Novel tin‐coupled star‐shaped medium vinyl butadiene rubber. I. Arm number and its effect on properties

To achieve low rolling resistance, high wet grip, and favorable overall performance, star‐shaped medium vinyl butadiene rubber (S‐MVBR) was designed and prepared by “core‐first” method, where novel multifunctional organolithium containing Sn atom as initiator, THF as structure regulator, and carbon–hydrogen compound as solvent. The results showed that coupling reaction between SnCl₄ and dilithium is stoichiometrical, and this method has much higher efficiency than the “arm‐first” method. When dilithium is composed of 4–10 repeating units, the average arm number of S‐MVBR is conveniently controlled between 3 and 5 by initiator functionality, which can be easily regulated by the mole ratio of active lithium of dilithium short chain to Cl^? in SnCl₄. As Sn coupling decreases numbers of noncrosslinking free ends, S‐MVBR has lower rolling resistance, dynamic heating and higher wet grip than linear MVBR. Meanwhile, mechanical properties and processing properties are improved. And the formation of multiarm structure has little effect on viscosity. S‐MVBR with arm number of 3.8 has optimal overall performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3917–3923, 2007     

Microhardness of styrene/butadiene block copolymer systems: Influence of molecular architecture

The influence of molecular architecture on the mechanical properties of styrene/butadiene block copolymers was investigated by means of the microhardness technique. It was found that the microhardness of the styrene/butadiene block copolymers is dictated by the nature of microphase separated morphology. In contrast to polymer blends and random copolymers, in which the microhardness generally follows the additivity rule, the behavior of the investigated block copolymers was found to significantly deviate depending on their molecular architecture. The glass‐transition temperature of the polystyrene phase (T_g‐PS), which practically remained constant and that of the polybutadiene phase (T_g‐PB), which varied with the change in the block copolymer architecture, apparently do not influence the microhardness values of the block copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1670–1677, 2003     

Molecular architectures of four‐arm star‐shaped styrene‐butadiene copolymer

To understand the molecular architectures of styrene‐butadiene four‐arm star (SBS) copolymers, a size exclusion chromatography combined with laser light scattering (SEC‐LLS) has been used to determine their weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^1/2), and a new method for the establishment of the Mark‐Houwink equation from one sample has been developed. Based on the Flory viscosity theory, we successfully have reduced the 〈S²〉^1/2 values of numberless fractions estimated from many experimental points in the SEC chromatogram to intrinsic viscosities ([η]). For the first time, the dependences of 〈S²〉^1/2 and [η] on M_w for the four‐arm star SBS in tetrahydrofuran at 25°C were found, respectively, to be 〈S²〉^1/2 = 2.62 × 10^?2 M (nm) and [η] = 3.68 × 10^?2 M (mL/g) in the M_w range from 1.4 × 10⁵ to 3.0 × 10⁵. From data of [η] and 〈S²〉^1/2 for linear and star SBS, we have obtained the information about the branching, namely, the ratios (g and g′) of 〈S²〉 and [η] for star SBS to that of the linear SBS of the same molecular weight, which agree with theoretical predictions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 961–965, 2005     

Molecular weight and arm number of a star‐shaped styrene–butadiene block copolymer synthesized on a pilot‐vessel scale

To improve the rheological properties and processability of industrial rubbers, star‐shaped styrene–butadiene–styrene (SBS) block copolymers were synthesized and characterized in this work. Through the variation of the ratio of divinylbenzene to the diblock anion, a series of SBS samples with three to six arms were prepared. Multi‐angle laser light scattering (MALLS) and size exclusion chromatography (SEC) combined with light scattering (LS) were used to determine the weight‐average molecular weight (M_w), radius of gyration (〈S²〉^1/2), arm number, and chain conformation. The results from MALLS indicated that the M_w values of the star‐shaped SBS copolymers were 9.0, 13.0, 14.9, and 18.1 × 10⁴, which corresponded to three, four, five, and six arms, respectively. There was a lot of M_w and 〈S²〉^1/2 data for the many fractions in the SEC chromatograms of the SBS copolymers in tetrahydrofuran (THF) detected by LS, so the exponent of 〈S²〉^1/2 = KM_w^α was determined to range from 0.59 to 0.30 for the samples having three to six arms. An analysis of the results revealed that the star SBS copolymers existed in a sphere conformation in THF, and their chain density increased with an increase in the arm number. The viscosity of the six‐arm SBS copolymer was reduced significantly, compared with that of the SBS samples having three to five arms, when their M_w values were similar. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1853–1859, 2007     

Compatibilization efficiency of styrene‐butadiene block copolymers as a function of their block number

Effect of block number in linear styrene‐butadiene (SB) block copolymers (BCs) on their compatibilization efficiency in blending polystyrene (PS) with polybutadiene (PB) was studied. Di‐, tri‐, or pentablocks of SB copolymers as well as their combinations were blended with the mentioned homopolymers; supramolecular structure determined by small angle X‐ray scattering method (SAXS), morphology using scanning electron microscopy (SEM) combined with image analysis (IA), and stress transfer characteristics of the blends were chosen as criteria of compatibilization efficiency of the copolymers used. It was proved that the addition of SB BCs led to remarkably finer phase structure and substantially higher toughness of PS/PB blends. Triblock copolymer showed to be the compatibilizer with higher efficiency than diblock, pentablock, and the di/triblock copolymer mixture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

对称型双端过渡态丁二烯/苯乙烯嵌段共聚物的性能研究

采用以双卤代烷烃取代型双锂齐聚物为引发剂、环己烷为溶剂、丁二烯 (B)、苯乙烯 (S)单体一次加入的方法 ,合成了对称型双端过渡态丁二烯 /苯乙烯嵌段共聚物S— (S/B)—B— (B/S)—S ,并对其性能进行了研究。结果表明 ,对称型双端过渡态丁二烯 /苯乙烯嵌段共聚物具有明显的海岛两相结构 ,嵌段共聚物存在两个玻璃化温度 ;随着单体配比 (质量比 )S/B的增大 ,嵌段共聚物的各项物理性能变化趋势不明显。     

Water‐soluble macromolecular co‐assemblies of star‐shaped polyelectrolytes

This mini‐review reports on complex macromolecular architectures (interpolyelectrolyte complexes) based on star‐shaped polyelectrolytes. These complexes can be prepared in aqueous media via electrostatically driven co‐assembly of star‐shaped polyions (a) with oppositely charged linear homopolyelectrolytes or (b) with oppositely charged double hydrophilic (ionic/non‐ionic) diblock copolymers. In case (a), the complexes can be water‐soluble if the charge of the star‐shaped macromolecule is only partially compensated by a linear polyion. In case (b), the complexes retain their solubility in aqueous media even under a full charge compensation of the polymeric components. In both cases, the complex macromolecular architectures based on star‐shaped polyelectrolytes are characterized by a distinct compartmentalized structure of a micellar (‘core–corona’) type with an insoluble core, which is assembled from coupled monomer units of the oppositely charged polymeric components, and a hydrophilic, either ionic or non‐ionic, corona. Copyright © 2012 Society of Chemical Industry     

Styrene‐butadiene‐styrene copolymer compatibilized interfacial modified multiwalled carbon nanotubes with mechanical and piezoresistive properties

In this study, styrene‐butadiene‐styrene tri‐block copolymer/multiwalled carbon nanotubes (SBS/MWNTs) were prepared by means of a solution blending method. To enhance the compatibility between SBS and MWNTs, the SBS grafted MWNTs (SBS‐g‐MWNTs) were used to replace MWNTs. The MWNTs were chemically hydroxylated by the dissolved KOH solution with ethanol as solvent and then reacted with 3‐Aminopropyltriethoxysilane (APTES) to functionalize them with amino groups (MWNT‐NH₂). The SBS‐g‐MWNTs were finally obtained by the reaction of MWNT‐NH₂ and maleic anhydride grafted SBS (MAH‐g‐SBS). The SBS‐g‐MWNTs were characterized by X‐ray photoelectron spectroscopy (XPS), Fourier transform‐infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The results showed that the SBS molecules were homogeneously bonded onto the surface of the MWNTs, leading to an improvement of the mechanical and electrical properties of SBS/SBS‐g‐MWNTs composites due to the excellent interfacial adhesion and dispersion of SBS‐g‐MWNTs in SBS. A series of continuous tests were carried out to explore the electrical‐mechanical properties of the SBS/SBS‐g‐MWNTs composites. We found out that, near the percolation threshold, the well‐dispersed SBS/SBS‐g‐MWNTs composites showed good piezoresistive characteristics and small mechanical destructions for the development of little deformation under vertical pressure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42945.     

Synthesis of star–comb‐shaped polymer with porphyrin‐core and its self‐assembly behavior study

5,10,15,20‐tetra(4‐hydroxyphenyl)porphyrin (THPP) was synthesized by the condensation of pyrrole with 4‐hydroxybenzaldehyde in the presence of solvent (propionic acid). Subsequently, the resulting THPP was converted to a tetrafunctional star‐shaped macroinitiator (porphyrin‐Br₄) by esterification of it with 2‐bromopropanoyl bromide, and then atom transfer radical polymerization (ATRP) of styrene was conducted at 110°C with CuCl/2,2′‐bipyridine as the catalyst system. The resulting product was reacted with NBS to obtain star‐shaped initiator porphyrin‐(PSt‐Br)₄, which was used the following ATRP of the GMA to synthesize star–comb‐shaped grafted polymer porphyrin‐(PSt‐g‐PGMA)₄. The number molecular weight was 2.3 × 10⁴ g/mol, and the dispersity was narrow (M_w/M_n = 1.32). The structure of the polymers was investigated by NMR, UV–vis, IR, and GPC measurement. The self‐assembly behavior of the polymer porphyrin‐(PSt‐g‐PGMA)₄ was studied by DLS and AFM. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and micromechanical deformation behavior of styrene–butadiene block copolymers. IV. Structure–property correlation in binary block copolymer blends

The structure–property correlation in blends consisting of styrene/butadiene block copolymers forming alternating polystyrene (PS) and polybutadiene (PB) lamellae, and PS domains in rubbery matrix was investigated by different microscopic techniques (transmission electron microscopy, scanning force microscopy, and scanning electron microscopy), uniaxial tensile testing, and dynamic mechanical analysis. Unlike the pure lamellar block copolymer, the blends showed predominantly disordered wormlike morphology formed by the intermolecular mixing. These structures allowed a precise control of stiffness/toughness ratio of the blends over a wide range. The blends showed a gradual transition from predominantly viscoplastic to elastomeric behavior with increasing triblock copolymer content. The results demonstrated that the binary block copolymer blends provide the unique possibility of tailoring mechanical properties on the basis of nanostructured polymeric materials. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1219–1230, 2004     

Role of crystalline ethylene‐propylene copolymer on mechanical properties of impact polypropylene copolymer

Impact polypropylene copolymer (IPC) has been known as a multiphase material in which an ethylene‐propylene (EP) random copolymer, serves as toughening component, is dispersed in the homo‐polypropylene hPP matrix. The crystalline EP copolymer (cEP) is another component whose role and microstructural effect on the IPC properties has not been well understood. This work reveals the relationship between the microstructure of cEP and the mechanical properties, that is, impact and tensile resistance, of IPC. We clarify that IPC comprising high contents of cEP with long homo‐PP segment can extend the elongation at break while cEP with high content of homo‐PE segment contributes to high impact strength. Mechanisms for both of these processes have been proposed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of the extrusion process on the morphology and micromechanical behavior of polystyrene‐block‐(polystyrene‐co‐butadiene)‐block‐polystyrene star block copolymer/homopolystyrene blends

The influence of the extrusion process on the morphology and micromechanical behavior of an asymmetric polystyrene‐block‐(polystyrene‐co‐butadiene)‐block‐polystyrene (SBS) star block copolymer and its blends with general‐purpose homopolystyrene (hPS) was studied with films prepared with a single‐screw extruder. The techniques used were transmission electron microscopy and uniaxial tensile testing. Unlike the pure SBS block copolymer possessing a gyroid‐like morphology, whose deformation was found to be insensitive to the processing conditions, the mechanical properties of the blends strongly depended on the extrusion temperature as well as the apparent shear rate. The deformation micromechanism was primarily dictated by the blend morphology. The yielding and cavitation of the nanostructures were the principal deformation mechanism for the blends having a droplet‐like microphase‐separated morphology, whereas cavitation dominated for the blends containing macrophase‐separated layers of polystyrene. The mechanical properties of the blends were further examined with respect to the influence of the temperature and shear rate on the phase behavior of the blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Morphology and micromechanical deformation behavior of styrene–butadiene block copolymers. III. Binary blends of asymmetric star block copolymer with general‐purpose polystyrene

The correlation between morphology, mechanical properties, and micromechanical deformation behavior of the blends consisting of an asymmetric styrene/butadiene star block copolymer (ST2‐S74, total styrene volume content Φ_PS = 0.74) and general‐purpose polystyrene (GPPS) was investigated using transmission electron microscopy and uniaxial tensile testing. Addition of 20 wt % of GPPS to the block copolymer resulted in a drastic reduction in strain at break, indicating the existence of critical PS lamella thickness D_c. Above D_c lamellar block copolymers displayed a transition from ductile to brittle behavior, substantiating the mechanism of thin layer yielding proposed for lamellar star block copolymers. The blends showed a variety of deformation structures ranging from classical crazelike zones to those with internal shearlike components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1208–1218, 2004     

Enhancement of the high‐temperature utility of a polystyrene‐b‐poly(ethylene‐co‐butylene)‐b‐polystyrene block copolymer by friedel–crafts naphthoylation

A procedure was developed for the Friedel–Crafts naphthoylation of the polystyrene segments of a polystyrene‐b‐poly(ethylene‐co‐butene)‐b‐polystyrene (SEBS) triblock copolymer. It was possible to obtain up to 72% 1‐naphthoylation or 100% 2‐naphthoylation of the polystyrene segments in the copolymer. Naphthoylation could also be accomplished using trifluoromethanesulfonic acid as a catalyst. The naphthoylated products were characterized by ¹H‐NMR spectroscopy, size‐exclusion chromatography, and dynamic mechanical thermal analysis. The mechanical properties of the original and naphthoylated polymers were measured from 25 to 125°C. The results obtained indicate that naphthoylation enhances the tensile properties of the polymers at elevated temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1289–1295, 2003     

Toughening of poly(l‐lactide) modified by a small amount of acrylonitrile−butadiene−styrene core‐shell copolymer

A small amount of acrylonitrile‐butadiene‐styrene (ABS) core shell copolymer particles are used to improve the toughness of poly(l ‐lactide) (PLLA) matrix. The incorporation of ABS copolymer dramatically increased the elongation yield at break of PLLA. For PLLA blend with 6.0 wt % ABS copolymer particles, the elongation yield at break increased by 28 times and the notched impact strength improved by 100% comparing with those of neat PLLA. Fourier transformed infrared (FTIR) and dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) measurement results indicated that the special polarity interaction between ester group of PLLA matrix and nitrile group of PSAN shell phase enhanced the interfacial adhesion between PB rubber phase and PLLA matrix and promoted the fine dispersion of ABS particles in PLLA matrix. Meanwhile, ABS core shell particles also showed a certain extent of effects on the crystallinity behavior of PLLA. A small amount of ABS particles became the nucleating sites, and then the degree of crystallinity of PLLA/ABS blends increased. However, the notched impact of PLLA blends decreased because of the aggregation of more ABS particles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42554.     

Synthesis of star‐shaped poly(ϵ‐caprolactone) by samarium‐based tetrafunctional initiator and its dilute‐solution properties

An in situ–generated tetrafunctional samarium enolate from the reduction of 1,1,1,1‐tetra(2‐bromoisobutyryloxymethyl)methane with divalent samarium complexes [Sm(PPh₂)₂ and SmI₂] in tetrahydrofuran has proven to initiate the ring‐opening polymerization of ?‐caprolactone (CL) giving star‐shaped aliphatic polyesters. The polymerization proceeded with quantitative conversions at room temperature in 2 h and exhibited good controllability of the molecular weight of polymer. The resulting four‐armed poly(?‐caprolactone) (PCL) was fractionated, and the dilute‐solution properties of the fractions were studied in tetrahydrofuran and toluene at 30°C. The Mark–Houwink relations for these solvents were [η] = 2.73 × 10^?2M_w^0.74 and [η] = 1.97 × 10^?2M_w^0.75, respectively. In addition, the unperturbed dimensions of the star‐shaped PCL systems were also evaluated, and a significant solvent effect was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 175–182, 2006     

Preparation and characterization of a type of ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone

Combination of the organic–inorganic hybrid such as silsesquioxane with ε‐caprolactone will lead to materials expected to be environmentally friendly and applicable to biomedical usages. A ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone was prepared by ring opening polymerization of ε‐caprolactone catalyzed by Sn(Oct)₂ with hydroxyl terminated ladder‐like poly(phenyl silsesquioxane) as initiator. The copolymers were characterized by proton nuclear magnetic resonance (¹H‐NMR), silicon nuclear magnetic resonance (²⁹Si‐NMR), Fourier‐transform infrared spectrometer (FT‐IR), size exclusion chromatography (SEC), thermo gravimetric analysis (TGA), and differential scanning calorimetry (DSC) in detail. Furthermore, the enzymatic degradation property of the copolymers was also investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42335.     

Synthesis and properties of amphiphilic star block copolymers with star macroinitiators based on a one‐pot approach

Previously, star polystyrenes (PSs) have been prepared by atom transfer radical polymerization (ATRP) of N‐[2‐(2‐bromoisobutyryloxy)ethyl]maleimide (BiBEMI) with a large excess of styrene (St) in one pot. But linear PSs were also present during the formation of the star polymers. In the work reported here, we found that control of the formation of star polymers using a one‐pot approach can be improved by using a two‐step process. The polymerization was conducted first at a low temperature to form multifunctional cores by copolymerization of BiBEMI and St. Second, on increasing the temperature, homopolymerization of St occurred to grow PS arms. Then a series of amphiphilic star polystyrene‐block‐poly(acrylic acid)s, (S₁₄A_x)₁₆, were prepared by ATRP of tert‐butyl acrylate with the star PSs as macroinitiators, followed by selective acidolysis of the poly(tert‐butyl acrylate) blocks. Their micellization was studied using dynamic light scattering, which suggested that (S₁₄A₁₁₂)₁₆ amphiphilic star block copolymers could form unimolecular micelles in a basic aqueous solution. Then pyrene molecules were encapsulated using the (S₁₄A₁₁₂)₁₆ amphiphilic star copolymers and the loading capacity was investigated with UV and fluorescence spectroscopy. © 2013 Society of Chemical Industry     

苯乙烯/异戊二烯/丁二烯(S/I/B)星型嵌段聚合物的研制方法

介绍了近年来的苯乙烯／异戊二烯／丁二烯（S／I／B）星型嵌段聚合物的发展与研制方法。重点评述了星型嵌段聚合物SIB、IB、IBI、SIS的研制方法，提出应用阴离子聚合方法合成星型聚合物的巨大潜力以及目前的任务。     

Graft copolymers and high‐molecular‐weight star‐like polymers by atom transfer radical polymerization

Grafting of tert‐butyl acrylate (tBuA), methyl methacrylate (MMA), and styrene (St) monomers (M) by Cu(I)‐mediated ATRP from polystyrene (PSt) macroinitiator (M_n = 5620, polydispersity index, PDI = 1.12), containing initiating 2‐bromopropionyloxy groups (I) (bound to 34% of aromatic cores; 11 groups per backbone), was performed using conditions suitable for the respective homopolymerizations. The preparation of PSt‐g‐PtBuA in bulk using an initial molar ratio [M]₀/[I]₀ = 140 had a controlled character up to M_n = (132–148) × 10³ (PDI = 1.08–1.16). With MMA and St and using the same [M]₀/[I]₀, preliminary experiments were made; the higher the monomer conversion, the broader was the distribution of molecular weight of the products. Graft copolymerizations of all these monomers at [M]₀/[I]₀ = 840 or 1680 were successfully conducted up to high conversions. Low‐polydispersity copolymers, with very long side chains, in fact star‐like copolymers, were obtained mainly by tuning the deactivator amount in the reaction mixture. (PSt‐g‐PtBuA, DP_n,sc (DP of side chain) = 665, PDI = 1.24; PSt‐g‐PMMA, DP_n,sc = 670, PDI = 1.43; PSt‐g‐PSt, DP_n,sc = 324, PDI = 1.11). Total suppression of intermolecular coupling was achieved here. However, the low concentrations of initiator required long reaction times, leading sometimes to formation of a small amount (～5%) of low‐molecular‐weight polymer fraction. This concomitant process is discussed, and some measures for its prevention are proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3662–3672, 2006