Alternating copolymerizations of styrene derivatives and carbon monoxide in the presence of a palladium (II) catalyst

A series of styrene derivatives were synthesized from aromatic substances by Friedel-Crafts acylation, reduction, and dehydration. Alternating copolymers of styrene derivatives and carbon monoxide were prepared in the presence of a palladium(II) catalyst. The characterization of the polyketones produced was performed by use of ¹H-NMR, IR, WXRD, and EA methods. The thermal degradation of the regular alternating copolymer of carbon monoxide and styrene (STCO) has been studied by thermal gravimetry (TG). The TG spectra of solid samples were recorded both in nitrogen and in air. The degradation reaction order and activation energy were determined. The photodegradation of STCO was investigated. In addition, the block copolymerization of STCO with methyl methacrylate under UV irradiations was also studied. It is found that the tertiary amine can promote this photopolymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1283–1291, 1997     

AB and ABA type butyl acrylate and styrene block copolymers via RAFT‐mediated miniemulsion polymerization

Two trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agents are compared in miniemulsion polymerization of styrene and butyl acrylate and the formation of seeded emulsion block copolymers. The order of block synthesis and the number of block segments per polymer are discussed. The use of nonionic surfactants is examined and the type of surfactant in relation to the monomer used is found to have a significant affect on latex formation. Conditions are shown by which AB and ABA type block copolymers can be successfully prepared via a seeded RAFT‐mediated emulsion polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 588–604, 2007     

Ambipolar charge transport in a donor–acceptor–donor‐type conjugated block copolymer and its gate‐voltage‐controlled thin film transistor memory

We demonstrate a fully conjugated donor–acceptor–donor (D–A–D) triblock copolymer, PBDTT–PNDIBT–PBDTT, which contains PBDTT as the donor block and PNDIBT as the acceptor block. The polymer was synthesized by end‐capping each block with a reactive unit, followed by condensation copolymerization between the two blocks. The physical, optical, and electrochemical properties of the polymer were investigated by comparing those of donor‐ and acceptor‐homopolymers (i.e., PBDTT and PNDIBT), which are the oligomeric monomers, and their blends. On using the newly synthesized block copolymer, ambipolar charge transport behavior was observed in the corresponding thin‐film transistor, and the behavior was compared to that of blend film of donor‐ and acceptor‐homopolymers. Owing to the presence of donor and acceptor blocks in a single polymer chain, it was found that the triblock copolymer can store two‐level information; the ability to store this information is one of the most intriguing challenges in memory applications. In this study, we confirmed the potential of the triblock copolymer in achieving distinct two‐stage data storage by utilizing the ambipolar charge trapping phenomenon, which is expected in donor and acceptor containing random and block copolymers in a thin‐film transistor. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3223–3235     

Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin‐based block copolymers by reversible addition–fragmentation chain‐transfer (RAFT) polymerization

Reversible addition–fragmentation chain transfer (RAFT) was applied to the copolymerization of styrene and maleic anhydride. The product had a low polydispersity and a predetermined molar mass. Novel, well‐defined polyolefin‐based block copolymers were prepared with a macromolecular RAFT agent prepared from a commercially available polyolefin (Kraton L‐1203). The second block consisted of either polystyrene or poly(styrene‐co‐maleic anhydride). Furthermore, the colored, labile dithioester moiety in the product of the RAFT polymerizations could be removed from the polymer chain by UV irradiation. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3596–3603, 2000     

Covalent stabilization of nanostructures: Robust block copolymer templates from novel thermoreactive systems

Structurally robust block copolymer templates with feature sizes of approximately 10 nm were prepared from functionalized poly(methyl methacrylate)‐b‐polystyrene block copolymers. By the inclusion of benzocyclobutene crosslinking groups in the polystyrene block, the covalent stabilization of thin films to both thermal treatment and solvent exposure became possible. In addition, the crosslinking of the poly(styrene‐benzocyclobutene) domains at 220 °C, followed by the removal of poly(methyl methacrylate), provided a robust, crosslinked nanostructure with greater processing and fabrication potential. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1028–1037, 2005     

Synthesis and characterization of random hydrophilic/hydrophobic copolymers of styrene and D-lactose-O-vinylbenzylhydroxime

D -Lactose-O-(vinylbenzyl)oxime (LVO), prepared from α-D -lactose and [O-(vinylbenzyl)oxy]amine ( 1 ) was copolymerized with styrene (ST) in dimethylsulfoxide (DMSO)-toluene (1 : 1, v/v) at 65°C using 2,2′-azobisisobutyronitrile (AIBN) as a free radical initiator. The polymerization was rapid when using AIBN as the initiator. The resultant copolymers were characterized by elemental analyses, infrared, viscometry, TGA, DSC, and ¹H-NMR spectroscopy. The poly(ST-co-LVO) had an intrinsic viscosity in the range of 0.11–0.51 dL/g in DMSO at 30°C. The molecular weight was determined by gel permeation chromatography (GPC), and the molecular weight of the resulting polymers ranged from 2.11 × 10⁴ to 6.53 × 10⁷ with low polydispersities. The solubility of the copolymers with different monomer compositions in solvents of varied polarities was also studied. Incorporation of up to 65% (mol %) of lactose-based monomer onto polystyrene backbone led to a water-soluble polymer. Thermal behavior of the synthesized copolymers was evaluated by thermogravimetric analysis (TGA) and correlated very well with the polymer composition. Introduction of a pendant disaccharide compromised the thermal stability of the copolymer. The synthetic approach described in this report provides a route to prepare a novel disaccharide surfactant polymer with well-defined structures and hydrophilic/hydrophobic balances, by adjusting feed ratio of the lactose-based monomer ( 1 ) to styrene. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2971–2978, 1998     

Dispersion copolymerization of polyoxyethylene macronomer and styrene 4. Solution properties of polystyrene-graft-polyoxyethylene copolymers

The graft copolymers (polystyrene-graft-polyoxyethylene) (PSt-graft-PEO) were prepared by the radical dispersion copolymerization of methacryloyl (MA)-terminated PEO macromonomer and styrene. By means of size-exclusion chromatography, liquid chromatography at the critical adsorption point, and light scattering, the molecular weight parameters and the solution properties of PSt-graft-PEO were investigated. The apparent average molecular weight and the molecular weight distribution (MWD) of graft copolymers were found to decrease with increasing molecular weight of PEO-MA macromonomer. This decreased molecular weight was attributed to the chain transfer to PEO unit and increased contribution of the solution polymerization. The broad MWD varied with the ratio of the polymerization in the continuous phase and the polymer particles. The number of PEO grafts per PSt backbone decreased with increasing molecular weight of the PSt-graft-PEO copolymer, which was attributed to the intramolecular association of PEO segments. The intrinsic viscosity or the coil size of graft copolymer molecules varied with temperature as a result of the dehydration of PEO segments. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3087–3097, 1999     

Block copolymer preparation by atom transfer radical polymerization under emulsion conditions using a nanoprecipitation technique

Living‐radical polymerization of acrylates were performed under emulsion atom transfer radical polymerization (ATRP) conditions using latexes prepared by a nanoprecipitation technique previously employed and optimized for the polymerization of styrene. A macroinitiator of poly(n‐butyl acrylate) prepared under bulk ATRP was dissolved in acetone and precipitated in an aqueous solution of Brij 98 to preform latex particles, which were then swollen with monomer and heated. Various monomers (i.e. n‐butyl acrylate, styrene, and tert‐butyl acrylate) were used to swell the particles to prepare homo‐ and block copolymers from the poly(n‐butyl acrylate) macroinitiator. Under these conditions latexes with a relatively good colloidal stability were obtained. Furthermore, amphiphilic block copolymers were prepared by hydrolysis of the tert‐butyl groups and the resulting block copolymers were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The bulk morphologies of the polystyrene‐b‐poly(n‐butyl acrylate) and poly(n‐butyl acrylate)‐b‐poly(acrylic acid) copolymers were investigated by atomic force microscopy (AFM) and small angle X‐ray scattering (SAXS). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 625–635, 2008     

Poly(3‐hexyl thiophene)‐b‐poly(N‐isopropyl acrylamide): Synthesis and its composition dependent structural,solubility, thermoresponsive,electrochemical, and electronic properties

Conjugated block copolymers consisting of poly(3‐hexyl thiophene) (P3HT) and a thermoresponsive polymer poly(N‐isopropyl acrylamide) (PNIPAM) with varying composition have been synthesized by facile click reaction between alkyne terminated P3HT and azide terminated PNIPAM. The composition‐dependent solubility, thermoresponsive property in water, phase behavior, electrochemical, optical, and electronic properties of the block copolymers were systematically investigated. The block copolymers with higher volume fraction of PNIPAM form thermoresponsive spherical micelles with P3HT‐rich crystalline cores and PNIPAM coronas. Both X‐ray and atomic force microscopic studies indicated that the blocks copolymers showed well‐defined microphase separated nanostructures and the structure depended on the composition of the blocks. The electrochemical study of the block copolymers clearly demonstrated that the extent of charge transport through the block copolymer thin film was similar to P3HT homopolymer without any significant change in the band gap. The block copolymers showed improved or similar charge carrier mobility compared with the pure P3HT depending on the composition of the block copolymer. These P3HT‐b‐PNIPAM copolymers were interesting for fabrication of optoelectronic devices capable of thermal and moisture sensing as well as for studying the thermoresponsive colloidal structures of semiconductor amphiphilic systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1785–1794     

Mechanical properties of gradient copolymers of styrene and n‐butyl acrylate

The mechanical properties of linear and V‐shaped compositional gradient copolymer of styrene and n‐butyl acrylate with composition of around 55 wt % styrene were investigated by comparing with their block copolymer counterparts. Compared with their block copolymer counterparts, the gradient copolymers showed lower elastic modulus, much larger elongation at break, and similar ultimate tensile strength at room temperature. This performance could be ascribed to that the local moduli continuously change from the hardest nanodomains to the softest nanodomains in the gradient copolymer, which alleviates the stress concentration during tensile test. Compared with the V‐shaped gradient (VG) copolymer, the linear gradient copolymer showed much higher elastic modulus but lower elongation at break. The mechanical properties of the gradient copolymers were more sensitive to the change in temperature from 9 °C to 75 °C. With recovery temperature increased from 10 °C to 60 °C, the strain recovery of VG copolymer would change steadily from 40% to 99%. However, the elastic recovery of linear and triblock copolymer was poor even at 60 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 860–868     

Detection of free surface composition and molecular-level structural development of styrene(S)/butadiene(B) block copolymer films during a solution-to-film process

The surface chemical structure development in solution-cast styrene(S)/butadiene(B) block copolymer films as a function of solvent evaporation time was investigated using sum frequency generation vibrational spectroscopy(SFG).The surface structure formation of the styrene(S)/butadien(B) block copolymer(30 wt% PS) films during the solution-to-film process was found to be controlled mainly by dynamic factors,such as the mobility of the PB block in solution.For SB diblock copolymers,a pure PB surface layer was formed only when the film was cast by dilute toluene solution.With increasing concentration of casting solution,PB and PS components were found to coexist on the film surface,and the morphology of the PB component on the film surface changed from cylindrical rods to spheres.For SBS triblock copolymers,a small amount of PS component existed on the surface even if the film was cast by 1.0 wt% toluene solution.In addition,PS components at the outermost layer of the film increased and the length of PB cylindrical rods on the surface decreased with increasing concentration of casting solution.     

Facile one‐pot synthesis of linear and radial block copolymers of styrene and isoprene through a novel coupling agent by living anionic polymerization

A new methodology is successfully used for the concurrent synthesis of three different copolymers; diblock, triblock, and three‐armed star‐block copolymers of styrene and isoprene via the living anionic polymerization with control over the molecular weight and weight fractions of each block. The room temperature polymerization process has resulted in the well defined linear and radial block copolymers, when the living di‐block of poly(styrene‐b‐isoprene) was coupled using cheap and readily available malonyl chloride as a novel coupling agent giving nearly 100% yield. The resulting block copolymers have narrow polydispersity index (PDI = 1.01–1.09) with a good agreement between the calculated and the observed molecular weights. The results are further supported by fractionation of the block copolymers by reversed‐phase temperature gradient interaction chromatography (RP‐TGIC) technique followed by size exclusion chromatography (SEC). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2636–2641, 2010     

Living radical copolymerization of styrene/maleic anhydride

Styrene/maleic anhydride (MA) copolymerization was carried out using benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Styrene/MA copolymerization proceeded faster and yielded higher molecular weight products compared to styrene homopolymerization. When styrene/MA copolymerization was approximated to follow the first‐order kinetics, the apparent activation energy appeared to be lower than that corresponding to styrene homopolymerization. Molecular weight of products from isothermal copolymerization of styrene/MA increased linearly with the conversion. However products from the copolymerization at different temperatures had molecular weight deviating from the linear relationship indicating that the copolymerization did not follow the perfect living polymerization characteristics. During the copolymerization, MA was preferentially consumed by styrene/MA random copolymerization and then polymerization of practically pure styrene continued to produce copolymers with styrene‐co‐MA block and styrene‐rich block. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2239–2244, 2000     

Thermal‐initiating potentialities of poly(methyl methacrylate) peroxide: Metamorphosis of block‐into‐block copolymer and comparative studies on surface texture and morphology

This is the first report concerning the use of vinyl polyperoxide, namely, poly(methyl methacrylate) peroxide (PMMAP), as a thermal initiator for the synthesis of active polymer PMMAP‐PS‐PMMAP by free‐radical polymerization with styrene. The polymerizations have been carried out at different concentrations of macroinitiator PMMAP. The active polymers have been characterized by ¹H NMR, DSC, thermogravimetric analysis, and gel permeation chromatography. PMMAP‐PS‐PMMAP is further used as the thermal macroinitiator for the preparation of another block copolymer, PMMA‐b‐PS‐b‐PMMA, by reacting the active polymers with methyl methacrylate. The block copolymers have been synthesized by varying the concentrations of the active polymers. The mechanism of block copolymers has been discussed, which is also supported by thermochemical calculations. Studies on the surface texture and morphology of the block copolymer of polystyrene (PS) and PMMA material have been carried out using scanning electron microscopy. Furthermore, in this article, a blend of the same constituent materials (PS and PMMA) in proportions (v/v) similar to that contained in block copolymers has been formulated, and the morphology and surface textures of these materials were also investigated. A comparative microscopical evaluation between two processing methods was done for a better understanding of the processing route dependence of the microstructures. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 546–554, 2001     

Diblock and triblock copolymers of styrene and acetoxymethylstyrene by one‐pot ATRP

We describe the synthesis of diblock and triblock copolymers by sequential atom transfer radical polymerization of styrene and acetoxymethylstyrene. Contrary to the usual block copolymerization involving isolation of the macroinitiator, a convenient one‐pot procedure is developed. This is possible because of the preferential polymerization of acetoxymethylstyrene, even in the presence of residual styrene, as inferred from characterization of the intermediate polystyrenes and the block copolymers by size exclusion chromatography, ¹H NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and GPEC techniques. The latent acetoxy functionalities in these block copolymers are shown to be easily unmasked to ? OH and ? Br functionalities, with the potential for block ionomers and dense graft architectures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 575–583, 2005     

Random and AB diblock copolymers of tricyclodecanemethanol urethane methacrylate with styrene: Synthesis and morphology characterization

A monomer design having a bulky terminal tricyclodecane (TCD) unit linked via hydrogen bondable urethane to an ethyleneoxy methacrylate unit, and capable of generating three‐dimensional honeycomb patterns upon solvent casting has been investigated. Random copolymers as well as a diblock copolymer Poly(Sty₄₂‐b‐TCD₁₈) of this monomer with styrene were prepared by free‐radical polymerization route and atom transfer radical polymerization (ATRP) route. Morphology characterization was carried out using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis. Particle size was measured by dynamic light scattering measurements (DLS). Irrespective of the wide differences in molecular weight and polydispersity index values, the random copolymers having TCD content >30 mol % were found to form microporous films upon solvent casting from a THF/water 9:1 solvent combination. The amount of TCD in the copolymer was found to have an influence on the pore size formed. The diblock copolymer formed microspheres ～200 nm in diameter. The thermal properties of all the polymers were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and the copolymers were found to have good thermal stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1278–1288, 2008     

Supramolecular Complex of Poly(styrene)-b-Poly(4-vinylpyridine) and 1-Pyrenebutyric Acid in Thin Film

Summary: Here, we have described a novel supramolecular complex (SMC) between poly(styrene)-b-poly(4-vinylpyridine) (PS-b-P4VP) and 1-pyrenebutyric acid (PBA) and studied of its self assembly in thin film. PBA will make supramolecular complex with the P4VP block due to strong hydrogen bonding between the carboxylic group of 1-pyrenebutyric acid and pyridine ring of P4VP. The formation of supramolecular complex between PS-P4VP and PBA through hydrogen bonding is investigated through FTIR study. The supramolecular complex of PS-b-P4VP and 1-pyrenebutyric acid changed the block copolymer morphology from cylindrical to lamella in thin film due to the increase of the volume fraction of P4VP (PBA). In both cases (parent block copolymer and SMC), the microdomains are oriented normal to the substrate after annealing in a selective solvent. Pure block copolymer shows cylindrical morphology with a periodicity of ∼26 nm, whereas the SMC shows lamellar morphology with a periodicity of ∼ 29 nm. After fabricating the thin film from SMC, 1-pyrenebutyric acid can be easily removed by dissolving the thin film in ethanol to transform the block copolymer thin film into nanotemplate or membrane.     

Selective control over the lamellar thickness of one domain in thin binary blends of block copolymer films

Thin binary blends of poly(styrene‐b‐methyl methacrylate) (PS‐PMMA) block copolymers in films where the lamellar thickness of one domain is controlled while preserving the thickness of the other domain were demonstrated without microphase separation. One of the block copolymers used here was short and symmetric, and the other was long and asymmetric; the molecular weights of the PMMA block chains in the constituents were similar. A random copolymer brush was introduced and film thickness and composition of brush were adjusted to induce perpendicular orientation in thin film. As the blend composition of the long asymmetric block copolymer increased, the PS lamellar thickness increased from 15.8 to 25.1 nm, whereas the PMMA lamellar thickness remained constant at approximately 14 nm (the thickness decreased slightly from 14.0 to 13.3 nm). The domain spacing behavior in thin film was consistent in the bulk. These results were compared with the Birshtein, Zhulina, and Lyatskaya model and the theories for pure block copolymers in the strong segregation limit and in the intermediate segregation regime. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1393–1399     

SELF ASSEMBLY OF ABC TRIBLOCK COPOLYMER THIN FILMS ON A BRUSH-COATED SUBSTRATE

Self assemblies of ABC triblock copolymer thin films on a densely brush-coated substrate were investigated by using the self-consistent field theory.The middle block B and the coated polymer form one phase and the alternating phase A and phase C occur when the film is very thin either for the neutral or selective hard surface(which is opposite to the brushcoated substrate).The lamellar phase is stable on the hard surface when it is neutral and interestingly,the short block tends to stay on this hard surf...     

A solvent‐free method for the synthesis of block copolymers with fluorinated pendant groups by a hydrosilylation reaction

A solvent‐free method for the hydrosilylation of pendant double bonds in block copolymers is reported in this article. An anionically prepared block copolymer, poly(styrene‐b‐1,2‐butadiene), was heated with 1H,1H,2H,2H‐perfluorooctyldimethylhydrosilane in the presence of a nonacidic platinum catalyst for 24–26 h to obtain a quantitatively hydrosilylated block copolymer. Gel permeation chromatography, IR, and thermogravimetric analysis were used to characterize the block copolymers obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1179–1183, 2000