Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004     

Synthesis and characterization of novel polystyrene‐block‐polyurethane‐block‐polystyrene tri‐block copolymers through atom transfer radical polymerization

Background: Radical polymerization is used widely to polymerize more than 70% of vinyl monomers in industry, but the control over molecular weight and end group of the resulting polymers is always a challenging task with this method. To prepare polymers with desired molecular weight and end groups, many controlled radical polymerization (CRP) ideas have been proposed over the last decade. Atom transfer radical polymerization (ATRP) is one of the successful CRP techniques. Using ATRP, there is no report on the synthesis of polystyrene‐block‐polyurethane‐block‐polystyrene (PSt‐b‐PU‐b‐PSt) tri‐block copolymers. Hence this paper describes the method of synthesizing these tri‐block copolymers. To accomplish this, first telechelic bromo‐terminated polyurethane was synthesized and used further to synthesize PSt‐b‐PU‐b‐PSt tri‐block copolymers using CuBr as a catalyst and N,N,N,N″,N″‐pentamethyldiethylenetriamine as a complexing agent. Results: The ‘living’ nature of the initiating system was confirmed by linear increase of number‐average molecular weight and conversion with time. A semi‐logarithmic kinetics plot shows that the concentration of propagating radical is steady. The results from nuclear magnetic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry show that the novel PSt‐b‐PU‐b‐PSt tri‐block copolymers were formed through the ATRP mechanism. Conclusion: For the first time, PSt‐b‐PU‐b‐PSt tri‐block copolymers were synthesized through ATRP. The advantage of this method is that the controlled incorporation of polystyrene block in polyurethane can be achieved by simply changing the polymerization time. Copyright © 2007 Society of Chemical Industry     

Efficiencies of various metallocene/reducing agent catalyst systems in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene block copolymers

Various metallocenes, including bis(η⁵‐cyclopentadienyl)cobalt, bis(η⁵‐cyclopentadienyl)nickel, and bis(η⁵‐cyclopentadienyl)titanium dichloride, combined with various reducing agents, including n‐butyllithium, phenyllithium, and triethylaluminum, have been evaluated for their catalytic efficiencies in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene (SBS) block copolymer. The efficiencies were determined by monitoring the extent of saturation of double bonds on the polybutadiene segment of the copolymer using FTIR and ¹H‐NMR spectroscopy. The cobaltocene/n‐butyllithium catalyst system was found the most active. The effects of H₂ pressure and the ratio of n‐butyllithium to cobaltocene ratio on the hydrogenation efficiency were also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1807–1815, 1999     

Synthesis and characterization of Pst‐b‐PDMS‐b‐PSt copolymers by atom transfer radical polymerization

Polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (Pst‐b‐PDMS‐b‐PSt) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide, resulting in the PDMS macroinitiators for the ATRP of styrene (St). The latter procedure was carried out at 130°C in a phenyl ether solution with CuCl and 4, 4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. By using this technique, triblock copolymers consisting of a PDMS center block and polystyrene terminal blocks were synthesized. The polymerization was controllable; ATRP of St from those macroinitiators showed linear increases in M_n with conversion. The block copolymers were characterized with IR and ¹H‐NMR. The effects of molecular weight of macroinitiators, macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3764–3770, 2004     

Synthesis and characterization of PBMA‐b‐PSt‐b‐PBMA triblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate)‐b‐polystyrene‐b‐poly(n‐butyl methacrylate) (PBMA‐b‐PSt‐b‐PBMA) triblock copolymers were successfully synthesized by emulsion atom transfer radical polymerization (ATRP). Difunctional polystyrene (PSt) macroinitiators that contained alkyl chloride end‐groups were prepared by ATRP of styrene (St) with CCl₄ as initiator and were used to initiate the ATRP of butyl methacrylate (BMA). The latter procedure was carried out at 85°C with CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as catalyst and polyoxyethylene (23) lauryl ether (Brij35) as surfactant. Using this technique, triblock copolymers consisting of a PSt center block and PBMA terminal blocks were synthesized. The polymerization was nearly controlled, ATRP of St from those macroinitiators showed linear increases in the number average molecular weight (Mn) with conversion. The block copolymers were characterized with infrared (IR) spectroscopy, hydrogen‐1 nuclear magnetic resonance (¹HNMR), and differential scanning calorimetry (DSC). The effects of the molecular weight of macroinitiators, concentration of macroinitiator, catalyst, emulsion, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were also reported. POLYM. ENG. SCI., 45:1508–1514, 2005. © 2005 Society of Plastics Engineers     

Study on a new kind of polypropylene‐graft‐ polystyrene: Preparation and application

A novel synthetic route for preparing polypropylene‐graft‐polystyrene (PP‐g‐PSt) was set up. With this synthetic route, a series of PP‐g‐PSt copolymers containing different percentages of polystyrene chain were synthesized, based on the different reactivities of two kinds of C? C double bonds on 4‐(3‐butenyl) styrene. Characterization data, including ¹H‐NMR, ¹³C‐NMR, GPC, and DSC, demonstrated that the graft copolymers were all very pure. Furthermore, it was also attempted to use this new kind of propylene–styrene graft copolymer as a compatibilizer. DMA and SEM results illustrated that the PP‐g‐PSt obtained is an efficient compatibilizer for the polypropylene–polystyrene blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 314–322, 2004     

Synthesis and characterization of poly (styrene‐b‐[(butadiene)1−x‐(ethylene‐co‐butylene)x] ‐b‐styrene) star‐like molecular polymers produced by partial hydrogenation of SBS

This article reports the synthesis and characterization of four arm star‐shaped poly(styrene‐b‐[(butadiene)_1?x‐(ethylene‐co‐butylene)_x]‐b‐styrene) (SBEBS) copolymers. A series of SBEBS copolymers with different compositions of the elastomeric block were produced by hydrogenating a given poly(styrene‐b‐butadiene‐b‐styrene) (SBS) copolymer using a catalyst prepared from bis(η⁵‐cyclopentadienyl)titanium(IV) dichloride and n‐butyllithium. The characterization was accomplished by proton nuclear magnetic resonance spectroscopy (¹H NMR), infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The results indicate that there is a selective saturation of the polybutadiene block over the polystyrene block; this selectivity was determined by the Ti/Li molar ratio and the concentration of Ti. It was observed that the saturation rate of the 1,2‐vinyl was higher than that of the 1,4‐trans and 1,4‐cis poly(butadiene)‐b isomers. The DSC and DMA results indicate that the degree of hydrogenation had a profound effect on the polymer's relaxation behavior. All samples exhibited a biphasic system behavior with two distinct transitions corresponding to the elastomeric and polystyrene blocks. SBEBS copolymers with higher saturation levels (>33%) exhibited a crystalline character. The TGA results indicated a characteristic weight loss temperature in all samples, with slightly higher thermal degradation stabilities in the materials with higher degrees of saturation. POLYM. ENG. SCI., 54:2332–2344, 2014. © 2013 Society of Plastics Engineers     

Synthesis and characterization of block comb‐like copolymers P(A‐MPEO)‐block‐PSt

Amphiphilic block comb‐shaped copolymers, poly[poly(ethylene oxide) methyl ether acrylate]‐block‐polystyrene [P(A‐MPEO)‐block‐PSt] with PSt as a handle, were successfully synthesized via a macromonomer technique. The reaction of MPEO with acryloyl chloride yielded a macromonomer, A‐MPEO. The macroinitiator PSt capped with the dithiobenzoate group (PSt‐SC(S)Ph) was prepared by reversible addition–fragmentation transfer (RAFT) polymerization of styrene in the presence of benzyl dithiobenzoate, and used as macroinitiator in the controlled radical block copolymerization of A‐MPEO at room temperature under ⁶⁰Co irradiation. After the unreacted macromonomer A‐MPEO had been removed by washing with hot saturated saline water, block comb‐shaped copolymers were obtained. Their structure was characterized by ¹H NMR spectroscopy and gel permeation chromatography. The phase transition and self‐assembling behaviour were investigated by atomic force microscope and differential scanning calorimetry. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of PSt‐b‐PHEMA metal hybrids

The block copolymer polystyrene‐b‐poly[2‐(trimethylsilyloxy)ethylene methacrylate] (PSt‐b‐PTMSEMA) was synthesized using atom‐transfer radical polymerization (ATRP). The hydrolysis of PSt‐b‐PTMSEMA led to the formation of an amphiphilic block copolymer, polystyrene‐b‐poly(2‐hydroxylethyl methacrylate) (PSt‐b‐PHEMA), which was characterized by GPC and ¹H‐NMR. TEM showed that the PSt‐b‐PHEMA formed a micelle, which is PSt as the core and PHEMA as the shell. Under appropriate conditions, the nickel or cobalt ion cause chemical reactions in these micelles and could be reduced easily. ESCA analysis showed that before reduction the metal existed as a hydroxide; after reduction, the metal existed as an oxide, and the metal content of these materials on the surface is more than that on the surface of the copolymer metal ion. XRD analysis showed that the metal existed as a hydroxide before reduction and existed as a metal after reduction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2883–2891, 2002; DOI 10.1002/app.10278     

Study of a new titanium dual initiator for the synthesis of poly(ε‐caprolactone)‐b‐polystyrene block copolymers by the combination of coordination and nitroxide mediated polymerizations

Poly ε‐caprolactone‐polystyrene block‐copolymers (PCL‐b‐PSt) were synthesized using a modified titanium catalyst as the dual initiator. Alcoholysis of Ti(OPr)₄ by 4‐hydroxy 2,2,6,6 tetramethyl piperidinyl‐1‐oxyl (HO‐TEMPO) gave a bifunctional initiator Ti(OTEMPO)₄. Poly ε‐caprolactone prepolymer end‐capped with the nitroxide group was first prepared by ring opening polymerization of ε‐caprolactone with this initiator at high conversion. The nitroxide‐end‐capped structure and molar mass (M_n) of the polymers were demonstrated by typical UV absorption band. This analytical technique indicates a near‐quantitative nitroxide functionality and a M_n in good agreement with size exclusion chromatography (SEC) ones. This polyester prepolymer was used to further initiate the radical polymerization with styrene and reach the block copolymers (PCL‐b‐PSt). All the prepolymers and block copolymers were characterized by SEC and NMR spectroscopy. Additionally, the preparation of star polymers bearing two kinds of arms (PCL and PSt) was envisaged and a preliminary result was given. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (C_{tr, PEO‐I} = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and ¹H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

Synthesis,characterization, and application of novel amphiphilic poly(D‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐ poly(D‐gluconamidoethyl methacrylate) triblock copolymers

Novel amphiphilic ABA‐type poly(D ‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐poly(D ‐gluconamidoethyl methacrylate) (PGAMA‐b‐PU‐b‐PGAMA) tri‐block copolymers were successfully synthesized via the combination of the step‐growth and copper‐catalyzed atom transfer radical polymerization (ATRP). Dihydroxy polyurethane (HO‐PU‐OH) was synthesized by the step‐growth polymerization of hexamethylene diisocyanate with poly(tetramethylene glycol). PGAMA‐b‐PU‐b‐PGAMA block copolymers were synthesized via copper‐catalyzed ATRP of GAMA in N, N‐dimethyl formamide at 20°C in the presence of 2, 2′‐bipyridyl using Br‐PU‐Br as macroinitiator and characterized by ¹H‐NMR spectroscopy and GPC. The resulting block copolymer forms spherical micelles in water as observed in TEM study, and also supported by ¹H NMR spectroscopy and light scattering. Miceller size increases with increase in hydrophilic PGAMA chain length as revealed by DLS study. The critical micellar concentration values of the resulting block copolymers increased with the increase of the chain length of the PGAMA block. Thermal properties of these block copolymers were studied by thermo‐gravimetric analysis, and differential scanning calorimetric study. Spherical Ag‐nanoparticles were successfully synthesized using these block copolymers as stabilizer. The dimension of Ag nanoparticle was tailored by altering the chain length of the hydrophilic block of the copolymer. A mechanism has been proposed for the formation of stable and regulated Ag nanoparticle using various chain length of hydrophilic PGAMA block of the tri‐block copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, and properties of amphiphilic block copolymer of acrylamide‐styrene by self‐emulsifying microemulsion method

The copolymerization system of acrylamide (AM) and styrene (St) was acquired by using amphiphilic block copolymer PAM‐b‐PSt with lower molecular weight as polymeric surfactant, and then the microemulsion phase diagram was drawn. The appropriate copolymerization systems were chosen in the phase diagram, and higher molecular weight amphiphilic block copolymers PAM‐b‐PSt were prepared by self‐emulsifying microemulsion method. The chemical composition and structure of the products were analyzed by FTIR, ¹H‐NMR, ¹³C‐NMR, GPC, and UV; the block structure of products was characterized by DSC, and the hydrophobic association property of the products was studied by the fluorescence probe and rotating viscosity measurement. The results showed that O/W microemulsion was also acquired by using the polymeric surfactant; 3 g polymeric surfactant was only used to disperse 0.25 g St into aqueous solution, which showed higher emulsifying efficiency. At the same time, the use of self‐emulsifying microemulsion copolymerizing system can avoid back treatment of small molecular surfactant and the purified block polymer was prepared in one step; the prepared copolymers have good hydrophobic association properties and their aqueous solution showed evident viscosity increment. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of block copolymers from PDMS macroinitiators

The synthesis of polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (PSt‐b‐PDMS‐b‐PSt) copolymers is described. Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide resulting in the PDMS macroinitiators. The terminal alkyl bromide groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. ATRP of St from those macroinitiators showed linear increases in M_n with conversion, demonstrating the effectiveness of ATRP to synthesize a variety of inorganic/organic polymer hybrids. Copyright © 2004 Society of Chemical Industry     

Poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene by combination of ATRP and aminolysis processes

Block copolymers of very hydrophilic poly(N‐hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene in well‐defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100°C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Compositional differences of propylene–ethylene block copolymers manufactured by degradation and hydrogenation techniques

The purpose of the present work is to investigate the compositional difference of polypropylene–polyethylene block copolymers (PP‐b‐PE) manufactured industrially by the process of degradation and hydrogenation, respectively. Each of the PP‐b‐PE copolymers was fractionated into three fractions with heptane and chloroform. The compositions of the three fractions were characterized by ¹³C nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy, as well as differential scanning calorimetry (DSC) and thermal fractionation. The results showed that the Chloroform‐soluble fraction was amorphous ethylene‐propylene rubber, and the content of the rubber in PP‐b‐PE manufactured by hydrogenation was less than that by degradation. The degree of crystallinity of the chloroform‐insoluble fraction of the PP‐b‐PE manufactured by hydrogenation is higher than that of by degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3301–3306, 2006     

Controlled/living RAFT polymerization of N‐phenyl maleimide and synthesis of its block copolymers

The controlled/living radical polymerization of N‐phenyl maleimide (NPMI) was achieved using 2,2′‐azobisisobutyronitrile as the initiator and 2‐cyanopropyl‐2‐yl dithiobenzoate as the reversible addition‐fragmentation chain transfer agent at 75°C in dichloroethane/ethylene carbonate (60/40, w/w) mixed solvent. The block copolymers of polystyrene‐b‐polyNPMI and poly(n‐butyl methacrylate)‐b‐polyNPMI were successfully prepared by chain extension from dithiobenzoate‐terminated polystyrene and poly (n‐butyl methacrylate) to NPMI, respectively. The obtained NPMI‐based (co)polymers were characterized by gel permeation chromatography and ¹H‐NMR spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Low molecular weight block copolymers as plasticizers for polystyrene

Polystyrene‐b‐alkyl, polystyrene‐b‐polybutadiene‐b‐polystyrene, and polystyrene‐b‐poly(propylene glycol)monotridecyl ether were synthesized using macro initiators and atom transfer radical polymerization or by esterifications of homopolymers. The aim was a maximum molecular weight of 4 kg/mol and minimum polystyrene content of 50 w/w %, which by us is predicted as the limits for solubility of polystyrene‐b‐alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene‐b‐alkyl is found to be an efficient plasticizer also for polystyrene‐b‐polyisoprene‐b‐polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene‐b‐alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene‐b‐polybutadiene‐b‐polystyrene and polystyrene‐b‐poly(propylene glycol)monotridecyl ether series were only partially soluble in polystyrene and insoluble in the polystyrene phase of SIS. For the lowest molecular weight samples, this leads to measurable plasticization of polystyrene but no plasticization of SIS. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 981–991, 2005