Crystallization behavior and morphology of poly(ethylene 2,6-naphthalate)

The crystallization behavior and morphology of poly(ethylene 2,6-naphthalte) (PEN) were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and transmission electron microscopy (TEM). POM results revealed that PEN crystallized at 240 °C shows the coexistence of α and β-form spherulite morphology with different growth rates. In particular, when PEN crystallized at 250 °C, the morphology of spherulites showed a squeezed peanut shape. The Avrami exponents decreased from 3 to 2.8 above the crystallization temperature of 220 °C, indicating a decrease in growth dimension. Analysis from the secondary nucleation theory suggests that PEN crystallized at 240 °C has crystals with both regime I and regime II. In TEM observation, the ultra-thin PEN film crystallized at 200 °C showed the spherulitic texture with characteristic diffractions of α-form, while PEN crystallized at 240 °C generated an axialite structure with only β-form diffraction patterns. In addition, despite a long crystallization time of 24 h, amorphous regions were also observed in the same specimen. It was inferred that the initiation of PEN at 240 °C generates only β-form crystals from axialite structures.     

Preparation and properties of poly(amideether-imide)s derived from 1,4-bis(4-aminophenoxy)benzene,trimellitic anhydride,and various aromatic diamines

An imide ring containing dicarboxylic acid, 1,4-bis(4-trimellitimidophenoxy)benzene (III), was prepared by the condensation of 1,4-bis(4-aminophenoxy)benzene and trimellitic anhydride. A series of new poly(amide-ether-imide)s were prepared by the direct polycondensation of diimide-diacid III with various aromatic diamines using triphenyl phosphite and pyridine as condensing agents inN-methyl-2-pyrrolidone (NMP) in the presence of calcium chloride. The highest inherent viscosity value of a poly(amide-ether-imide) obtained was 1.78 dL/g (inN,N-dimethylacetamide, DMAc, at 30 °C). Flexible films with excellent tensile properties were cast from DMAc solutions. Glass transition temperatures of these poly(amide-ether-imide)s were recorded in the range of 248–297 C. These polymers do not show obvious weight loss before 400°C; the decomposition temperatures at which 10% weight loss in nitrogen and in air were observed for these poly(amide-ether-imide)s in the range of 521–564°C and 501–539°C, respectively. The polymers derived fromp-phenylenediamine or the diamines containing 1,4-bisphenoxy units exhibited a higher degree of crystallinity and higher initial decomposition temperatures but poor solubility in organic solvents.     

Synthesis of new poly(amide-imide)s XX. Preparation and properties of poly(amide-Imide)s derived from 1,7-Bis(4-aminophenoxy) naphthalene,trimellitic anhydride,and various aromatic diamines

A dicarboxylic acid (1,7-BTMPN) bearing two preformed imide rings, was prepared from the condensation of 1,7-bis(4-aminophenoxy)naphthalene and trimellitic anhydride. A new family of poly(amide-imide)s with inherent viscosities up to 1.56 dL/g (0.5g/dL in DMAc at 30 °C) was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid 1,7-BTMPN with various aromatic diamines in a medium consisting ofN-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers were readily soluble in polar solvents such as NMP and DMAc. All the soluble poly(amide-imide)s can form transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 185–267°C and the 10% weight loss temperatures were above 430 °C in nitrogen.     

Hetero-stereocomplex formation between substituted poly(lactic acid)s with linear and branched side chains,poly(l-2-hydroxybutanoic acid) and poly(d-2-hydroxy-3-methylbutanoic acid)

Differential scanning calorimetry and wide-angle X-ray diffractometry first revealed the formation of hetero-stereocomplex (HTSC) between biodegradable, optically active, and isotactic poly(2-hydroxyalkanoic acid)s having different chemical structures and opposite configurations, i.e., l-configured substituted poly(lactic acid) (PLA) [poly(l-2-hydroxybutanoic acid), P(l-2HB)] with linear side chains (ethyl groups) and d-configured substituted PLA [poly(d-2-hydroxy-3-methylbutanoic acid), P(d-2H3MB)] with branched side chains (isopropyl groups) in solution and in bulk from the melt. The melting temperature of P(l-2HB)/P(d-2H3MB) HTSC crystallites was 197–204 °C, which is much higher those of P(l-2HB) and P(d-2H3MB) homo-crystallites (100–101 °C and 158–165 °C, respectively). The interplain distances and crystalline lattice sizes of P(l-2HB)/P(d-2H3MB) HTSC crystallites were respectively larger and smaller than those of P(l-2HB)/P(d-2HB) and P(l-2H3MB)/P(d-2H3MB) homo-stereocomplexes. The HTSC formation of substituted PLA with opposite configurations reported in the present study will provide a versatile way to prepare poly(2-hydroxyalkanoic acid)-based biodegradable materials having a wide variety of physical properties and biodegradability.     

Crystallization, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) segmented block copolymers

A new type of poly(ether-ester) based on poly(trimethylene terephthalate) as rigid segments and poly(ethylene oxide terephthalate) as soft segments was synthesized and its crystallization behavior and morphology were investigated. Differential Scanning Calorimetry revealed that the copolymer containing 57 wt% soft segments presented a low glass transition temperature (−46.4 °C) and a high melting temperature (201.8 °C), suggesting that it had the typical characteristic of thermoplastic elastomer. With increasing soft segment content from 35 to 57 wt%, the crystallization morphology transformed from banded spherulites to compact seaweed morphology at a certain film thickness, which was due to the change of surface tension and diffusivity caused by increasing the soft segment content. Moreover, with the decrease of film thickness from 15 to 2 μm, the crystallization morphology of the copolymer (57 wt% soft segment) changed from wheatear-like, compact seaweed to dendritic. Scanning Electron Microscopy revealed that some flower-like crystals presenting in the bulk, which had been surprisingly found in the poly(ether-ester) segmented block copolymers for the first time. Possible mechanism was discussed in the text.     

Hetero-stereocomplex formation of stereoblock copolymer of substituted and non-substituted poly(lactide)s

The crystallization behavior of the stereoblock copolymer of substituted and non-substituted poly(lactide)s, i.e., poly(d-2-hydroxybutyrate) and poly(l-lactide) chains having the opposite configurations [P(D-2HB)-b-PLLA] and the reference block copolymer of poly(d-2-hydroxybutyrate) and poly(d-lactide) chains with the identical configurations [P(D-2HB)-b-PDLA] was investigated. At the crystallizable temperature range of 60-160 °C, the crystallized P(D-2HB)-b-PLLA contained solely the hetero-stereocomplex crystallites as a crystalline species, without formation of poly(d-2-hydroxybutyrate) or poly(l-lactide) homo-crystallites, in contrast with their polymer blends. On the other hand, at the crystallizable temperature range of 60-140 °C, the crystallized P(D-2HB)-b-PDLA had only PDLA homo-crystallites as crystalline species, reflecting no co-crystallites formation between poly(d-2-hydroxybutyrate) and poly(d-lactide) chains having the same configurations. The equilibrium melting temperature of hetero-stereocomplex crystallites in P(D-2HB)-b-PLLA was 189.0 °C, which was higher than 171.3 °C of PDLA homo-crystallites in P(D-2HB)-b-PDLA. Although the final crystallinity of P(D-2HB)-b-PLLA was higher than those of P(D-2HB)-b-PDLA, the spherulite growth rate of P(D-2HB)-b-PLLA was lower.The regime analysis indicated unusual nucleation mechanism of P(D-2HB)-b-PLLA.     

Synthesis and photoluminescent property of star polymers with carbzole pendent and a zinc porphyrin core by ATRP

Styrene-type monomer 9-(4-vinylbenzyl)-9H-carbazole (VBCz) and methacrylate-type monomer 2-(9H-carbazole-9-yl)-ethyl methacrylate (CzEMA) were polymerized to star polymers respectively via atom transfer radical polymerization (ATRP) using zinc 5,10,15,20-tetrakis(4-(2-methyl-2-bromopropoxy) phenyl) porphyrin as an initiator. The emission spectra of two star polymers (star poly(VBCz) and star poly(CzEMA)) in the solid state displayed red light emission, while those of two monomers showed blue light emission. The result demonstrates that effective energy transfer occurs from the carbazole to the Zn porphyrin core. However, two star polymers in DMF solution emit week red light and strong UV light at 350-400 nm, it points that energy transfer cannot occur from the carbazole to the Zn porphyrin core effectively. They exhibit good thermal stability with T_{d poly(VBCz)} = 374 °C and T_{d poly(CzEMA)} = 297 °C at 5% weight loss. The DSC curves show that the glass transition temperature of styrene-type (T_{g poly(VBCz)} = 177 °C) was better than that of methacrylate-type (T_{g poly(CzEMA)} = 148 °C).     

An unusual branching in single crystals of isotactic poly(4-methyl-1-pentene)

Single crystals of low M_w poly(4-methyl-1-pentene) (P4MP1) in its form I display an unusual streaking of their diffraction pattern. The crystals also frequently give rise to composite diffraction patterns made of two patterns rotated by 37°. The streaking indicates a structural disorder, namely a shift of nearby layers along the a or b axis by one quarter of the unit-cell edge. The daughter crystals, rotated by 37°, are produced on the edges of the parent crystals via an epitaxial growth that is a direct consequence of the structural disorder.     

Synthesis and thermally responsive characteristics of dendritic poly(ether-amide) grafting with PNIPAAm and PEG

A series of thermally responsive dendritic core-shell polymers were prepared based upon dendritic poly(ether-amide) (DPEA), modified with carboxyl end-capped linear poly(N-isopropylacrylamide) (PNIPAAm-COOH) or both PNIPAAm-COOH and carboxyl end-capped methoxy polyethylene glycol (PEG-COOH) in different ratios via an esterification process to obtain DPEA-PNIPAAm or DPEA-PNIPAAm-PEG. Their molecular structures were verified by gel permeation chromatography, and ¹H NMR and FTIR spectroscopy. The temperature-dependent characteristics study has revealed that DPEA-PNIPAAm exhibits a lower critical solution temperature (LCST) of about 34 °C, whereas DPEA-PNIPAAm-PEG polymers with the PNIPAAm/PEG ratio of about 1.0 and 0.4 possess about 36 °C and 39 °C, respectively, compared with 32 °C for homopolymer PNIPAAm. The critical aggregation temperature was investigated using fluorescence excitation spectrum of pyrene as a sequestered guest molecule based upon the sharp increase of the I₃₃₈/I₃₃₃ value.     

Synthesis of polyether-based block copolymers based on poly(propylene oxide) and terephthalates

Poly(propylene oxide) (PPO) is a low reactive telechelic polyether and the synthesis of high molecular weight poly(propylene oxide)-based block copolymers was studied. The poly(propylene oxide) used was end capped with 20 wt % ethylene oxide and had a molecular weight of 2300 g/mol (ultra-low monol PEO-b-PPO-b-PEO). The type of terephthalic acid based precursors was varied: terephthalic acid, dimethyl terephthalate, diphenyl terephthalate, di(trifluoro ethyl) terephthalate, di(p-nitrophenyl) terephthalate) and terephthalic acid chloride. High molecular weight poly(propylene oxide) based segmented block copolymers were obtained with diphenyl terephthalate (inherent viscosity: 1.6 dl/g).The synthesis of polyether(ester-amide)s comprising PPO and isophthalamide-based segments was also studied by varying the polymerization temperature and time. High molecular weight poly(propylene oxide) block copolymers could be obtained if the reaction was carried out for 2 h at 250 °C under vacuum. Higher temperatures (280 °C) and longer times result in lower inherent viscosities, probably due to degradation of the polyether.     

Linear-hyperbranched copolymerization as a tool to modulate thermal properties and crystallinity of a para-poly(ether-ketone)

The AB₂ monomer, 3,5-bis(4-fluorobenzoyl)phenol was synthesized via an improved four-step scheme. It was polymerized to form the corresponding fluoride-terminated hyperbranched polymer with higher molecular weight than previously reported, as evidenced by higher glass-transition temperature (T_g=159 °C vs. 140-143 °C). The homopolymerization showed a bimodal molecular weight distribution that was also observed for other related linear-hyperbranched systems. The AB₂ monomer was then copolymerized with 4-fluoro-4′-hydroxybenzophenone (AB monomer), in weight ratios of 1:3, 1:1 and 3:1 to afford the respective hyperbranched poly(ether-ketones) with variable degrees of branching. The 1:1 copolymer had T_g value (212 °C) that was significantly (35 °C) higher than both linear and hyperbranched homopolymers. Only the 1:3 copolymer was semi-crystalline, displaying melting at 340 °C and its wide angle X-ray scattering (WAXS) pattern indicated that its crystal structure is exactly the same as that of the linear homopolymer. The WAXS results of the copolymers correlated well with differential scanning calorimetry and themogravimetric analysis results.     

The evolution of poly(hydroxyamide amic acid) to poly(benzoxazole) via stepwise thermal cyclization: Structural changes and gas transport properties

The thermally induced structure transformation and polymer chain rearrangement of a thermally rearranged (TR) material for gas separation has been explored in this work. A tremendous enhancement as high as 215 folds in CO₂ permeability has been achieved by converting the pristine poly(hydroxyamide amic acid) (PHAA) to the final polybenzoxazole (PBO) via thermal cyclization at 400 °C for 2 h. The evolution of the pristine polymer PHAA derived from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluropropane (BisAPAF) and trimellitic anhydride chloride (TAC) by thermal treatment from 130 °C to 400 °C has been examined by various characterization techniques including elemental analysis, TGA, TGA-IR, DSC, ATR-FTIR, XPS, XRD and Positron Annihilation Lifetime Spectroscopy (PALS). The stepwise cyclization process commences with cyclodehydration followed by cyclodecarboxylation. At the first step, PHAA transforms to poly(imide benzoxazole) (PIBO) up to 300 °C, while at the second step, the final structure of PBO is formed at 400 °C. Following the changes in the cyclization process, gas transport properties also show the stepwise changes. The significant enlargements of polymer inter-chain distance and free volume cavity radius provide the fundamental understanding for the changes of gas transport properties at the molecular level.     

Autocatalytic hydrolysis of amorphous-made polylactides: effects of l-lactide content, tacticity, and enantiomeric polymer blending

Poly(dl-lactide), i.e., poly(dl-lactic acid) (PDLLA), poly(l-lactide), i.e. poly(l-lactic acid) (PLLA), and poly(d-lactide), i.e., poly(d-lactic acid) (PDLA) were synthesized to have similar molecular weights. The non-blended PDLLA, PLLA, and PDLA films and PLLA/PDLA(1/1) blend film were prepared to be amorphous state, and the effects of l-lactide unit content, tacticity, and enantiomeric polymer blending on their autocatalytic hydrolysis were investigated in phosphate-buffered solution (pH7.4) at 37 °C for up to 24 months. The results of gravimetry, gel permeation chromatography (GPC), and tensile testing showed that the autocatalytic hydrolyzabilities of polylactides, i.e. poly(lactic acid)s (PLAs) in the amorphous state decreased in the following order: nonblended PDLLA>nonblended PLLA, nonblended PDLA>PLLA/PDLA(1/1) blend. The high hydrolyzability of the nonblended PDLLA film compared with those of the nonblended PLLA and PDLA films was ascribed to the lower tacticity of PDLLA chains, which decreases their intramolecular interaction and therefore the PDLLA chains are susceptible to the attack from water molecules. In contrast, the retarded hydrolysis of PLLA/PDLA(1/1) blend film compared with those of the nonblended PLLA and PDLA films was attributable to the peculiar strong interaction between PLLA and PDLA chains in the blend film, resulting in the disturbed interaction of PLLA or PDLA chains and water molecules. The X-ray diffractometry and differential scanning calorimetry (DSC) elucidated that all the initially amorphous PLA films remained amorphous even after the autocatalytic hydrolysis for 16 (PDLLA film) and 24 [nonblended PLLA and PDLA films, PLLA/PDLA(1/1) blend film] months and that the melting peaks observed at around 170 and 220 °C for the PLLA/PDLA(1/1) blend film after the hydrolysis for 24 months were ascribed to those of homo- and stereocomplex crystallites, respectively, formed during heating at around 100 and 200 °C but not during the autocatalytic hydrolysis.     

Radiation-induced synthesis of poly(vinylpyrrolidone) nanogel

Studies of the radiation-induced synthesis of poly(vinylpyrrolidone) (PVP) nanogels, intended to provide a basis for obtaining intra-molecular cross-linked products, which are more useful in drug delivery, show that a sharp change in the controlling mechanism from inter-molecular to intra-molecular cross-linking occurs above a threshold temperature around 50 °C-55 °C, even though the rate of inter-molecular cross-linking is enhanced as the temperature is raised. When aqueous solutions of PVP are irradiated, the activation energy of the decay of the PVP· radical is observed to rise sharply above this threshold temperature. This can be attributed to the collapse of the polymer chains, which occurs at temperatures above approximately 55 °C and leads to a reduction of the R_h of the irradiated polymer molecules at 77 °C to (44 ± 3) % of that of PVP molecules that were not irradiated at 20 °C, as shown by the results of AFFFF measurements. The abrupt transition to a mechanism controlled by intra-molecular cross-linking is due to the thermal collapse of the polymer structure. This accounts for the observation that activation energy is higher within the temperature range above 55 °C. Higher pulse repetition rates during electron irradiation also promote intra-molecular cross-linking.     

Aliphatic poly(alkylene dithiocarbonate)s: Thermal properties and structural characteristics of poly(hexamethylene dithiocarbonate)

Aliphatic poly(alkylene dithiocarbonate)s are an interesting class of potentially biodegradable and biocompatible materials in analogy with their homologous poly(alkylene carbonate)s. In this paper, the properties of poly(hexamethylene dithiocarbonate) (SSR6) are compared to those of poly(hexamethylene carbonate) (HMC) in order to study the effect of the substitution of oxygen atoms with sulphur atoms in the polymer backbone. SSR6 presents a higher level of crystallinity and a faster crystallisation rate with respect to HMC. The melting temperature in SSR6 is about 60 °C higher, due to a solid-solid transition between phase I, stable at room temperature, and phase II, present at high temperature. HMC crystallises only in phase I and melts at a relatively low temperature (30 °C). The capacity of SSR6 to crystallise in phase II has been attributed to the higher flexibility and mobility of the chains containing -S-CO-S- groups with respect to the chains containing -O-CO-O- groups. The pure phase II in SSR6 has been obtained in isothermal conditions and its crystallisation rate and mechanism have been analysed.     

Synthesis and characterization of polyketones containing pendant carbazoles

Condensation of 9-(4-aminobenzene)-carbazole with 4,4′-difluorobenzophenone afforded a carbazole-functionalized poly(aryl amino ketone) (PAK-Cz). Similarly, a series of poly(ether ether ketone)s (PEEK-Cz) and poly(arylene ether ketone)s (PAEK-Cz) containing pendant carbazoles were synthesized from the copolymerization of 9-(4-aminobenzene)-carbazole, 4,4′-difluorobenzophenone and 4,4′-biphenol or 4,4′-isopropylidenebiphenol, respectively. The aforementioned polymers exhibited polystyrene equivalent number average molecular weights of up to 36 kDa, and were found to be thermally stable with high decomposition (T_d) (469-569 °C) and glass transition temperatures (T_g) (155-256 °C). UV-vis absorption and fluorescence spectra revealed that these materials exhibited highly efficient (Φ_f = 0.41-0.66) yellow-green emission (λ_em = 500-514 nm) in solution.     

Conductivity hysteresis in polymer electrolytes incorporating poly(tetrahydrofuran)

Conductivity hysteresis and room temperature ionic conductivities >10⁻³ S/cm were recently reported for electrolytes prepared from blends of an amphiphilic comb copolymer, poly[2,5,8,11,14-pentaoxapentadecamethylene (5-hexadecyloxy-1,3-phenylene)] (polymer I), and a linear multiblock copolymer, poly(oligotetrahydrofuran-co-dodecamethylene) (polymer II), following thermal treatment [F. Chia, Y. Zheng, J. Liu, N. Reeves, G. Ungar, P.V. Wright, Electrochim. Acta 43 (2003) 1939]. To investigate the origin of these effects, polymers I and II were synthesized in this work, and the conductivity and thermal properties of the individual polymers were investigated. AC impedance measurements were conducted on I and II doped with LiBF₄ or LiClO₄ during gradual heating to 110 °C and slow cooling to room temperature. Significant conductivity hysteresis was seen for polymer II, and was similarly observed for poly(tetrahydrofuran) (PTHF) homopolymer at equivalent doping levels. From thermogravimetic analysis (TGA), gel permeation chromatography (GPC) and ¹H NMR spectroscopy, both polymer II and PTHF were found to partially decompose to THF during heat treatment, resulting in a self-plasticizing effect on conductivity.     

Synthesis and test of styrene—Cyclosiloxane and butadiene-cyclosiloxane block copolymers containing ultraviolet (UV) absorber and antioxidant groups

Block copolymers of polystyrene and poly(dimethylsiloxane) or of polybutadiene and poly(dimethylsiloxane) with nonhydrolyzably bound 2-hydroxybenzophenone and 2,6-di-tert-butylphenol residues were prepared by terminating the living block copolymers with glacial acetic acid to form siloxanol end groups, followed by condensation with diethoxysilyl derivatives of the stabilizers in the presence of dibutyltin dilaurate. The polymeric UV absorbers were proved to be nonextractable from polystyrene. At Xenotest aging (40°C) the polymeric UV absorbers were less effective than 2-hydroxy-4-octyloxybenzophenone. The polymeric antioxidants were superior to antioxidants of low molecular weight both in thermooxidative aging of vulcanized polybutadiene films at 70°C and in oxygen-uptake studies with stabilized polypropylene at 180°C over long periods.Siloxanes with Functional Groups, XII. XIth communication, cf. Ref. 1. Long-Term Stabilization of Polymers, VI. Vth communication, cf. Ref. 2.     

Synthesis of nitrile and benzoyl substituted poly(biphenylene oxide)s via nitro displacement reaction

A series of substituted poly(biphenylene oxide)s (PBPOs) was synthesized via nucleophilic nitro displacement reactions. High molecular weight PBPO's with nitrile groups were effectively synthesized from the polymerization of A-B type monomers with K₂CO₃ as a base in N-methyl-2-pyrrolidinone (NMP) at 140 °C. The polymers are completely amorphous, soluble in polar aprotic solvents, and formed flexible films on solution casting. Para-linked PBPO with nitrile groups showed excellent thermal properties such as high 5% weight loss temperature above 530 °C and T_g at 241 °C which is higher than those of commercially available PPO™ (T_g=210 °C). The pendent nitrile groups of PBPO were easily transformed to carboxylic acid groups by acidic hydrolysis.     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-T_m component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-T_m component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.