Viscoelastic properties of heterophase blends of homopolymers and block copolymers

Stress relaxation and dynamic mechanical measurements were carried out for two types of heterophase polyblends. One is obtained by blending homopolymers of butadiene and styrene (high impact polystyrene or HIPS); the other by blending homopolymer of butadiene with a triblock copolymer of styrene-butadiene-styrene (SBS/B). It was found that for HIPS, time temperature superposition is difficult, and the shift factors cannot be adequately interpreted by a reasonable model. For SBS/B it is impossible to carry out superposition. Modulus-temperature and loss tangent curves determined by dynamic mechanical experiments indicate the presence of new transition near ?40°C. Possible mechanisms giving rise to this new transition are discussed.     

Multivariate analysis of C NMR spectra of methacrylate copolymers and homopolymer blends

¹³C NMR spectra of copolymers of methyl methacrylate and tert-butyl methacrylate with various chemical compositions, the homopolymers of the two methacrylates, and blends of the homopolymers with various blend ratios were subjected to principal component analysis. The first and second principal components correlated chemical composition and the randomness of comonomer sequence, respectively. Chemical composition of the copolymers was determined with high accuracy and precision by the partial least-squares regression without assignment of individual resonance peaks.     

Processing and mechanical properties of recycled PVC and of homopolymer blends with virgin PVC

Mechanical and processing properties of recycled polyvinylchloride (PVC, from bottles and pipes) were compared with those of virgin pipe grade PVC. Blends of recycled and pipe grade PVC were also prepared and characterized. It was found that the particle size and the restabilization of the recycled PVC are the two main points to be considered for obtaining virgin/recycled PVC blends with uniform and good mechanical properties. In general, recycled PVC not only does not significantly reduce the modulus and tensile strength, but also improves the impact strength and processing behavior of pipe grade virgin PVC. Only the thermomechanical resistance is slightly lowered. The latter points hold, of course, only when the recycled PVC contains both reinforcing and modifier agents. © 1996 John Wiley & Sons, Inc.     

Optical properties of the thin films of poly(methylpentoxysilane) homopolymers and copolymers

The optical properties of the thin films of asymmetrically substituted polysilane homopolymers and copolymers were studied. A conformational change in the organopolysilanes having (pentoxy,methyl) or (hexyl,methyl) groups was observed by polarized UV spectrometry and a wide angle X-ray diffraction. The polysilanes and polysilane copolymers having hexyl and pentoxy side chains were crystallized to form oriented films along the direction of the mechanically oriented polytetrafluoroethylene (PTFE) films. The bathochromic shifts were observed for polysilane and the polysilane copolymer having pentoxy side chains when the film thickness was small (ca. <50 nm). The influence of the thickness of the films on the spectral change was significant when the substituent was a pentoxy group, however, not when it was a hexyl group.     

Optical and electroluminescent properties of polyfluorene copolymers and their blends

Light emitting properties of several polyfluorene (PF) copolymers (P1-P4) and their blends have been investigated. Light emitting diodes were fabricated with the configuration of ITO/PEDOT:PSS/polymer/Ca/Al. The EL peak wavelengths were 421 nm (violet), 505, 513 nm (green) and 570 nm (yellow) for PF copolymers and 510, 535 nm (green) for P1/P2 and P1/P3 blends, respectively. Förster energy transfer in the photoluminescence and electroluminescence of the polymer blends P1/P2 and P1/P3 was studied. The LED using the polymer blend P1/P2 showed a turn-on voltage of 2.5 V and a brightness of 5×10⁴ cd/m² at 7 V. The highest external quantum efficiency was observed to be 3.71% at 5 V. Upon addition of 20 wt% of the green emitter P2 to the violet emitter P1, the device efficiency increased from 1.18 to 3.71%.     

Synthesis,characterization and properties evaluation of copolymers of 2,3,4,5,6‐pentafluorostyrene and N‐phenylmaleimide

Copolymers of 2,3,4,5,6‐pentafluorostyrene (PFS) having a combination of high hydrophobicity and high glass transition temperature (T_g) are reported here for the first time. The copolymerization was carried out using N‐phenylmaleimide (NPM) as the comonomer and azobisisobutyronitrile (AIBN) as the initiator under both conventional thermal heating and microwave heating. The initial copolymerization rate was found to be higher under microwave heating than under thermal heating. The copolymerization parameters were determined using the Fineman–Ross method and were found to be r₁ (NPM) = 0.28 and r₂ (PFS) = 0.86. Increased incorporation of NPM in the copolymers led to an increase in T_g of the copolymers without significantly affecting the hydrophobicity of poly(2,3,4,5,6‐pentafluorostyrene). Thermal stability of the copolymers is also reported. Copyright © 2005 Society of Chemical Industry     

苯乙烯-丁二烯-苯乙烯-甲基丙烯酸酯嵌段共聚物的合成与表征

用正丁基锂为引发剂,环已烷和四氢呋喃为混合溶剂,以苯乙烯、丁二烯、甲基丙烯酸酯为单体,按阴离子顺序加料方法合成了聚苯乙烯-丁二烯-苯乙烯-甲基丙烯酸酯嵌段共聚物,共聚物经GPC、IR、DSC、TEM等测试方法表征。结果表明,在30 ℃左右、1,1-二苯基乙烯(DPE)戴帽和LiCl配合的条件下,合成了窄分布(MWD<1.3)聚苯乙烯-丁二烯-苯乙烯-甲基丙烯酸酯嵌段共聚物,成功地在SBS中引入了一小段极性链段。     

Gel permeation and thin-layer chromatographic characterization and solution properties of butadiene and styrene homopolymers and copolymers

Gel permeation chromatographic (GPC) and thin-layer chromatographic (TLC) studies of polystyrene, polybutadienes (BR), and their copolymers (SBR) have been carried out. GPC primarily separates them on the basis of molecular size, and TLC, on the basis of composition. Methods of obtaining absolute molecular weight distributions for BR and SBR based upon variations of the Strasbourg Universal Calibration procedure are described. In particular, [η]–M relationships in both the GPC solvent (THF) and in a second solvent (toluene) were used; in addition, results of statistical mechanical calculations for \documentclass{article}\pagestyle{empty}\begin{document}$\overline {s^2 }$\end{document} (based on the assumption of negligible steric hindrance and freely rotating bonds) were applied. An experimental comparison of these methods was carried out, and use of the [η]–M relationships for both solvents was found to give satisfactory results. The predictions of the statistical theory were too low. A detailed study of polymer–solvent–gel interaction in the GPC unit was made through investigation of ternary phase equilibrium in the (polystyrene)–THF–(polymer) system. The polymers studied included BR and SBR with varying styrene contents. Experimental techniques for TLC separations of BR, SBR, and polystyrene according to the composition are described.     

Polyaldehydes: homopolymers,block copolymers and promising applications

This minireview gives a brief overview on the polymerization of higher aldehydes, discusses current applications of certain polyaldehydes, and points toward potential future applications of these interesting materials. Although it was discovered long ago that several aldehydes can be polymerized, the application potential of these polymers was largely overlooked. This is somewhat surprising as many polyaldehydes show interesting properties such as fast and complete depolymerization triggered by chemical or thermal stimuli. Such stimuli‐responsive polymers can be useful materials in many applications in for example nanotechnology or drug delivery. By incorporating polyaldehydes into functional block copolymers even more versatile materials can be created. The increasing number of recent research examples demonstrates the growing interest in polyaldehydes as smart materials and their potential for novel applications. Copyright © 2012 Society of Chemical Industry     

NMR and FT-IR studies of sulfonated styrene-based homopolymers and copolymers

A series of sodium poly(styrene sulfonate)-block-poly(4-tert-butylstyrene) (NaPSS-b-PtBS) copolymers and related homopolymers were characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The homopolymers included polystyrene (PS), poly(4-tert-butylstyrene) (PtBS), sodium poly(4-styrene sulfonate) (NaP4SS), sodium poly(styrene sulfonate) (NaPSS) with various sulfonation levels, and partially sulfonated PtBS (PtBSS). The structures of NaPSS and PtBSS were elucidated, and the effect of sulfonation level on the NaPSS FT-IR spectrum was studied. The characteristic peaks for NaPSS and PtBSS in FT-IR and NMR spectra were identified.     

Alkaline hydrolysis of homopolymers and copolymers of 2-hydroxypropyl methacrylate

Homopolymers of 2-hydroxypropyl methacrylate (HPMA) and copolymers with acrylic acid (AA) were prepared in 1,4-dioxane. The reactivity ratios were determined to be r_AA = 0.27 ± 0.04 and r_HPMA = 2.2 ± 0.2. The alkaline hydrolysis by sodium hydroxide of the HPMA monomer and polymers showed that while the HPMA monomer hydrolyzed readily as expected for a low-molecular-weight carboxylic ester the HPMA homopolymer and water-soluble sodium acrylate (NaA) copolymers were extremely resistant to alkaline hydrolysis. The saponification reaction followed a second-order rate equation, being first order with respect to both HPMA and hydroxide ion concentration. The Arrhenius parameters, activation energy E and frequency factor A, for the alkaline hydrolysis of HPMA monomer in water were found to be E = 10.3 Kcal/mol and A = 1.5 × 10⁸ L/mol min, and those for the NaA–HPMA copolymers in water were found to be E = 24 kcal/mol and A = 4 × 10¹² L/mol min. The NaA–HPMA copolymers had a limiting extent of hydrolysis, ranging from 9–90% ester conversion. A sharp rate decrease at low conversion was noted during the HPMA homopolymer hydrolysis in 58/42 dimethyl sulfoxide/water, allowing the calculation of two distinct reaction rates. © 1992 John Wiley & Sons, Inc.     

甲基丙烯酸酯类光刻胶成膜树脂的合成与性能研究

以甲基丙烯酸(MAA)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为单体,偶氮二异丁腈为引发剂,采用溶液自由基聚合方法,合成了甲基丙烯酸酯类光刻胶成膜树脂,研究了合成工艺对产物分子量及分子量分布的影响,并对其在光刻胶中的应用性能,如碱溶性、涂膜表面干燥性、感度和分辨率等进行了初步考察。结果表明,在引发剂用量为单体用量的0.6%~1%、反应温度80~85℃、3次进料条件下,制得的聚合物的重均分子量为44 341~53 696,分子量分布为3.66~5.69,由单体质量比MAA∶MMA∶BA为25∶50∶25的成膜树脂配制的光刻胶,分辨率达35μm。     

The preparation and properties of chelates of transition metal ions with the homopolymer and copolymers of p-vinylbenzoylacetone

p-Vinylbenzoylacetone (VBA) was prepared by the condensation of p-vinylacetophenone and ethyl acetate. This monomer was homopolymerized and copolymerized with acrylamide or maleic anhydride to produce polymers which would chelate substantial amounts of transition metal ions such as Cu²⁺, Ni²⁺, Co²⁺, Eu³⁺, and VO²⁺. In the case of the Cu²⁺ and Ni²⁺ chelates, about 80–90% of the metal ion could be eluted by dilute mineral acids. The resulting eluted products apparently have a somewhat porous structure because they are capable of rechelating these ions from water solution, even though the solid homopolymer which had not been chelated and eluted is too hydrophobic to chelate very much metal ion from water solution. The eluted Cu²⁺ chelate readily reaccepted Cu²⁺ ions from water solution and discriminated against Ni²⁺ almost completely. However, the eluted Ni²⁺ chelate would reaccept both Cu²⁺ and Ni²⁺ ions, but exhibited a strong preference for Cu²⁺ ions in competitive batch experiments. The VO²⁺ chelate was an effective heterogeneous phase catalyst for the epoxidation of allyl alcohols such as geraniol with tert-butylhyroperoxide. The chelate was stable under these oxidative conditions and could be recovered unchanged and reused.     

Dispersion of polymer-grafted magnetic nanoparticles in homopolymers and block copolymers

The dispersion of magnetic nanoparticles (NPs) in homopolymer poly(methyl methacrylate) (PMMA) and block copolymer poly(styrene-b-methyl methacrylate) (PS-b-PMMA) films is investigated by TEM and AFM. The magnetite (Fe₃O₄) NPs are grafted with PMMA brushes with molecular weights from M = 2.7 to 35.7 kg/mol. Whereas a uniform dispersion of NPs with the longest brush is obtained in a PMMA matrix (P = 37 and 77 kg/mol), NPs with shorter brushes are found to aggregate. This behavior is attributed to wet and dry brush theory, respectively. Upon mixing NPs with the shortest brush in PS-b-PMMA, as-cast and annealed films show a uniform dispersion at 1 wt%. However, at 10 wt%, PS-b-PMMA remains disordered upon annealing and the NPs aggregate into 22 nm domains, which is greater than the domain size of the PMMA lamellae, 18 nm. For the longest brush length, the NPs aggregate into domains that are much larger than the lamellae and are encapsulated by PS-b-PMMA which form an onion-ring morphology. Using a multi-component Flory-Huggins theory, the concentrations at which the NPs are expected to phase separate in solution are calculated and found to be in good agreement with experimental observations of aggregation.     

Mesoscopic simulation of asymmetric-copolymer/homopolymer blends: Microphase morphological modification by homopolymer chains solubilization

In this work we present the results of a mesoscopic dynamic simulation study of ordered microphases modification in asymmetric-copolymer/homopolymer binary blends, where we explore the influence of the composition, packing density and solubilization of homopolymer chains into the compatible microdomains of the asymmetric copolymer. The poly(styrene)-poly(isoprene) (PS-PI) and homopoly(styrene) (HPS) molecules were built and represented by Gaussian chain models. The pure asymmetric copolymer generates spherical microdomains of poly(styrene) (PS) in the matrix of majority component, poly(isoprene) (PI), and is taken as the base for the binary blends. The mesoscopic dynamic evolution of asymmetric-PS-PI/HPS blends display a coarse-grained system sufficiently large to determine the separation of the microphase and the formation of ordered structures. The HPS chains tend to be selectively solubilized in the PS microdomains of the asymmetric copolymer, the repulsive interaction forces between homopoly(styrene) and poly(isoprene) chains assure that essentially all the HPS homopolymer exists in the PS microdomains. As the asymmetric-PS-PI/HPS composition is varied the mesoscale simulations predict ordered structures with defined morphologies of body-centred-cubic (BCC), hexagonal packed cylinders (HPC), hexagonal perforated layers (HPL) and lamellar phases (LAM). Ordered microphases appear in reverse order when the homopoly(styrene) composition is increased in the binary blend. The agreement between our mesoscopic simulation results and available experimental outcome open a new strategy to modify the microphase morphology of asymmetric copolymers.     

Viscoelastic properties of a styrene-isoprene-styrene triblock copolymer and its blends with polyisoprene homopolymer and styrene-isoprene diblock copolymer

The effects of added polyisoprene homopolymer (PI) and polyisoprene-blockstyrene diblock copolymer (SI) on the viscoelastic properties of a polystyrene-block-polyisoprene-block-polystyrene triblock copolymer (SIS) having a spherical domain morphology have been examined. The former two species are used to model the effects of imperfections in structures that result from triblock copolymers missing, respectively, two or one polystyrene end blocks. The results indicate that the loss modulus and tangent delta in the plateau region can be dominated by imperfections in the copolymer structure. The interpretation of viscoelastic data in the rubbery plateau region as an indication of interface structure in block copolymers is therefore greatly complicated. Small angle X-ray scattering (SAXS) and rheological tests were also used to determine the order-disorder transition temperature for an SIS triblock copolymer and its blend with an SI diblock. The SAXS data are consistent with Han's rheological criteria for determining the order-disorder transition temperature. However, the complex viscosity does exhibit Newtonian behavior for low rates at the highest temperatures, even though the domain morphology persists. Stress relaxation and dynamic modulus data at high temperatures clearly show a secondary “rubbery” plateau at long times, and we offer a qualitative explanation for this feature based on a proposed relaxation mechanism.     

Molecular modeling and atomistic simulation strategies to determine surface properties of perfluorinated homopolymers and their random copolymers

Molecular mechanics (MM) and molecular dynamics (MD) simulations on ten perfluoroalkyl methacrylates and four copolymers derived from methyl methacrylate (MMA) and 1,1-dihydroperfluorohendecyl methacrylate (F10MA) in different ratios have been performed to predict surface properties. 1,1-Dihydroperfluorohendecyl methacrylate, which contained highest number of fluorine atoms, exhibited lowest surface energy, a trend that is in accordance with experimental observations. Density calculations on selected perfluoroalkyl methacrylates have been performed using NPT dynamics, for which no experimental data are available. Computations were performed to obtain bulk properties like cohesive energy density and solubility parameter through MM and MD simulations in the NVT ensemble under periodic boundary conditions. From the equilibrated structures, surface energies were computed, which compared well with the experimental data reported in the literature. Surface energies of copolymers decreased with increasing number of perfluoroalkyl groups. Various components of energetic interactions have been examined in detail in order to gain a better insight into interactions between bulk structure and the film. The dominant contributions are from van der Waals and Coulombic energy terms. The computed mass density profile for thin films gave an indication whether the film is of sufficient thickness so that the interior of the film is indistinguishable from the bulk structure. The total pair correlation and bond correlation functions have been analyzed to confirm the amorphous nature of the simulated structures.     

Crystallization and morphology of ultrathin films of homopolymers and polymer blends

Ultrathin films of thicknesses below 100 nm are now considered in different areas of applications. Their behavior in term of kinetics of crystallization is very different from that of bulk samples due to the film confinement in two-dimensions, and their morphologies are unique. In this review, recent advances in the crystallization of ultrathin films of homopolymers and miscible polymer blends will be described, with an emphasis on morphologies and, in the case of blends, on mixtures made of two crystalline polymers.