The architecture of hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE via one‐pot strategy combining living free radical polymerization with coordination polymerization

The copolymerization of styrene with ethylene was promoted by CpTiCl₃/BDGE/Zn/MAO catalyst system combining free radical polymerization with coordination polymerization via sequential monomer addition strategy in one‐pot. The effect of polymerization conditions such as temperature, time, ethylene pressure, and Al/Ti molar ratio on the polymerization performance was investigated. The hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE triblock copolymer was obtained by solvent extraction and determined by GPC, DSC, WAXD, and ¹³C‐NMR. The DSC result indicated that the aPS‐b‐random copolymer‐b‐PE had a T_g at 87°C and a T_m at 119°C which attributed to the T_g of aPS segment and the T_m of PE segment, respectively. The microstructure of the hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE was further confirmed by WAXD, ¹³C‐NMR, and ¹H‐NMR analysis; and these results demonstrated that the obtained block copolymer consisted of aPS segment, S‐E random copolymer segment, and crystalline PE segment. The connection polymerization of the hydroxy‐functionalized aPS with random copolymer‐b‐PE was revealed by GPC results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Control of the confined and unconfined crystallization in glassy-crystalline poly(vinylcyclohexane)-b-poly(ethylene)-b-poly-(vinylcyclohexane) triblock copolymer in solution

The influence of the solvent evaporation rate on the crystallization of the poly(vinylcyclohexane)-b-poly(ethylene)-b-poly(vinylcyclohexane) (PVCH-PE-PVCH) triblock copolymer with the high T_g of PVCH segment in chloroform was investigated. The competition between the crystallization of PE block and the vitrification of PVCH in the triblock copolymer was controlled through changing the solvent evaporation rate in the solution system at different temperatures (T_e). It was found that the melting temperature (T_m) of PVCH-PE-PVCH samples increased with increasing the T_e when the T_e was lower than the solvent boiling point (bp), depending on the crystalline temperatures. However, when T_e was just a little above the solvent bp, two melting peaks, which corresponding to the fusion of the confined and unconfined crystals, respectively, were observed on the DSC curves of the samples. As T_e increased to be higher temperature, only one lower melting peak, which corresponding to the fusion of the confined crystals, existed for each samples. It was also found that the crystallinity (X_c) of the samples decreased gradually when T_e was lower than the solvent bp, and then decreased suddenly when T_e was just a little above the solvent bp, finally reached a plateau (about 13.5%) at higher T_e. The changes in X_c of the samples depend on the evaporating time in the solution. The results should be related to the competition between the crystallization of PE block in solvent and the vitrification of PVCH block with the solvent evaporation. Furthermore, the competition was controlled through changing the solvent evaporation rate. The confined and unconfined crystallization of the samples could be freely adjusted.     

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     

Synthesis and characterization of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers with dibutylmagnesium as catalyst

Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by ¹H NMR, ¹³C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (T_c) and melting endothermic peaks (T_m) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of amphiphilic pseudopolyamino acid‐containing ABC‐triblock copolymers and micellar characterizations

This study describes the synthesis of amphiphilic ABC‐triblock copolymers comprising a central pseudopoly(4‐hydroxy‐L ‐proline) segment and terminal hydrophilic poly(ethylene glycol)methyl ether as well as hydrophobic poly(ε‐caprolactone) blocks. Differential scanning calorimetry, ¹H‐NMR spectroscopy, and gel permeation chromatography are used to characterize the copolymers. The thermal properties (T_g and T_ms) of the triblock copolymers depend on the composition of polymers. Larger amounts of ε‐CL incorporated into the macromolecular backbone increased T_g and T_ms. Fluorescence spectroscopy, transmission electron microscopy, and dynamic light scattering are utilized to investigate their micellar characteristics in the aqueous phase. Observations showed a higher critical micelle concentration with higher hydrophilic components in the copolymers. The micelle exhibited a core‐shell‐corona and/or vesicle shape, and the average size was less than 300 nm. Drug entrapment efficiency and drug loading of micelles depending on the composition of block polymers are also described. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of supercritical carbon dioxide treatment on the morphology of poly(l‐lactide)

Synthetic l ‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO₂), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO₂ processing, three types of poly(l ‐lactide) having different properties were assessed. The T_m of one poly(l ‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l ‐lactide) REVODE exhibited a T_m of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the T_m value of the REVODE tended to decrease with increasing pressure. The T_g values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the T_g values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All T_g values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χ_{c DSC} of the H‐100 was 18% initially but increased to 20% upon scCO₂ processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χ_{c DSC} values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χ_{c XRD} values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO₂ treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l ‐lactide) samples treated with scCO₂, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44006.     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Thermal behaviour of polyethylene‐block‐poly(methyl methacrylate) block copolymer: effect of multiple heating and cooling rates versus mathematical artefact

The melting and crystallization behaviours of a polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) diblock copolymer and a PE homopolymer were investigated using multiple heating and cooling rate differential scanning calorimetry (DSC) experiments, and modelling of the crystallization kinetics and lamellar thickness distribution. This new model was first validated applying literature and experimental data. The model‐predicted morphology (n = 3.2) closely matched the spherulitic morphology (n = 3), which was determined using polarized optical microscopy. For each experimental cooling rate, the model predicted diblock copolymer crystallinity that well matched the entire DSC crystallinity curve, notably for an Avrami–Erofeev index of n = 2; and apparent crystallization activation energy that hardly varied with the cooling rates used, relative crystallinity (α), and crystallization temperature or time. This disfavours the concept of variable activation energy. The use of the right crystallization model and parameter estimation algorithm is important for addressing the mathematical artefact. Under non‐isothermal cooling, the PE‐b‐PMMA diblock copolymer, as per the model prediction, crystallized without confinement (n ≠ 1), preserving the cylindrical structure. From the characteristic shapes of the crystallization function f(α(T)) versus 1/T and crystallization rate versus α plots, the resulting T_cmax and narrow α_max range can guide the search for an appropriate crystallization model. The overall treatment illustrated in this study is not restricted to a PE homopolymer and a PE‐b‐isotactic PMMA block copolymer. It can be generally applied to crystalline homopolymers and copolymers (alternating, random and block), as well as their blends. The block copolymers and blends can be crystalline–amorphous as well as crystalline–crystalline. © 2014 Society of Chemical Industry     

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 block copolymers of trimethylene carbonate and ϵ‐caprolactone

This paper describes the synthesis of a series of ABA‐type triblock copolymers of trimethylene carbonate and ?‐caprolactone with various molar ratios and analyses the thermal and mechanical properties of the resulting copolymers. The structures of the triblock copolymers were characterized by ¹H and ¹³C nuclear magnetic resonance spectroscopy, FT‐IR spectroscopy and gel permeation chromatography. Results obtained from the various characterization methods proves the successful synthesis of block copolymers of trimethylene carbonate and ?‐caprolactone. The thermal properties of the block copolymers were investigated by differential scanning calorimetry. The T_m and ΔH_m values of the copolymers decrease with increasing content of trimethylene carbonate units. Two T_gs were found in the copolymers. Furthermore, both of the T_g values increased with increasing content of trimethylene carbonate units. The mechanical properties of the resulting copolymers were studied by using a tensile tester. The results indicated that the mechanical properties of the block copolymers are related to the molar ratio of trimethylene carbonate and ?‐caprolactone in the copolymers, as well as the molecular weights of the resulting copolymers. The block copolymer with a molar composition of 50/50 possessed the highest tensile stress at maximum and modulus of elasticity. Block copolymers possessing different properties could be obtained by adjusting the copolymer compositions. Copyright © 2004 Society of Chemical Industry     

Synthesis of polysiloxane with 5,5‐dimethylhydantoin‐based N‐halamine pendants for biocidal functionalization of polyethylene by supercritical impregnation

An N‐halamine precursor 3‐(3‐hydroxypropyl)‐5,5‐dimethylhydantoin (HPDMH) has been synthesized. The N‐halamine precursor was reacted with poly(methylhydrosiloxane) (PMHS) to produce a biocidal polysiloxane with 5,5‐dimethylhydantoin‐based N‐halamine pendants through silane alcoholysis and subsequent chlorination of hydantoin ring with tert‐butyl hypochlorite. The N‐halamine polysiloxane was impregnated into inert polyethylene (PE) fibers and formed a 68‐nm coating layer in supercritical carbon dioxide (scCO₂) for antibacterial application. The PE fibers before and after impregnation were characterized by XPS and SEM. The N‐halamine polysiloxane impregnated PE samples provided effective biocidal activities against both Staphylococcus aureus and Escherichia coli compared with unmodified ones that did not display obvious antibacterial activities. The coating layer on PE substrate was stable toward washing cycles, storage, and UV irradiation and the rechargeability of lost active chlorines was good. The scCO₂ impregnation approach uses environmentally friendly CO₂ as solvent and can be applied to both reactive and nonreactive substrates since it does not require covalent bonds to tether biocidal moieties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44721.     

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     

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     

PE/PE‐g‐MAH/Org‐MMT nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of high‐density polyethylene (HDPE) and polyethylene (PE)/PE‐grafted maleic anhydride (PE‐g‐MAH)/organic‐montmorillonite (Org‐MMT) nanocomposite were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny, Ozawa analysis, and a method developed by Liu well described the nonisothermal crystallization process of these samples. The difference in the exponent n, m, and a between HDPE and the nanocomposite indicated that nucleation mechanism and dimension of spherulite growth of the nanocomposite were different from that of HDPE to some extent. The values of half‐time (t_1/2), K(T), and F(T) showed that the crystallization rate increased with the increase of cooling rates for HDPE and composite, but the crystallization rate of composite was faster than that of HDPE at a given cooling rate. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. It was 223.7 kJ/mol for composite, which was much smaller than that for HDPE (304.6 kJ/mol). Overall, the results indicated that the addition of Org‐MMT and PE‐g‐MAH could accelerate the overall nonisothermal crystallization process of PE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3054–3059, 2004     

Synthesis and self‐assembly of amphiphilic star‐block copolymers consisting of polyethylene and poly(ethylene glycol) segments

We report on the synthesis and self‐assembly in water of well‐defined amphiphilic star‐block copolymers with a linear crystalline polyethylene (PE) segment and two or three poly(ethylene glycol) (PEG) segments as the building blocks. Initially, alkynyl‐terminated PE (PE‐?) is synthesized via esterification of pentynoic acid with hydroxyl‐terminated PE, which is prepared using chain shuttling ethylene polymerization with 2,6‐bis[1‐(2,6‐dimethylphenyl) imino ethyl] pyridine iron (II) dichloride/methylaluminoxane/diethyl zinc and subsequent in situ oxidation with oxygen. Then diazido‐ and triazido‐terminated PE (PE‐(N₃)₂ and PE‐(N₃)₃) are obtained by the click reactions between PE‐? and coupling agents containing triazido or tetraazido, respectively. Finally, the three‐arm and four‐arm star‐block copolymers, PE‐b‐(PEG)₂ and PE‐b‐(PEG)₃, are prepared by click reactions between PE‐(N₃)₂ or PE‐(N₃)₃ and alkynyl‐terminated PEG. The self‐assembly of the resultant amphiphilic star‐block copolymers in water was investigated by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. It is found that, in water, a solvent selectively good for PEG blocks; these star‐block copolymer chains could self‐assemble to form platelet‐like micelles with insoluble PE blocks as crystalline core and soluble PEG blocks as shell. The confined crystallization of PE blocks in self‐assembled structure formed in aqueous solution is investigated by differential scanning calorimetry. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a difunctional organolithium compound as initiator for the polymerization of styrene‐butadiene/isoprene‐styrene triblock copolymer

A difunctional organolithium compound was prepared by the addition of butyllithium (BuLi) to 1,4‐bis(4‐methyl‐1‐phenylethenyl)benzene (MPEB). The effects of the solvent, polar modifier (THF), butyl lithium structure, and reaction time on the formation of the difunctional organolithium compound were studied. Results showed that toluene as solvent was in favor of the addition reaction over cycohexane, in the absence of the polar modifier. However, cycohexane was a better option as solvent for the addition reaction, when polar modifier was employed. A small amount of polar modifier could efficiently accelerate the reaction rate and have no significant effect on the structure of the polydiene, which was initiated by the polar modifier containing organolithium compound. Results also showed that isobutyl lithium was more active in the addition reaction than n‐butyl lithium, because of inductive effect. The optimum molar ratio of THF/Li+ was determined as 4. The THF containing difunctional organolithium cyclohexane solution was sequentially used in the step‐wise polymerization of triblock thermoplastic copolymer SIBS. The so‐prepared SIBS shared the similar phase separation structure with SBS and exhibited excellent mechanic properties. As the content of the central polyisoprene block increases, the tensile strength of the copolymer is decreased, and the elongation at break is increased. The glass transition temperature T_g of the central block was correlated with its content as T_g = 0.33 × ?62.81, where × is the wt % of the central block, based on the triblock copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1395–1402, 2006     

Dynamic mechanical properties of polystyrene‐block‐poly[ethylene‐co‐(ethylene‐propylene)]‐block‐polystyrene triblock copolymer/hydrocarbon oil blends

Blend systems of polystyrene‐block‐poly(ethylene‐co‐(ethylene‐propylene))‐block‐polystyrene (SEEPS) triblock copolymer with three types of hydrocarbon oil of different molecular weight were prepared. The E″ curves as a function of temperature exhibited two peaks; one peak at low temperature (? ?50°C), arising from the glass transition of the poly[ethylene‐co‐(ethylene‐propylene)] (PEEP) phase and a high temperature peak (? 100°C), arising from the glass transition of the polystyrene (PS) phase. The glass transition temperature (T_g) of the PEEP phase shifted to lower temperature with increasing oil content. The shifted T_g depended on the types of oil and was lower for the low molecular weight oil. The T_g of PS phase of the present blend system, were found to be constant and independent of the oil content, when molecular weight of the oil is high. However, for the lower molecular weight oil, the T_g of the PS phase also shifted to lower temperatures. This fact indicates that the oil of high molecular weight is merely dissolved in the PS phase. The E′ at (75°C, at which temperature both of PEEP and PS phases are in glassy state, was found to be independent of oil content. In contrast, at 25°C, at which temperature the PEEP phase is in rubbery state, the E′ decreased sharply with increasing oil content. This result indicates that the hydrocarbon oil was a selective solvent in the PEEP phase. It mainly dissolved in the PEEP phase, although slightly dissolved into the PS phase as well, when molecular weight of oil is low. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of biodegradable poly(butylene succinate‐co‐propylene succinate)s

Biodegradable polyesters such as poly(butylene succinate) (PBS), poly(propylene succinate) (PPS), and poly(butylene succinate‐co‐propylene succinate)s (PBSPSs) were synthesized respectively, from 1,4‐succinic acid with 1,4‐butanediol and 1,3‐propanediol through a two‐step process of esterification and polycondensation in this article. The composition and physical properties of both homopolyesters and copolyesters were investigated via ¹H NMR, DSC, TGA, POM, AFM, and WAXD. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), crystallinity (X), and thermal decomposition temperature (T_d) of these polyesters decreased gradually as the content of propylene succinate unit increased. PBSPS copolyesters showed the same crystal structure as the PBS homopolyester. Besides the normal extinction crosses under the polarizing optical microscope, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoplastic hydrogel based on pentablock copolymer consisting of poly(γ‐benzyl L‐glutamate) and poloxamer

A thermoplastic hydrogel based on a pentablock copolymer composed of poly(γ‐benzyl L ‐glutamate) (PBLG) and poloxamer was synthesized by polymerization of BLG N‐carboxyanhydride, which was initiated by diamine‐terminated groups located at the ends of poly(ethylene oxide) (PEO) chains of the poloxamer, to attain a new pH‐ and temperature‐sensitive hydrogel for drug delivery systems. Circular dichroism measurements in solution and IR measurements in the solid state revealed that the polypeptide block existed in the α‐helical conformation, as in the PBLG homopolymer. The intensity of the wide‐angle X‐ray diffraction patterns of the polymers depended on the poloxamer content in the copolymer and showed basically similar reflections to the PBLG homopolymer. The melting temperature (T_m) of the poloxamer in the copolymer was reduced with an increase of the PBLG block in comparison with the T_m of the poloxamer, which is indicative of a thermoplastic property. The water contents of the copolymers were dependent on the poloxamer content in the copolymers, for example, those for the GPG‐2 (48.7 mol % poloxamer) and GPG‐1 (57.5 mol % poloxamer) copolymers were 31 and 41 wt %, respectively, indicating characteristics of a polymeric hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2649–2656, 2003     

Film‐forming process from globular polytetrafluoroethylene latex particles

Film formation from an aqueous polytetrafluoroethylene (p‐TFE) latex dispersion on glass tissues was studied. The p‐TFE particles were of globular shape, had a diameter of 220 ± 20 nm, and were of high crystallinity (～ 100%). The melting point of the material was 332°C. For the study of the film formation, stripes of glass tissues were dipped in a concentrated p‐TFE latex dispersion and then removed. The samples were then dried in an oven at well‐defined temperatures below and above the melting temperature T_m of the p‐TFE latex. The film formation from the particles was then studied by taking SEM micrographs of the surface of the samples at various times and conditions. It was observed that the globular particles kept their globular shape and did not coalesce to a film as long as the temperature of the sample was kept below T_m. When the samples were tempered with T > T_m the film formation started. The neighboring globular particles coalesced into wormlike particles that grew in length with time. During the growth of the particles the thickness of the particles remained constant. In the first stages the film can be imagined as a porous network from short wormlike objects. It is concluded that the coalescence begins above T_m when the polymer chains become mobile along their axis. The chains of neighboring particles can therefore interdigitate into each other along their main axis and crosslink the particles. The proposed mechanism of film formation is confirmed by AFM micrographs on which the individual particles from the dispersion are still visible in the wormlike objects. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 733–742, 2004