超细全硫化粉末丁苯橡胶/三元乙丙橡胶共混物的结构与性能

制备了超细全硫化粉末丁苯橡胶(UFPSBR)/三元乙丙橡胶(EPDM)共混物,研究了其硫化特性、相态结构、动态力学性能及物理机械性能。透射电镜观察表明,无论UFPSBR与EPDM共混比如何,UFPSBR粒子始终保持为分散相。当UFPSBR用量为10份(质量)时,它在EPDM中的分散相尺寸为200 nm左右;用量较高时其分散相尺寸较大,存在大量的聚集体。动态力学分析结果显示共混物存在2个玻璃化转变温度,说明共混物存在两相结构。加工性能分析结果表明,UFPSBR粒子在EPDM基质中形成了网络结构,对EPDM基质起到了较好的增强作用,当UFPSBR与EPDM的质量共混比为50/50时,共混物的拉伸强度可达13.4 MPa。UFPSBR对EPDM的硫化特性有明显影响。     

Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

Influence of small rubber particles on the environmental stress cracking of high impact polystyrene

This article exploits the influence of rubber particle size (RPS) and rubber crosslinking on environmental stress cracking resistance (ESCR) of high impact polystyrene (HIPS), with special interest on the influence of small rubber particles fraction. Three commercial HIPS of high ESCR were selected and four batches of HIPS were prepared in‐house, including samples based on high cis and very high viscosity polybutadiene (PB). Their morphologies were analyzed by low angle laser light scattering, optical microscopy, and transmission electron microscopy, and the samples were submitted to flexural ESCR tests with fatty agents. The ESCR to sunflower oil was found to increase with the reduction of the rubber particles fraction smaller than 1–2 micron. Results have also confirmed that an increase in RPS is the key parameter to promote ESCR, although there is limit for RPS to be effective on ESCR improvement. The reduction of small rubber particles fraction in HIPS was achieved by using a high cis PB, that promotes low grafting efficiency of polystyrene onto PB backbone because of the low content of 1,2 vinyl isomer. Besides the ESCR improvements, HIPS with high cis PB showed higher elastic modulus and impact resistance than HIPS containing medium cis PB, which is desired for thickness reduction in food packaging and refrigeration cabinets. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tensile behavior of polypropylene blended with bimodal distribution of styrene‐ethylene‐butadiene‐styrene particle size

The objective is to characterize the effects of the bimodal distribution of rubber particles and its blend ratio on the mechanical properties of the thermoplastic polypropylene blended with two different styrene‐ethylene‐butadiene‐styrene triblock copolymer at the intermediate and high strain rates. Tensile tests are conducted at the nominal strain rates from 3 × 10^?1 to 10² (1/s). Phase morphology is investigated to estimate the bimodal rubber particle size distribution. In addition, the in situ observation is conducted during uniaxially stretching within transmission electron microscopy step by step to investigate the deformation events depending on the elongation of samples. The elastic modulus increased gradually as the blend ratio of large rubber particle increased. An increase in the rupture strain and the strain energy up to failure was found for the bimodal rubber particle distributed blend system where the blend ratios of small rubber particle and large rubber particle were same. This is because the smaller particles dominant blend systems show the bandlike craze deformation while the localized plastic deformation is taken place in the larger particles dominated blend systems. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber particle distributed polypropylene systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of solvent contents on the rubber‐phase particle size distribution of high‐impact polystyrene

High‐impact polystyrene (HIPS) was prepared by the bulk or low‐solvent polymerization of styrene in the presence of dissolved rubber and characterized to measure the dispersed particle size of the rubber phase. Before preparation, the prepolymerization time was established by measuring the evolution of particle size distribution of the dispersed phase as a function of reaction time. The measurement technique by laser light scattering was found to be efficient enough not only to lead to the right prepolymerization time but also to predict rubber‐phase particle size distribution. Polymerization experiments were then conducted to investigate the effect of solvent contents on the particle size distribution of the rubber phase, in which ethylbenzene was introduced as a solvent at levels of 0, 3, 10, and 15%. As the solvent content increased, the size of rubber‐phase particles initially increased, reaching a maximum, and then decreased. It is speculated that a decrease in the molecular weight of the matrix, a decrease in the viscosity ratio between polybutadiene to polystyrene phases, and a change in rubber morphology all contributed to the change in the rubber particle size of HIPS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3672–3679, 2003     

Material ductility and toughening mechanism of polypropylene blended with bimodal distributed particle size of styrene–ethylene–butadiene–styrene triblock copolymer at high strain rate

The material ductility and toughening mechanisms under high strain rate are characterized in the polypropylene (PP) blended with two different styrene–ethylene–butadiene–styrene triblock copolymer (SEBS) by the tensile tests at the nominal strain rates from 0.3 to 100 s^?1, fracture surface observations, interparticle distances, and the morphological finite element (FE) analyses. It is found that the bimodal‐distributed SEBS particle morphology enhances the impact material ductility by craze bands formation, which is caused by the stress interaction between large rubber particles with the highly elongated small rubber particles inside the fibrils of the craze. It is found that there are three conditions for craze bands formation. The first condition is that the total SEBS content is larger than 15 wt %. Second condition is that the weight ratio of small SEBS particles against total SEBS particles should be larger than 0.06. Third condition is that the interparticle distance of large SEBS particles should be larger than 100 nm. In the numerical aspects, the present constitutive law with the craze nucleation and growth can successfully predict the craze bands in the microstructural FE models, leading to the useful procedure for identifying the ductile brittle transition based on the microstructure. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber particle distributed PP systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The use of latex rubber-modified polystyrene as a model system for HIPS: Effect of particle size

The effect of particle size in high-impact polystyrene (HIPS) is difficult to determine because of a size polydispersity and changes in particle morphology during the HIPS synthesis process. In this study, poly(n-butyl acrylate) rubber core/polystyrene shell particles were made by emulsion polymerization methods such that the only difference was in particle diameter, which ranged from 0.4 to 6.2 μm. The latexes were subsequently incorporated into a polystyrene matrix to form a toughened composite that acted as a simple model for HIPS. Charpy impact energies (notched and unnotched) of the composites showed that there was no toughening for particle sizes less than 2μm in diameter. The optimal impact energy was obtained with particle diameters in the region of 2–3 μm at 8 wt % rubber loading. The results imply that craze stabilization is the most important aspect of the toughening process. A simple toughening model based on the crack opening displacement of craze breakdown between adjacent rubber particles is suggested, with interparticle distance as the most important variable. © 1993 John Wiley & Sons, Inc.     

Toughening of polyvinylchloride by methyl methacrylate–butadiene–styrene core–shell rubber particles: Influence of rubber particle size

An analysis was made on the effects of rubber particle size on the mechanical properties and deformation mechanisms of transparent polyvinyl chloride (PVC) blends containing core–shell methyl methacrylate–butadiene–styrene (MBS) impact modifiers. The critical interparticle distance was found not to be the criterion for the brittle‐ductile transition in the blends. In tensile tests, the blends with larger (100–280 nm) rubber particles exhibited intense stress‐whitening, while one blend with small (83 nm) rubber particles showed only slight stress‐whitening. These differences were due to an increase in resistance to cavitation with decreasing rubber particle size. Transmission electron microscopy studies on blends with a bimodal distribution of particle sizes showed that in the whitened zone of Izod specimens the larger rubber particles cavitated and expanded on yielding, while the smaller particles remained intact. However, Izod test results showed that small MBS rubber particles can toughen the PVC matrix very effectively, especially at low temperatures and at low rubber concentrations. The deformation mechanisms responsible for these effects were discussed. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

板材级ABS树脂专用聚丁二烯胶乳的研究

通过小粒径胶乳合成工艺制备粒径100 nm左右的聚丁二烯胶乳(PBL),然后通过附聚得到部分较大粒径PBL,从而获得具有双峰粒径分布的附聚胶乳,附聚胶乳接枝后再与(苯乙烯/丙烯腈)共聚物掺混造粒制得(丙烯腈/丁二烯/苯乙烯)共聚物(ABS)。结果表明,用该附聚PBL制得的ABS树脂具有冲击强度高、熔体流动速率低和断裂伸长率高等特点,适于进行挤出成型,说明该附聚PBL适合制备板材级ABS树脂。     

Toughness and morphology of radiation‐crosslinked natural rubber modified polystyrene

γ‐Radiation vulcanized natural rubber (RVNR)/phase transfer/suspension polymerization technique was used to prepare high‐impact polystyrene (HIPS) in bead form. The high notched Izod impact resistance of HIPS based on RVNR was observed and compared with that of unmodified PS. The impact resistance of HIPS based on RVNR was further enhanced by addition of 10% of polystyrene‐block‐polyisoprene‐block‐polystyrene copolymer. A mesh structure of all crosslinked rubber particles containing polystyrene and long crazes in HIPS were observed under electron microscopy. Copyright © 2003 Society of Chemical Industry     

Characterization of rubber particle size distribution of high-impact polystyrene using low-angle laser light scattering

A new application of low-angle laser light scattering has led to a new instrument capable of characterizing the rubber particle size distribution of high-impact polystyrene (HIPS) containing particles as small as 0.1 μ. Rubber particle size distributions of several HIPS resins have been characterized, and the particle size ranking of resins using light scattering parallels the ranking of resins using photomicroscopy. Several solvents have been employed to suspend the HIPS rubber particles for the scattering determination. Swelling of the rubber phase has been found to be relatively insensitive to variations in rubber phase crosslinking when methyl ethyl ketone is used to suspend the rubber particles. Particle swelling in methyl ethyl ketone does not detract from the usefulness of the light scattering method for HIPS rubber particle size characterization.     

Preparation and characterization of amphiphilic starch nanocrystals

In this article, amphiphilic starch nanocrystals were synthesized by graft copolymerization of starch nanocrystals with styrene in aqueous emulsion system. The starch nanocrystals of size around 50 nm were used, which were prepared by acid hydrolysis of corn starch. The structure of starch‐g‐polystyrene nanocrystals was characterized by Fourier transform infrared and ¹H nuclear magnetic resonance (¹H NMR). The crystalline structure as well as its particle morphology was studied by X‐ray diffraction and scanning electron microscopy, respectively. The results indicated that the amphiphilic starch nanocrystals obtained exhibit the size around 80–100 nm. Its crystalline structure is basically not changed after grafting polystyrene suggested that the polystyrene was essentially grafted on the surface of starch nanocrystals. Wettability experiments indicated that the prepared starch‐g‐polystyrene nanocrystals can be uniformly dispersed both in water phase and oil phase revealing excellent amphiphilicity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel synthesis of poly(methyl methacrylate) brush encapsulated silica particles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter = 20 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. The particle sizes of such core–shell structures [number‐average particle diameter (D_n) = 35–40 nm] were controlled by the variation of the feed amounts of the monomers and surfactant, or emulsion system. The size distributions were relatively narrow (weight‐average particle diameter/D_n ≈ 1.05). These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brush encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly1‐hexene: New impact modifier in HIPS technology

Poly1‐hexene was prepared using a conventional heterogeneous Ziegler–Natta catalyst and its stereoregularity was characterized using ¹³C‐NMR analysis. New kind of high impact polystyrene (HIPS) was prepared by radical polymerization of styrene in the presence of different amounts of synthesized poly1‐hexene (PH) as impact modifier (HIPS/PH) and compared with conventional high impact polystyrene with polybutadiene (HIPS/PB) as rubber phase. Scanning electron microscopy (SEM) revealed that the dispersion of poly1‐hexene in polystyrene matrix was more uniform compared with it in HIPS/PB. The impact strength of HIPS/PH was 29–79% and 80–289% higher than that in HIPS/PB and neat polystyrene, respectively. FTIR was used to confirm more durability of HIPS/PH samples toward ozonation. To study the effect of rubber type and amount on the T_gs of polystyrene, differential scanning calorimetry was employed. Results obtained from TGA demonstrated higher thermal stability of HIPS/PH sample in comparison with conventional HIPS/PB one. Our obtained results suggest new high impact polystyrene that in all studied aspects has better performance than the conventional HIPS. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43882.     

Characterization of rubber particle size distribution of high-impact polystyrene using an image analysis method

Accurate characterization of high-impact polystyrene (HIPS) rubber particle size distribution has been achieved using an automatic image analysis system. The new method involves preparation of a microscope slide consisting of a dilute suspension of HIPS particles in a polymer matrix. Images of silhouetted rubber particles of true diameter are obtained using an image processor and particle size calculations can be made with a minimum of editing of the binary image. The new method provides measurement of true rubber particle diameters because the particles in the prepared slide are not swollen by any solvent.     

Different deformation mechanisms of two modified‐polystyrene bimodal systems

It is well known that the dominant toughening mechanism of rubber‐modified polystyrene is multiple crazing. Some researchers have investigated polystyrene that can be modified by rubbers with dual particle sizes, leading to better mechanical properties. That is, the way to absorb energy during the deformation process is crazing and cavitation induced by rubber particles. Two types of polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber modifiers which have core‐shell structures were synthesized via an emulsion graft polymerization using redox and oil‐soluble initiators, respectively. To balance the yield strength, general‐purpose polystyrene was blended with the PB‐g‐PS modifiers, as well as commercial high‐impact polystyrene. Blends were defined as R‐bimodal and O‐bimodal corresponding to dispersed PB‐g‐PS particles formed using the redox and oil‐soluble initiators, respectively. The impact strength of R‐bimodal was improved significantly by altering the ratio of core to shell. However, little change of impact strength was observed for O‐bimodal. Transmission electron microscopy images of fracture surfaces indicated that the deformation mechanism of R‐bimodal is shear‐yielding induced by multi‐crazing. Moreover, PB‐g‐PS particles dispersed in O‐bimodal can form a ‘cluster’ structure, leading to crazing to absorb energy. Scanning electron microscopy images also showed obvious distinctness between the R‐bimodal and O‐bimodal systems due to different deformation mechanisms. Copyright © 2010 Society of Chemical Industry     

Toughness enhancement of high‐impact polystyrene based on γ‐radiation vulcanized natural rubber latex by using block copolymer

Polyisoprene‐block‐polystyrene‐block‐polyisoprene (ISI) was synthesized by the iniferter route and its use, as compared to a commercial polystyrene‐block‐polyisoprene‐block‐polystyrene (SIS), in the enhancement of the toughness of high‐impact polystyrene (HIPS), prepared by the γ‐radiation vulcanized natural rubber (RVNR) latex/phase transfer/bulk polymerization technique, was investigated. Addition of 5% SIS was adequate as an interfacial agent, which effectively increased the unnotched Izod impact energy of HIPS, whereas use of 10% of ISI was required. A long polyisoprene block with two polystyrene segments of SIS was favorable for compatibilization of HIPS. Transmission electron micrographs revealed the uniform distribution of the block copolymer at the shell region of the rubber particle. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1307–1316, 2002     

高抗冲聚苯乙烯(HIPS)连续生产的模拟

根据热引发连续本体聚合生产高抗冲聚苯乙烯 (HIPS)的动力学机理 ,建立了苯乙烯 /顺丁二烯橡胶本体聚合过程的多釜串联 (CSTR)数学模型 ,并由两个不同品牌的实际工业生产数据对模型进行了验证。得到了各釜出口苯乙烯单体的转化率、HIPS的接枝效率、接枝率以及自由PS的重均分子量及其分布     

ABS/HIPS blends obtained from WEEE: Influence of processing conditions and composition

The recycling of acrylonitrile–butadiene–styrene (ABS) and high‐impact polystyrene (HIPS) from postconsumer electronic equipment housing was investigated. A preliminary study of shot size and particle size effects on the mechanical properties of ABS/HIPS (50/50) blends obtained directly via injection molding was conducted. Injection‐molded specimens of ABS/HIPS blends, obtained at different compositions with or without previous extrusion, were subjected to mechanical, thermal, and morphological testing. Preliminary studies showed that a smaller particle size resulted in higher tensile and impact strength, regardless of the shot size used during injection molding. ABS/HIPS blends obtained using previous extrusion presented a slight increase in Young's modulus and a decrease in elongation at break and impact strength. The increase in glass‐transition temperature related to the Polybutadiene (PB) phases of these blends indicated a possible increase in crosslinking structures during extrusion. In addition, these blends showed a coarse and heterogeneous morphology, suggesting that ABS did not completely mix with HIPS. Compared to processing conditions, the blend composition appeared to have a much stronger effect on the mechanical properties. The results obtained suggest the possibility of obtaining ABS/HIPS blends directly via injection molding as long as small ground particles are used. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43831.     

苯乙烯—低顺式聚丁二烯预聚体的流变特性

以苯乙烯-低顺式聚丁二烯橡胶接技共聚制备高抗冲聚苯乙烯。研究了胶样、橡胶含量,搅拌转速、温度对预聚体的流变行为的影响。发现随着起始橡胶浓度增加,相转变点推迟,当起始浓度达10％时,体系不发生相转变。