Preparation and characterization of high‐impact polystyrene using different types of polybutadiene

The mechanical, morphological, and rheological properties of polymer blends based on polystyrene (PS) and three different types of polybutadiene (PB) were studied. The polymer blends containing 20% of PB were processed in a Haake mixer at 180°C and 60 rpm for 6 min. The materials exhibited impact strength superior to that of the PS. An increase was observed in the impact strength of 138, 208, and 823%, when low‐cis polybutadiene (PB_l), high‐cis polybutadiene (PB_h), and styrene–butadiene block copolymer (PB_co), were respectively used. The materials presented dispersed morphology with polybutadiene domains, with sizes inferior to 1 μm, randomly distributed in the PS matrix. The viscous and storage moduli increased as the applied frequency increased. The flow activation energy, calculated by Arrhenius equation, varied from 34 to 71 kJ/mol. In the rheological experiments all polymer blends presented pseudoplastic behavior, showing decreasing viscosities as the shear rate increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced miscibility and strain resistance of blended elastomer/π‐conjugated polymer composites through side chain functionalization towards stretchable electronics

This work presents improved compatibility in an elastomer/π‐conjugated polymer blend through side chain functionalization of the electronic polymer. Poly[(3‐(6‐bromohexyl)thiophene)‐ran‐(3‐hexylthiophene)] (P3Br_xHT, x = 0%–100%) was synthesized (i) to improve miscibility with polybutadiene (PB) elastomer through altered π–π interactions and (ii) to covalently bond across phase‐segregated interfaces. Functionalization led to morphology with reduced domain sizes to improve crack onset strain from 7% to 40%. Furthermore, UV‐activated crosslinking reinforced mechanically weak interfaces and yielded at least an additional 40% increase in crack onset strain. Charge mobility in PB/P3Br_xHT organic field‐effect transistors showed minimal dependence on bromide concentration and no negative effects from crosslinking. Functionalization was an effective method to reduce brittleness in PB/P3Br_xHT blends through morphology modification and crosslinking to improve stability towards strain for potential stretchable electronic applications. © 2019 Society of Chemical Industry     

Styrene–butadiene block copolymer with high cis‐1,4 microstructure

The sequential block copolymerization of styrene (St) and butadiene (Bd) was carried out with an activated rare earth catalyst composed of catalyst neodymium tricarboxylate (Nd), cocatalyst Al(i‐Bu)₃ (Al), and chlorinating agent (Cl). The microstructure, composition, and morphology of the copolymer were characterized by FTIR, ¹H NMR, ¹³C NMR, and TEM. The results show that styrene–butadiene diblock copolymer with high cis‐1,4 microstructure of butadiene units (～ 97 mol %) was synthesized. The cis‐selectivity for Bd units was almost independent on the content of styrene units in the copolymer ranging from 18.1 mol % to 29.8 mol %. The phase‐separated morphology of polystyrene (PS) domains of about 40 nm tethered by the elastomeric polybutadiene (PB) segments is observed. The PS‐b‐cis‐PB copolymer could be used as an effective compatilizer for noncompatilized binary PS/cis‐PB blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of the polybutadiene/poly(styrene‐co‐acrylonitrile) ratio in a polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) impact modifier on the morphology and mechanical behavior of acrylonitrile–butadiene–styrene blends

Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005     

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     

Morphology of the transparent IPN‐like system PE: (BMA‐co‐S)

In the study of interpenetrating polymer networks (IPN)‐like systems consisting of polyethylene (PE) and butyl methacrylate (BMA)–styrene (S) copolymer PE/(BMA‐co‐S), the effect of the crosslinker on the morphology of IPN by using electron microscopy and atomic force microscopy (AFM) was investigated. The IPN‐like system PE/(BMA‐co‐S) represents a two‐phase system with finely dispersed domains of crosslinked PE matrix. The interphase between dispersed domains and PE matrix is inhomogeneous and is considered the most interpenetrated part of this IPN‐like system. The size of the domains decreases with the content of crosslinker used. The AFM micrographs allowed the observation of PE lamellae with lengths of about 25 nm. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2615–2620, 2001     

Grafted stock synthesis of ABS at the ultimate high ratio of polybutadiene to poly(styrene‐co‐acrylonitrile)

This study describes the emulsion grafting of styrene and acrylonitrile onto 60–70% polybutadiene (PB), in the presence or absence of tert‐dodecanetiol as a chain transfer reagent with a radical initiator, and the properties of the obtained grafted stock. There was no significant difference in terms of effect of the initiation mode on the grafting efficiency resulting from the high grafting reactivity of PB. However, the grafted stock with 70% PB prepared in the presence of tert‐dodecanetiol and the adequate selection of an initiation system gave a homogeneous dispersion of the PB particles into poly(styrene‐co‐acrylonitrile) (SAN) matrix. The initiation system involves tert‐butyl peroxylaurate, tert‐butyl peroxyacetate, and tert‐butyl peroxyisopropylcarbonate coupled with ferrous sulfate. The efficient coverage of the SAN grafted layer around 70% PB particles was observed by TEM to eventually give excellent impact resistance, high surface gloss, and good thermal resistance. The absence of tert‐dodecanetiol resulted in a toughness reduction of ABS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3462–3470, 2001     

Effect of maleic anhydride grafted polybutadiene on the compatibility of polyamide 66/acrylonitrile‐butadiene‐styrene copolymer blend

The addition of maleic anhydride grafted polybutadiene (PB‐g‐MAH) can greatly improve the compatibility of polyamide 66 (PA66)/acrylonitrile‐butadiene‐styrene copolymer (ABS) blends. Unlike the commonly used compatibilizers in polyamide/ABS blends, PB‐g‐MAH is compatible with the ABS particles' core phase polybutadiene (PB), rather than the shell styrene‐acrylonitrile (SAN). The compatibility and interaction of the components in the blends were characterized by Fourier transform‐infrared spectra (FTIR), Molau tests, melt flow index (MFI), dynamic mechanical analyses (DMA), and scanning electron microscopic (SEM) observations. The results show that PB‐g‐MAH can react with the amino end groups in PA66 while entangle with the PB phase in ABS. In this way, the compatibilizer anchors at the interface of PA66/ABS blend. The morphology study of the fracture sections before and after tensile test reveals that the ABS particles were dispersed uniformly in the PA66 matrix and the interfacial adhesion between PA66 and ABS was increased significantly. The mechanical properties of the blends thus were enhanced with the improving of the compatibility. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Photochemistry of 2,6‐di(4′‐azidobenzylidene)‐methylcyclohexanone in polymer matrices

2,6‐Di(4′‐azidobenzylidene)‐methylcyclohexanone (ABC) was one of the most used photoinitiators in negative photoresists industry, rendering insolubility of the resist films at short UV exposure times (several minutes). Although the photodecomposition of aromatic azides is very well established, the peculiarities of the irradiation medium impose specific reaction pathways for arylnitrenes. In this study, photoreactions of arylnitrenes resulted from ABC photolysis were applied in the photoinitiated crosslinking of 1,2‐polybutadiene (1,2‐PB), under soft monochromatic UV irradiation (365 nm). To elucidate the crosslinking mechanism, studies on a model compound were performed. 3‐Methyl‐1‐butene was chosen to simulate the monomeric unit of 1,2‐PB. As a support in photoproducts identifying and with the purpose of a deeper investigation of the ABC photochemistry alone, ABC was photolysed in a rigid matrix of poly(methyl methacrylate). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44694.     

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.     

Preparation,structure, and properties of end‐functionalized miktoarms star‐shaped polybutadiene–sn–poly(styrene–butadiene) rubber

Two miktoarm star‐shaped rubbers with large‐volume functional groups of 1,1‐diphenylhexyl at the ends of arms (DMS–PB–SBR) and one miktoarm star‐shaped rubber with n‐butyl groups at the ends of arms (BMS–PB–SBR) were prepared by 1,1‐diphenylhexyllithium (DPHLi) and n‐butyl lithium as initiators, respectively. The molecular structures and morphological properties of the three rubbers (MS–PB–SBR) were studied and compared with those acquired from the blend consisting of star‐shaped solution‐polymerized butadiene styrene rubber (S‐SSBR) and butadiene rubber (PBR) prepared by ourselves. The results showed that MS–PB–SBR exhibited a more uniform distribution of PBR phase and a smaller phase size of PBR than that of S‐SSBR/PBR blend. It is found that MS–PB–SBR composites filled with CB showed the lower Payne effect than that of S‐SSBR/PBR/CB composite, suggesting that the MS–PB–SBR/CB composite (particularly the DMS–PB–SBR/CB composites) would possess excellent mechanical properties, high wet‐skid resistance, and low rolling resistance. For the studied MS–PB–SBR systems, the contribution of large‐volume functional groups at the end of PBR molecular chains to decrease the rolling resistance was larger than that of Sn coupling effect. It is envisioned that the miktoarm star‐shaped rubbers with 1,1‐diphenylhexyl groups at the molecular ends would be useful for making treads of green tires. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40002.     

Nanoscale Cellular Foams from a Poly(propylene)‐Rubber Blend

Plastic foams with nano/micro‐scale cellular structures were prepared from poly(propylene)/thermoplastic polystyrene elastomer (PP/TPS) systems, specifically the copolymer blends PP/hydrogenated polystyrene‐block‐polybutadiene‐block‐polystyrene rubber and PP/hydrogenated polystyrene‐block‐polyisoprene‐block‐polystyrene. These PP/TPS systems have the unique characteristic that the elastomer domain can be highly dispersed and oriented in the machine direction by changing the draw‐down ratio in the extrusion process. A temperature‐quench batch physical foaming method was used to foam these two systems with CO₂. The cell size and location were highly controlled in the dispersed elastomer domains by exploiting the differences in CO₂ solubility, diffusivity, and viscoelasticity between the elastomer domains and the PP matrix. The average cell diameter of the PP/TPS blend foams was controlled to be 200–400 nm on the finest level by manipulating the PP/rubber ratio, the draw‐down ratio of extrusion and the foaming temperature. Furthermore, the cellular structure could be highly oriented in one direction by using the highly‐oriented elastomer domains in the polymer blend morphology as a template for foaming.

     

Epifluorescence studies and secondary relaxation processes in immiscible blends of polybutadiene‐poly(2‐vinyl naphthalene) by fluorescence spectroscopy

The development of the morphology of polybutadiene/poly(2‐vinyl naphthalene) blends in five proportions by mass (5, 10, 50, 90, and 95%, w/w) is studied by epifluorescence and scanning electron microscopy (SEM) techniques. The phase separation process of these immiscible polymers produces a primary morphology that is formed by dispersed droplets in a continuous matrix. In the sequence a secondary phase separation inside the primary domains is detected by epifluorescence microscopy of the intrinsically fluorescent domains. Secondary phase separation is confirmed by SEM fracture surface analysis. The relative size of the droplets and the matrix composition depend on the proportion of the components of the blends. The mechanism of the phase separation process is preferentially by nucleation growth for either primary or secondary phase separation processes. Secondary relaxation processes involving the poly(2‐vinyl naphthalene) phase are studied by fluorescence spectroscopy. The profile of the steady‐state excimer fluorescence of poly(2‐vinyl naphthalene) with the temperature in the blend differs from that of the isolated homopolymer and is explained by the contribution from the interface to the radiationless deactivation. The Arrhenius plot for the temperature dependence exhibits slope changes that are related to the polymer relaxation processes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1637–1649, 2002; DOI 10.1002/app.10389     

Blending of styrene‐block‐butadiene‐block‐styrene copolymer with sulfonated vinyl aromatic polymers

Different polymers containing sulfonic groups attached to the phenyl rings were prepared by sulfonation of polystyrene (PS) and styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene (SEBS). The sulfonation degree (SD) was varied between 1 and 20 mol% of the styrene units. Polyphase materials containing sulfonated units were prepared by blending styrene‐block‐butadiene‐block‐styrene (SBS), with both sulfonated PS and sulfonated SEBS in a Brabender mixer. Such a procedure was performed as an alternative route to direct sulfonation of SBS which is actually not selective towards benzene rings because of the great reactivity of the double bonds in polybutadiene (PB) blocks to sulfonation agents. Thermal and dynamic‐mechanic analysis, together with morphology characterization of the blends, is consistent with obtaining partially compatible blends characterized by higher T_g of the polystyrene domains and improved thermal stability. © 2001 Society of Chemical Industry     

Synthesis of sub‐micrometer core–shell rubber particles with 1,2‐azobisisobutyronitrile as initiator and deformation mechanisms of modified polystyrene under various conditions

BACKGROUND: Sub‐micrometer core‐shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) copolymers with various ratios of polybutadiene (PB) core to polystyrene (PS) shell were synthesized by emulsion grafting polymerization with 1,2‐azobisisobutyronitrile (AIBN) as initiator. These graft copolymers were blended with PS to prepare PS/PB‐g‐PS with a rubber content of 20 wt%. The mechanical properties, morphologies of the core‐shell rubber particles and deformation mechanisms under various conditions were investigated. RESULTS: Infrared spectroscopic analysis confirmed that PS could be grafted onto the PB rubber particles. The experimental results showed that a specimen with a ‘cluster’ dispersion state of rubber particles in the PS matrix displayed better mechanical properties. Transmission electron micrographs suggested that crazing only occurred from rubber particles and extended in a bridge‐like manner to neighboring rubber particles parallel to the equatorial plane at a high speed for failure specimens, while the interaction between crazing and shear yielding stabilized the growing crazes at a low speed in tensile tests. CONCLUSION: AIBN can be used as an initiator in the graft polymerization of styrene onto PB. The dispersion of rubber particles in a ‘cluster’ state leads to better impact resistance. The deformation mechanism in impact tests was multi‐crazing, and crazing and shear yielding absorbed the energy in tensile experiments. Copyright © 2009 Society of Chemical Industry     

The preparation and characterization of high‐performance and thermally stable electroluminescent poly(p‐phenylene‐vinylene‐b‐oligoethylene oxide)

Two luminescent block copolymers (PPVPEO₂₀₀ and PPVPEO₆₀₀), composed of poly(p‐phenylene‐vinylene) (PPV) segments with three phenylene vinylene units and poly(ethylene oxide) (PEO) segments with molecular weight of 200 and 600, respectively, have been successfully synthesized. The structures of the copolymers were verified using FTIR, ¹H‐NMR, and elemental analysis. Single‐layer polymer light‐emitting electrochemical cells (LEC) devices fabricated on the bases of thin films of PPVPEO₆₀₀ and on the bases of thin films of blends of PPVPEO₂₀₀ with additional PEO both demonstrated good electroluminescent (EL) performance with the onset voltage of 2.6 V and EL efficiency of 0.64 cd/A and 0.68 cd/A at 3.2 V, respectively. Thermal analysis shows that the decomposition temperature of PPVPEO₆₀₀ is about 305°C, which is higher than that of PPVPEO₂₀₀ and PEO. AFM studies of PPVPEO₆₀₀ thin films exhibits that the block copolymer self‐assembles to form nanoscale network structures with pseudo‐cross‐linking points, thus accounting for its high thermal stability and good EL performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1118–1125, 2007     

The study of poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyrene)/poly(ethylene oxide) blends

Different hydroxyl content poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyene) [PS(OH)‐X] copolymers were synthesized and blends with 2,2,6,6‐tetramrthyl‐piperdine‐1‐oxyl end spin‐labeled PEO [SLPEO] were prepared. The miscibility behavior of all the blends was predicted by comparing the critical miscible polymer–polymer interaction parameter (χ_crit) with the polymer–polymer interaction parameter (χ). The micro heterogeneity, chain motion, and hydrogen bonding interaction of the blends were investigated by the ESR spin label method. Two spectral components with different rates of motion were observed in the ESR composite spectra of all the blends, indicating the existence of microheterogeneity at the molecular level. According to the variations of ESR spectral parameters T_a, T_d, ΔT, T_50G and τ_c, with the increasing hydroxyl content in blends, it was shown that the extent of miscibility was progressively enhanced due to the controllable hydrogen bonding interaction between the hydroxyl in PS(OH) and the ether oxygen in PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2312–2317, 2004     

Property enhancement in polypropylene ternary blend nanocomposites via a novel poly(ethylene oxide)‐grafted polystyrene‐block‐poly(ethylene/butylene)‐block‐polystyrene toughener–compatibilizer system

Synthesis and characterization of a novel toughener–compatibilizer for polypropylene (PP)–montmorillonite (MMT) nanocomposites were conducted to provide enhanced mechanical and thermal properties. Poly(ethylene oxide) (PEO) blocks were synthetically grafted onto maleic anhydride‐grafted polystyrene‐block‐poly(ethylene/butylene)‐block‐polystyrene (SEBS‐g‐MA). Special attention was paid to emphasize the effect of PEO‐grafted SEBS (SEBS‐g‐PEO) against SEBS‐g‐MA on morphology, static/dynamic mechanical properties and surface hydrophilicity of the resultant blends and nanocomposites. It was found that the silicate layers of neat MMT are well separated by PEO chains chemically bonded to nonpolar SEBS polymer without needing any organophilic modification of the clay as confirmed by X‐ray diffraction and transmission electron microscopy analyses. From scanning electron microscopy analyses, elastomeric domains interacting with MMT layers via PEO sites were found to be distributed in the PP matrix with higher number and smaller sizes than the corresponding blend. As a benefit of PEO grafting, SEBS‐g‐PEO‐containing nanocomposite exhibited not only higher toughness/impact strength but also increased creep recovery, as compared to corresponding SEBS‐g‐MA‐containing nanocomposite and neat PP. The damping parameter of the same nanocomposite was also found to be high in a broad range of temperatures as another advantage of the SEBS‐g‐PEO toughener–compatibilizer. The water contact angles of the blends and nanocomposites were found to be lower than that of neat hydrophobic PP which is desirable for finishing processes such as dyeing and coating. © 2018 Society of Chemical Industry     

Reaction‐induced phase separation and resulting thermomechanical and surface properties of epoxy resin/poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) blends cured with 4,4′‐diaminodiphenylsulfone

We investigated the phase separation, cure kinetics and thermomechanical properties of diglycidyl ether of bisphenol‐A/4,4′‐diaminodiphenylsulfone/poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer (TBCP) blends. Fourier transform infrared spectroscopy, differential scanning calorimetry, and atomic force microscopy revealed that the blends exhibited heterogeneous phase morphology in which the TBCP formed dispersed domains in epoxy matrix, due to reaction induced phase separation. A fraction of phase‐separated PEO phase underwent partial crystallization whereas another fraction formed interphases between the dispersed domains and epoxy matrix. Moreover, the dispersed PEO chains improved the compatibility and interfacial adhesion between the matrix and domains and, consequently, significantly improved the mechanical properties of epoxy resin. Furthermore, the thermal degradation studies and contact angle measurements disclosed that the dispersed domains were well protected by the epoxy matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44406.     

Synthesis and characterization of graft copolymers of syndiotactic polystyrene with polybutadiene and 4‐methylstyrene

The basic method for synthesizing syndiotactic polystyrene‐g‐polybutadiene graft copolymers was investigated. First, the syndiotactic polystyrene copolymer, poly(styrene‐co‐4‐methylstyrene), was prepared by the copolymerization of styrene and 4‐methylstyrene monomer with a trichloro(pentamethyl cyclopentadienyl) titanium(IV)/modified methylaluminoxane system as a metallocene catalyst at 50°C. Then, the polymerization proceeded in an argon atmosphere at the ambient pressure, and after purification by extraction, the copolymer structure was confirmed with ¹H‐NMR. Lastly, the copolymer was grafted with polybutadiene (a ready‐made commercialized unsaturated elastomer) by anionic grafting reactions with a metallation reagent. In this step, poly(styrene‐co‐4‐methylstyrene) was deprotonated at the methyl group of 4‐methylstyrene by butyl lithium and further reacted with polybutadiene to graft polybutadiene onto the deprotonated methyl of the poly(styrene‐co‐4‐methylstyrene) backbone. After purification of the graft copolymer by Soxhlet extraction, the grafting reaction copolymer structure was confirmed with ¹H‐NMR. These graft copolymers showed high melting temperatures (240–250°C) and were different from normal anionic styrene–butadiene copolymers because of the presence of crystalline syndiotactic polystyrene segments. Usually, highly syndiotactic polystyrene has a glass‐transition temperature of 100°C and behaves like a glassy polymer (possessing brittle mechanical properties) at room temperature. Thus, the graft copolymer can be used as a compatibilizer in syndiotactic polystyrene blends to modify the mechanical properties to compensate for the glassy properties of pure syndiotactic polystyrene at room temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009