Photoelectric properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with polyhedral oligomeric silsesquioxane

4,4′‐(Hexafluoro‐isopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) was synthesized and reacted with polyhedral oligomeric silsesquioxane (POSS) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The solid‐state and optical properties of the resulting copolymers were systematically investigated, and their electronic states were analyzed. As the POSS concentration increased, the transparency across the entire wavelength range increased. In the ABA‐type triblock copolymers, a new transition was observed between the highest occupied molecular orbital in POSS and the lowest unoccupied molecular orbital in 6FDA‐TeMPD because of their high molecular size dispersion. Since the refractive index of 6FDA‐TeMPD decreased linearly as the POSS concentration increased, the refractive index of the ABA‐type triblock copolymers of 6FDA‐TeMPD with POSS could be easily controlled. POLYM. ENG. SCI., 57:1207–1213, 2017. © 2017 Society of Plastics Engineers     

Synthesis and gas permeability of ABA‐type triblock copolymers derived from fluorine‐containing polyimide with polyhedral oligomeric silsesquioxane

ABA‐type triblock copolymers derived from 4,4'‐(hexafluoroisopropylidene)diphthalicanhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and methacryl phenyl polyhedral oligomeric silsesquioxane (MPPOSS) were synthesized by atom transfer radical polymerization. The chemical structure of the synthesized ABA‐type triblock copolymer was confirmed by ¹H NMR, ¹³C NMR, ²⁹Si NMR and Fourier transform infrared analyses. The ratios of 6FDA‐TeMPD and MPPOSS determined by TGA were 94/6, 85/15, 77/23, 68/32, 57/43 and 31/69. The film density of the ABA‐type triblock copolymer films did not conform to the mixing rule because of polyimide (PI) chain aggregation. Based on contact angle and water uptake analyses, the hydrophobicity of the ABA‐type triblock copolymer film was determined to be higher than the theoretical value because of POSS cage effects and PI chain aggregation. The gas permeability coefficient of the ABA‐type triblock copolymer decreased compared with that of PI because of aggregation of PI chains and inhibition of solubility decreases by substitutes with high affinity. ABA‐type triblock copolymer CO₂/H₂ separation performance increased compared with that of PI. The ABA‐type triblock copolymer derived from PI and MPPOSS can be described as a polymer material with higher hydrophobicity and higher CO₂/H₂ selectivity than PI. © 2015 Society of Chemical Industry     

Preparation of porous membranes by selective decomposition of adamantane unit in ABA‐type triblock copolymer

The mechanism of pore formation by selective decomposition of adamantane unit in an ABA‐type triblock copolymer derived from 4,4‐(hexafluoroisopropylidene)diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and poly(2‐methyl‐2‐adamantylmethacrylate) (PMAdMA) was investigated on this basis. This study aims to developing a novel method of material design for high‐precision gas separation membranes and application to electric devices by improving dielectric constant. Scanning electron microscopy images showed that the membrane structure changed considerably after heating; the difference increased with the increase in adamantane content. Interestingly, the internal structure of Block(36 mol%6FDA‐TeMPD/64 mol%PMAdMA) membrane was almost unchanged although its surface structure was changed. These results suggest that the mechanism of formation of porous membrane involves the decomposition of adamantane unit from surface. In addition, more adamantane units inside the membrane were discharged to the surface of the membrane through a path formed by decomposed adamantane units. POLYM. ENG. SCI., 56:1191–1200, 2016. © 2016 Society of Plastics Engineers     

Characterization and water vapor sorption property of ABA‐type triblock copolymers derived from polyimide and poly(methyl methacrylate)

The characterization of ABA‐type triblock copolymer films derived from polyimide (PI) macroinitiator and poly(methyl methacrylate) (PMMA) synthesized by atom transfer radical polymerization was investigated by focusing on different block lengths of PMMA. The hydrophobic property tends to increase with increasing PMMA content in the triblock copolymers, while the PMMA blocks enhance the charge transfer interaction between the PI segments. The water vapor sorption measurement of triblock copolymers was determined at 35 °C. The water vapor solubility of triblock copolymers tends to decrease with increasing PMMA content. In addition, linear correlations were observed between the solubility and polymer‐free volume and polymer molecular polarity in triblock copolymers as well as in other conventional polymer families. According to Zimm?Lundberg analysis, the PMMA block segments in the triblock copolymers accelerate water vapor clustering due to the high mobility of PMMA. The mobility of PMMA block segments strongly affected not only physical properties but also the water vapor solubility of the triblock copolymers. The ABA triblock copolymerization composed of PI and PMMA is one of the effective ways to improve the hydrophobic property. © 2013 Society of Chemical Industry     

Solid and thermal properties of ABA‐type triblock copolymers designed using difunctional fluorine‐containing polyimide macroinitiators with methyl methacrylate

BACKGROUND: ABA‐type poly(methyl methacrylate) (PMMA) and fluorine‐containing polyimide triblock copolymers are potentially beneficial for electric materials. In the work reported here, triblock copolymers with various block lengths were prepared from fluorine‐containing difunctional polyimide macroinitiators and methyl methacrylate monomer through atom‐transfer radical polymerization. The effects of structure on their solid and thermal properties were studied. RESULTS: The weight ratios of the triblock copolymers derived using thermogravimetric analysis were shown to be almost identical to the ratios determined using ¹H NMR. The solid properties (film density and maximum d‐spacing value) and thermal properties (glass transition and thermal expansion) were shown to be strongly dependent on the weight ratios of both PMMA and polyimide components. Furthermore, a porous film, which showed a lower dielectric constant of 2.48 at 1 MHz, could be prepared by heating a triblock copolymer film to induce the thermal degradation of the PMMA component. CONCLUSION: The use of the polyimide macroinitiator was useful in the preparation of ABA‐type triblock copolymers to control each block length that influences the solid and thermal properties. Additionally, the triblock copolymers have great potential in preparing porous polyimides in the application of electric materials as interlayer insulation membranes of large‐scale integration. Copyright © 2009 Society of Chemical Industry     

Nanostructured polymer blends based on polystyrene‐b‐polybutadiene‐b‐poly(methyl methacrylate) triblock copolymers modified with polystyrene and/or poly(methyl methacrylate) homopolymers

Morphologies of polymer blends based on polystyrene‐b‐ polybutadiene‐b ‐poly(methyl methacrylate) (SBM) triblock copolymer were predicted, adopting the phase diagram proposed by Stadler and co‐workers for neat SBM block copolymer, and were experimentally proved using atomic force microscopy. All investigated polymer blends based on SBM triblock copolymer modified with polystyrene (PS) and/or poly(methyl methacrylate) (PMMA) homopolymers showed the expected nanostructures. For polymer blends of symmetric SBM‐1 triblock copolymer with PS homopolymer, the cylinders in cylinders core?shell morphology and the perforated lamellae morphology were obtained. Moreover, modifying the same SBM‐1 triblock copolymer with both PS and PMMA homopolymers the cylinders at cylinders morphology was reached. The predictions for morphologies of blends based on asymmetric SBM‐2 triblock copolymer were also confirmed experimentally, visualizing a spheres over spheres structure. This work presents an easy way of using PS and/or PMMA homopolymers for preparing nanostructured polymer blends based on SBM triblock copolymers with desired morphologies, similar to those of neat SBM block copolymers. © 2017 Society of Chemical Industry     

Surface microphase separation in PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films

Well‐defined poly(dimethylsiloxane)‐block‐poly(methyl methacrylate)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) (PDMS‐b‐PMMA‐b‐PHFBMA) triblock copolymers were synthesized via atom transfer radical polymerization (ATRP). Surface microphase separation in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films was investigated. The microstructure of the block copolymers was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Surface composition was studied by X‐ray photoelectron spectroscopy (XPS). The chemical composition at the surface was determined by the surface microphase separation in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films. The increase of the PHFBMA content could strengthen the microphase separation behavior in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films and reduce their surface tension. Comparison between the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymers and the PDMS‐b‐PHFBMA diblock copolymers showed that the introduction of the PMMA segments promote the fluorine segregation onto the surface and decrease the fluorine content in the copolymers with low surface energy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Relationship between the gas transport properties and the refractive index in high‐free‐volume fluorine‐containing polyimide membranes

The refractive index and gas transport properties (i.e., permeability, diffusivity, and solubility) in the 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA)‐based polyimides were systematically investigated in terms of their polymer fractional free volumes (FFVs). The permeability and diffusion coefficients of the 6FDA‐based polyimide membranes to hydrogen, oxygen, nitrogen, methane, and carbon dioxide were correlated with their FFVs, which were estimated with van Krevelen's group contribution method. Linear correlations were also observed between the gas transport properties and the refractive index of these polyimides. We described FFV as a function of the refractive index based on the Lorentz–Lorenz equation. Linear correlations were observed between their refractive‐index‐based FFVs and the gas permeability, diffusivity, and solubility coefficients of these 6FDA‐based polyimides membranes. However, the FFVs of the 6FDA‐based polyimides calculated from refractive index were 1.16–1.37 times larger than their FFV values. This FFV was dependent on the free‐volume space and optical factors, such as the refractive index and molar refraction, which affected the electronic structure and the interactions between the gas molecules and the polymer segments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene blends

An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene (PDMS‐b‐PMMA‐b‐PS) triblock copolymer was synthesized by the atom‐transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS‐b‐PMMA‐b‐PS blends were studied within the whole range of concentration. In this A‐b‐B‐b‐C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self‐assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 °C reveals that both α and β crystalline phases of PVDF are present in PVDF/PDMS‐b‐PMMA‐b‐PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of β to α phase of semicrystalline PVDF. Introduction of PDMS‐b‐PMMA‐b‐PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small‐angle X‐ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. © 2019 Society of Chemical Industry     

Synthesis and characterization of star‐branched polyisobutylene with SIpS triblock copolymer core

Well‐defined polystyrene‐b‐polyisoprene‐b‐polystyrene (SIpS) triblock copolymers with different microstructures were synthesized by living anionic polymerization. The synthesis of star‐branched polyisobutylene (PIB) was accomplished by the cationic polymerization in 2‐chloro‐2,4,4‐trimethylpentane/titanium tetrachloride/SIpS triblock copolymer/2,6‐di‐tert‐butylpyridine initiating system. The double bonds in SIpS triblock copolymer were activated as starting points for isobutylene polymerization. The formation of star‐branched architecture was demonstrated by size‐exclusion chromatography with quadruple detection: refractive index, multiangle laser light scattering, viscometric, and ultraviolet detectors. SIpS triblock copolymer with high 3,4‐PIp content is more reactive than that with high 1,4‐PIp content in cationic initiating stage. The yields of star‐branched PIB were remarkably dependent on the reaction time of TMP⁺ with SIpS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Membrane color and gas permeability of 6FDA‐TeMPD polyimide membranes prepared with various membrane preparation protocols

The relations among polyimide membrane colors, their gas transport and separation properties, and their fluorescence spectra were systematically investigated using fluorine‐containing aromatic polyimide, 6FDA‐TeMPD {[4,4‐(hexafluoroisopropylidene) diphthalic anhydride] [(6FDA)‐2,3,5,6‐tetramethyl‐1,4‐phenylene‐diamine (TeMPD)]}, which was used in electronic device and gas separation materials. Different molecular ordering structures of 6FDA‐TeMPD polyimides were prepared by controlling kinds of casting solvents and dry conditions. This difference was based on the effect of charge transfer (CT) interaction formed by π electrons of ring structures in polyimide. Membrane color measured using spectrophotometer determined colors as intrinsic parameters without sample collection. The permeability coefficients of oxygen and nitrogen of the 6FDA‐TeMPD polyimide membranes were correlated with membrane color index parameters such as L*, a*, b*, and ΔE*, and fluorescence properties such as maximum peak emission wavelength λ_max and intensity I_max, which reflect molecular ordering affected by CT interaction in polyimide membranes. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

AB‐ and ABC‐type di‐ and triblock copolymers of poly[styrene‐block‐(ε‐caprolactone)] and poly[styrene‐block‐(ε‐caprolactone)‐block‐lactide]: synthesis,characterization and thermal studies

Polystyrene terminated with benzyl alcohol units was employed as a macroinitiator for ring‐opening polymerization of ε‐caprolactone and L ‐lactide to yield AB‐ and ABC‐type block copolymers. Even though there are many reports on the diblock copolymers of poly(styrene‐block‐lactide) and poly(styrene‐block‐lactone), this is the first report on the poly(styrene‐block‐lactone‐block‐lactide) triblock copolymer consisting of two semicrystalline and degradable segments. The triblock copolymers exhibited twin melting behavior in differential scanning calorimetry (DSC) analysis with thermal transitions corresponding to each of the lactone and lactide blocks. The block derived from ε‐caprolactone also showed crystallization transitions upon cooling from the melt. In the DSC analysis, one of the triblock copolymers showed an exothermic transition well above the melting temperature upon cooling. Thermogravimetric analysis of these block copolymers showed a two‐step degradation curve for the diblock copolymer and a three‐step degradation for the triblock copolymer with each of the degradation steps associated with each segment of the block copolymers. The present study shows that it is possible to make pure triblock copolymers with two semicrystalline segments which also consist of degradable blocks. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of ABA‐type triblock copolymers derived from polyimide and poly(2‐methyl‐2‐adamantyl methacrylate)

ABA‐type triblock copolymers derived from 4,4‐(hexafluoroisopropylidene)diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine and 2‐methyl‐2‐adamantyl methacrylate (2‐MAdMA) were synthesized via atom transfer radical polymerization. The component ratios of polyimide (PI) and poly(2‐MAdMA) (PMAdMA) were about 8/2, 6/4 and 3/7, as determined using ¹H NMR spectroscopy and thermogravimetric analysis (TGA). The film structure of the triblock copolymers was dependent on the PI structure. Hydrophobicity increased as the component ratio of PMAdMA increased. Based on TGA, three‐step decomposition behaviors of all triblock copolymers derived from PI and PMAdMA in nitrogen and air atmosphere were observed. The gas permeability of the triblock copolymers was lower than that of PI. This finding can be attributed to the decrease in fractional free volume by the adamantane component and the decrease in permeability of the triblock copolymers compared with PI. The dielectric constant of the triblock copolymers was lower than that of PI. The dielectric constant was dependent on molar volume and molar porlarizability, and the dielectric constant derived from the symmetric structure of adamantane was reduced. The ABA‐type triblock copolymers derived from PI and PMAdMA can be considered as new polymer materials with high hydrophobicity, high H₂/CO₂ selectivity and low dielectric constant. © 2013 Society of Chemical Industry     

The characteristic properties of poly(methyl methacrylate)/polystyrene core‐shell composite polymer latex

In this study, the poly(methyl methacrylate/polystyrene (PMMA/PS) core‐shell composite latex was synthesized by the method of soapless seeded emulsion polymerization. The morphology of the PMMA/PS composite latex was core‐shell structure, with PMMA as the core and PS as the shell. The core‐shell morphology of the composite polymer latex was found to be thermally unstable. Under the effect of thermal annealing, the PS shell region first dispersed into the PMMA core region, and later separated out to the outside of the PMMA core region. This was explained on the basis of lowing interfacial tension between the PMMA and PS phases owing to the interpenetration layer. The interpenetration layer, which was located at the interface of the core and shell region, contained graft copolymer and entangled polymer chains. Both the graft copolymer and entangled polymer chains had the ability to lower the interfacial tension between the PMMA and PS phases. Also, the effect of thermal annealing on the morphology of commercial polymer/composite latex polymer blends was examined. The result showed that the core‐shell composite latex had the ability to enhance the compatibility of the components of polymer blends. The compatibilizing ability of the core‐shell composite latex was better than that of a random copolymer. Moreover, the effect of the amount of core‐shell composite latex on the morphology of the polymer blend was investigated. The polymer blends, which contained composite latex above 50% wt, showed the morphology of a double sea‐island structure. In addition, the composite latex was completely dissolved in solvent to destroy the core‐shell structure and release the entangled polymer chains, and then dried to form the entangled free composite polymer. The entangled free composite polymer had the ability to enhance the compatibility of the components of the polymer blend as usual. The weight ratio 3/7 commercial polymer/entangled free composite polymer blend showed the morphology of the phase inversion structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 312–321, 2003     

Phototransparency and water vapor sorption properties of ABA‐type triblock copolymers derived from 6FDA‐TeMPD and poly(2‐methyl‐2‐adamantylmethacrylate)

The phototransparency and water vapor sorption properties of ABA‐type triblock copolymer membranes derived from 4,4‐(hexafluoroisopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (PI) and poly(2‐methyl‐2‐adamantylmethacrylate) (PMAdMA) were investigated, with focus on the effect of the adamantane component. The phototransparency of PMAdMA‐block‐PI‐block‐PMAdMA [Block(PI/PMAdMA)] was about 10–20% higher than that of poly(methyl methacrylate)‐block‐PI‐block‐Poly(methylmethacrylate) [Block(PI/PMMA)] because the high symmetric structure of adamantane inhibited photoabsorbance. The water vapor solubility of Block(PI/PMAdMA) decreased with increased PMAdMA because the PMAdMA had a hydrophobic property. Interestingly, in all relative‐pressure regions, Block(PI/PMAdMA) with the least PMAdMA content showed a higher solubility coefficient than PI because the high mobility of PMAdMA in Block(PI/PMAdMA) resulted in additional sorption sites in the PI segment. A comparison of Block(PI/PMAdMA) with Block(PI/PMMA) in terms of relative pressure at the beginning of clustering further revealed that cluster formation in Block(PI/PMAdMA) was inhibited compared with Block(PI/PMMA) because bulky structure of adamantane restricted the mobility of the polymer main chain. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43795.     

Effects of thermal treatment on the CO2 sorption of triblockcopolymers derived from polyimide and poly(methylmethacrylate)

ABA‐type triblock copolymers were synthesized using 4,4‐(hexafluoroisopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and poly(methyl methacrylate) (PMMA). The films were characterized by determining the effects of different content ratios and thermal decomposition of PMMA block on CO₂ sorption properties. TGA results showed that a thermal labile block can be completely decomposed under a previously reported thermal condition. SEM results presented that the asperity was micro‐phase separation caused by the PMMA block content rate. Numerous pores with sizes of approximately 10 to 50 nm were detected on Block(28/72) and Block(10/90). The isotherms of all films fitted the dual‐mode sorption model, and CO₂ sorption decreased with increased PMMA content rate. Infinite‐dilution CO₂ solubility depended on the Langmuir's site of each polymer because S_H0/S₀ of PI and Block(PI/PMMA) varied from 0.84 to 0.92 CO₂ affinity was increased by thermal treatment as indicated by the higher b and S₀ values of thermally treated films than those of nontreated films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42208.     

The effect of the addition of poly(styrene‐co‐glycidyl methacrylate) copolymer on the properties of polylactide/poly(methyl methacrylate) blend

The effect of the addition of poly(styrene‐co‐glycidyl methacrylate) P(S‐co‐GMA) copolymer on the properties of melt blended polylactide/poly(methyl methacrylate) (PLA/PMMA) 80/20 (wt %) composition was studied. In the literature high ductility levels were achieved by melt blending PLA with different additives. However, the gained ductility was counter balanced with drastic drops in strength and modulus values. The novelty of this work was the preparation of PLA‐based blends with polylactide content higher than 75 wt % which showed an impact resistance value improvement of about 60% compared with the neat PLA and maintained similar tensile strength and modulus values as well as glass transition temperature to neat PLA. The addition of only 3 pph of copolymer to PLA/PMMA blend improved the impact resistance almost 100%. The chemical reaction between PLA/PMMA blend and P(S‐co‐GMA) copolymer were analyzed by FTIR, rotational rheometry, and GPC/SEC. Phase structure and morphology were studied by Differential Scanning Calorimetry and Scanning Electronic Microscopy. Tensile and impact properties as well as thermal stability were also studied. Results showed that as the amount of copolymer in the blend was increased then higher was average molecular weight and polydispersity index. After the addition of P(S‐co‐GMA) copolymer to the PLA/PMMA blend the impact resistance, elongation at break and thermal stability were improved while tensile strength and elastic modulus remained almost unaltered. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43935.     

Melt rheological behavior of a triblock copolymer based on aramide end‐segments

Melt rheological behavior of a ABA triblock polymer made of poly(tetramethylene oxide) (PTMO) (M_n = 2,900 g mol^?1) soft segment and aramide hard segment was studied. The aramide end‐segments ( A ) were short and mono‐disperse in length. The mid‐segment ( B ) consisted of PTMO₂₉₀₀ extended with terephthalate units to a molecular weight of 9000 g mol^?1. The molecular weight of the triblock was 9700 g mol^?1. Rheological behavior of this material was studied by parallel‐plate and capillary method. The ABA triblock copolymer was compared with a B polymer (PTMO‐terephthalate) of a similar molecular weight. The low molecular weight B polymer had a Newtonian behavior. The low molecular weight triblock copolymer had at high frequencies a low complex viscosity. However, at low frequencies the triblock copolymer had a very high complex viscosity. Also the G″/G′ ratio decreased with decreasing frequency to values less then one and the G′ seemed to have at low frequencies a plateau value. The activation energy of the process increased in value with decreasing shear rate. All these results indicate that the triblock copolymer at low frequencies had a gel‐like behavior and this probably due to the clustering of the aramide segments. The aramide clusters are thought to be the (weak) network points of the gel. This network was also found to have a time dependant rheological response and thus a thixotropic behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Highly transparent thermoplastic elastomer from isotactic polypropylene and styrene/ethylene‐butylene/styrene triblock copolymer: Structure‐property correlations

Polypropylene (PP) is one of the most useful general purpose plastics. However, the poor transparency and brittleness of PP restricts its applications in the field of medical and personal care where silicone and polyvinyl chloride (PVC) are presently used. This work concentrates on developing highly transparent elastomeric PP blends and also thermoplastic elastomer by blending isotactic polypropylene (I‐PP) with styrene/ethylene‐butylene/styrene (SEBS) triblock copolymer. PP/SEBS blend derived from high melt flow index (MFI) PP and high MFI SEBS exhibit remarkable transparency (haze value as low as 6%) along with good percentage of elongation and processability. The reduction in difference of refractive index (RI) between PP and SEBS has been observed by blending SEBS with PP. The wide angle X‐ray diffraction studies show that there is significant reduction in the percentage crystallinity of PP by the addition of SEBS block copolymer. Temperature‐dependent polarized light microscopy studies reveal the reduction in spherulites size by the addition of SEBS block copolymer. Transmission electron micrographs show that the SEBS polymer forms a fine lamellar structure throughout the PP matrix with phase inversion at higher SEBS concentration. Development of phase morphology, crystalline morphology, and crystallinity in different blends has been analyzed and microstructure‐haze correlations have been developed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Crystallization behavior of dry‐brush PEO‐PS block copolymer and PEO homopolymer blend

The crystallization behavior of semicrystalline PEO homopolymer/triblock PS‐PEO‐PS copolymer blend system, which exhibited “Dry‐Brush” in the melt. A symmetric polystyrene–poly(ethylene oxide)–polystyrene triblock copolymer was blended with PEO homopolymer (h‐PEO) having the same molecular weight as that of the PEO block in the copolymer. Considering the composition of the blend (W_ps ≥ 0.8), PEO spheres were formed in the blend. Because of the dry‐brush phase behavior of this blend, h‐PEO added was localized in the PEO microdomains, which increases the domain size without changing the microdomain morphology. The crystallization of PEO block was confined within the microdomains and the crystallization temperature was about 60°C lower than normal. Self‐seeding tests were performed to clarify the nucleation mechanism of the blend. Because the droplets size varies greatly, multicrystallization peaks were witnessed in the self‐seeding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007