, and Mechanical Properties of Polylactide/Methyl Methacrylate-Butadiene-Styrene Copolymer/Poly(propylene carbonate) Polyurethane Ternary Blends

Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.

Volatile Substances in Polymer Toys Made from Butadiene and Styrene

The residual levels and migration behavior of volatile substances were detected using HS-GC/MS for acrylonitrile-butadiene-styrene copolymer (ABS) toys, thermoplastic elastomer toys, and rubber toys made from 1,3-butadiene and styrene found on the Japanese market. The maximum residual level of these volatile substances was 2600 μg/g of styrene in ABS toys. In particular, the levels of known carcinogens 1,3-butadiene, benzene, and acrylonitrile are 5.3, 2.5 and 55 μg/g, which are much lower than the EU limit of 0.1%. Furthermore, some volatile substances migrated from ABS toys into water in amounts of 3 -40 ng/mL. Thermoplastic elastomer toys and rubber toys contained these volatile substances at significantly lower levels than ABS toys.

POLYMER-SUPPORTED LANTHANIDE COMPLEXES FOR THE POLYMERIZATION OF BUTADIENE

The characteristics of styrene-acrylic acid copolymer supported lanthanide complexes (SAAC Ln) (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb, and Lu) were described. A comparison of the activities of SAAC·Ln was made. It was found that in the polymerization of butadiene, a peak in activity appeared at Nd and Pr, Sin, Eu and the heavy lanthanides exhibited low or no activities. The effects of some factors on the activities were discussed. The microstructure of the polymers obtained with all the lanthanides in the series were the same and the content of cis-1, 4 polybutadiene attained was more than 98%.

Comparison of Two Methods in Determining the Composition Distribution of SBS Copolymers

The comparison of the determination of chemical composition distributions of butadiene-styrene copolymers, obtained by the formula method and experimental method of GPC, is given in this paper. The relative error of average composition was shown to be less than 5%. The formula method was found to be a more convenient and time-saving approach in the characterization of the copolymer composition distribution.

我国SBS的供需现状及发展前景分析

随着多套新建或者扩建装置的建成投产,我国苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)的生产能力稳步增长。2023年,我国SBS的生产能力达到161.5万t,表观消费量为91.5万t,预计2028年生产能力和消费量将分别达到200万和100万t。我国SBS产能过剩,市场竞争将更加激烈。今后应该慎重新建或者扩建产能,而是着力于完善现有生产技术,加快新产品和新技术的研究,不断提高产品质量,降低生产成本,在满足国内需求的同时积极开拓国外市场。

FDM用ABS复合材料的改性及其应用研究进展

丙烯腈-丁二烯-苯乙烯共聚物(ABS)具有良好的力学性能和可加工性。近年来,随着熔融沉积成型(FDM)三维(3D)打印技术的不断成熟和发展,ABS及其各类改性复合材料也相应被广泛应用于FDM。本文重点基于FDM技术,首先系统整理了金属类填料、无机非金属类填料、有机高分子类填料、回收废旧聚合物类填料等改性ABS基复合材料的现状,并对其相关性能进行了归纳。同时,对相应的各类ABS改性复合材料的FDM打印制品在医学、民用工业、军用电磁与吸波等领域的前沿应用进行了综述。最后,结合FDM打印技术和ABS改性现状,对未来FDM打印方法以及ABS改性技术提出了几点思考。

星形多臂丁苯共聚物的分子结构设计与合成

以正丁基锂为引发剂、苯乙烯与丁二烯为单体、双四氢糠丙烷为极性结构调节剂、六氯乙硅烷为偶联剂,采用活性负离子聚合技术设计并合成了一系列具有星形结构的多臂丁苯共聚物(S-g-SSB-6)。使用凝胶渗透色谱分析了S-g-SSB-6的分子量及其分布、偶联臂数和偶联效率,使用旋转流变仪测试了S-g-SSB-6、以SiCl_(4)为偶联剂的星形多臂丁苯共聚物及线型结构丁苯共聚物(L-SSB)的流变性能,并考察了支链长度和支链柔顺性对S-g-SSB-6流变性能的影响。结果表明,S-g-SSB-6的偶联臂数达到4.1、偶联效率均大于80%;相同重均分子量下S-g-SSB-6的熔体黏度较L-SSB更低、流体流动性更好;当支化度相同时,S-g-SSB-6的熔体黏度随着单臂分子量和分子链刚性的增加而增大。

EAA-NMP-H_(2)O膨润体系中EAA体积分数对PC-ABS膨润效果的影响

为了考察膨润体系中乙酰乙酸乙酯(EAA)浓度和膨润时间对聚碳酸酯-聚丙烯腈-丁二烯-苯乙烯共聚物(PC-ABS)膨润效果的影响,通过EAA-氮甲基吡咯烷酮(NMP)-水体系对PC-ABS基板进行膨润处理,然后在70℃下,以H_(2)SO_(4)-MnO_(2)-H_(2)O体系为微蚀体系,对PC-ABS基板微蚀20 min。结果表明,当膨润体系中EAA体积分数为50%,膨润温度为55℃时,膨润5 min后PC-ABS可以获得合适的膨润度。通过此条件膨润及微蚀处理后的PC-ABS基板表面形成了分布均匀且致密的孔洞,基板表面与水的接触角减小,基板表面的亲水性增强,后续化学镀铜层与PC-ABS基板间的粘接强度达到4.03 N/cm,获得了理想的膨润和微蚀效果。

基于可低温加工SEBS的发泡母粒及微发泡热塑性弹性体的制备

以可低温加工的氢化苯乙烯-丁二烯嵌段共聚物(SEBS)为基体,将偶氮二甲酰胺(AC)发泡剂、助发泡剂和表面活性剂制备成基于SEBS的发泡母粒,并采用双螺杆挤出机将发泡母粒与动态硫化三元乙丙橡胶(EPDM)/聚丙烯(PP)热塑性弹性体材料(TPE)共混熔融挤出,制备了微发泡TPE材料。研究了SEBS引入量与发泡母粒添加量对微发泡TPE样品的密度、拉伸性能以及泡孔形貌的影响。结果表明,当SEBS的质量分数低于6%,发泡母粒的质量分数为3%时,制备的微发泡TPE材料具有较低的密度、较高的拉伸性能,且泡孔规整度达到最优。

宽频带周期吸波结构设计及3D打印

在轻量化吸波结构的设计中,在减轻质量的同时保持吸波性能是一个巨大的挑战。本文以导电丙烯腈-丁二烯-苯乙烯共聚物(ABS)为吸波材料,设计了不同的吸波结构,采用CST Studio Suite仿真软件优化了吸波结构的几何参数,并通过熔融沉积(FDM)3D打印技术制备出优化的吸波结构进行实验验证,研究了导电ABS的打印参数及不同吸波结构的吸波性能。结果表明,打印温度对打印试样力学性能有一定影响,打印温度为265℃时,打印试样的综合力学性能最佳。3D打印的蜂窝吸波结构的最低反射损耗为-19.1 dB,有效频宽达到5.4 GHz,而模拟最低反射损耗-36.9 dB,有效频宽为6.1 GHz;木堆吸波结构的最低反射损耗达到-21.0 dB,有效频宽为10.6 GHz,优于模拟值(最低反射损耗-18.3 dB,有效频宽5.9 GHz);角锥吸波结构的最低反射率达到-40.9 dB,有效频宽为12.0 GHz,模拟最低反射损耗-35 dB,有效频宽为13.2 GHz。不同填充率对于角锥结构吸波性能有影响,在填充率100%的情况下,达到最低反射损耗,在填充率30%的情况下,有效吸波频宽达到最宽。这项研究为宽频吸波材料的设计和制备提供了新的思路,对于电磁波吸收领域的发展和应用具有重要的指导意义。

不同附聚法聚丁二烯胶乳对ABS性能的影响

采用高分子附聚法和醋酸附聚法获得了大粒径聚丁二烯胶乳(PBL),然后与丙烯腈(AN)和苯乙烯(St)发生乳液接枝聚合反应,制得了丙烯腈-丁二烯-苯乙烯共聚物(ABS)高胶粉。将ABS高胶粉与丙烯腈-苯乙烯共聚物(SAN)共混挤出,制得了ABS树脂。研究了2种附聚法对PBL的粒子形态、粒径大小、粒径分布指数以及ABS树脂性能的影响。结果表明:与醋酸附聚法PBL相比,高分子附聚法PBL的粒径分布指数更大,普遍大于0.10,粒径均一性更差,且存在团聚现象;高分子附聚法PBL接枝后出现黏结现象;由高分子附聚法PBL所得ABS样条断面无明显的“海-岛”结构,抗冲击性能普遍较差。