Organocatalyzed ring‐opening polymerization of cyclic butylene terephthalate oligomers

In this study, various organic compounds, with different activation modes, have been tested as catalysts for the ring‐opening polymerization (ROP) of cyclic butylene terephthalate oligomers (CBT) in bulk at 210 °C, using tert‐butylbenzyl alcohol (tBnOH) as initiator. Among them, 1,3,5‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) appeared to be the most efficient, achieving high monomer conversions in short reaction times (within minutes). Analysis by size‐exclusion chromatography (SEC) of the poly(butylene terephthalate) (PBT) synthesized using this catalyst also showed that the polymerization follows the expected theoretical M _n trend for molecular weights up to 50 kg·mol^?1. Chain‐end fidelity relatively to the alcohol initiator has been confirmed by MALDI‐TOF mass spectroscopy, which showed that all polymer chains possess the tert‐butylbenzyl moiety as chain‐end. Finally, to demonstrate the potential of this system for the synthesis of PBT‐based block copolymers, a monomethyl ether poly(ethylene glycol) (PEG) of 5000 g·mol^?1 has been employed as initiator for the ROP of CBT. A PEO‐b‐PBT block copolymer of 15,000 g·mol^?1 could thus been obtained, as confirmed by the shift of the SEC traces towards higher molecular weights and the same diffusion coefficient determined for ¹H NMR signals of the PEO block and the PBT block. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1611–1619     

Effects of comonomer sequential structure on thermal and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)s

In this work, new investigations on the effect of comonomer sequential structure on the thermal and crystallization behaviors and biodegradability have been implemented for the biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) as well as aliphatic poly(butylene succinate) (PBS). At first, these copolyesters were efficiently synthesized from dimethyl succinate and/or dimethyl terephthalate and 1,4‐butanediol via condensation polymerization in bulk. Subsequently, their molecular weights and macromolecular chain structures were analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. By means of differential scanning calorimeter (DSC) and wide‐angle X‐ray diffractometer (WAXD), thermal and crystallization behaviors of these synthesized aromatic–aliphatic copolyesters were further explored. It was demonstrated that the synthesized copolyesters were revealed to have random comonomer sequential structures with thermal and crystallization properties strongly depending on their comonomer molar compositions, and that crystal lattice structures of the new crystallizable copolyesters shifted from the monoclinic crystal of semicrystalline PBS to triclinic lattice of the poly(butylene terephthalate) (PBT) with increasing the terephthalate comonomer composition, and the minor comonomer components were suggested to be trapped in the crystallizable component domains as defects. In addition, the enzymatic degradability was also characterized for the copolyesters film samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1635–1644, 2006     

A modulated dsc study on the in situ polymerization of cyclic butylene terephthalate oligomers

The polymerization of a cyclic butylene terephthalate (CBT) oligomer was studied as a function of temperature (T=200 and 260°C, respectively) by modulated DSC (MDSC). The first heating was followed by cooling after various holding times (5, 15 and 30 min) prior to the second heating which ended always at T=260°C. This allowed us to study the crystallization and melting behavior of the resulting polybutylene terephthalate (PBT), as well. In contrary to the usual belief, the CBT polymerization is exothermic and the related process is superimposed to that of the CBT melting. The melting behavior of the PBT was affected by the polymerization mode (performed below or above the melting temperature of the PBT product) of the CBT. Annealing above the melting temperature of PBT yielded a product featuring double melting. This was attributed to the presence of crystallites with different degrees of perfection. The crystals perfection which occurred via recrystallization/remelting was manifested by a pronounced exothermic peak in the non-reversing trace.     

Morphology of poly(butylene terephthalate)–poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) segmented copolyesters

Segmented copolyesters, namely, poly(butylene terephthalate)–poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) (PBT‐PETIS), were synthesized with the melting transesterification processing in vacuo condition involving bulk polyester produced on a large scale (PBT) and ternary amorphous random copolyester (PETIS). Investigations on the morphology of segmented copolyesters were undertaken. The two‐phase morphology model was confirmed by transmission electron microscopy and dynamic mechanical thermal analysis. One of the phases was composed of crystallizable PBT, and the other was a homogeneous mixture of PETIS and noncrystallizable PBT. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2257–2263, 2003     

Preparation and characterization of novel transparent plasticized poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) gel

Transparent plasticized gels with good mechanical, optical, and dielectric properties have important applications in various fields. We prepared a new gel using a poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) (PBT‐co‐PAGT) copolymer and a plasticizer, dibutyl adipate (DBA). This method improved the polymer crystallinity, and suppressed particle formation in cast‐films when the polymer was dissolved in 1,1,1,3,3,3‐hexafluoro‐2‐propanol, followed by solvent evaporation, and enabled uniform swelling of the polymer network by the plasticizer to form a transparent and flexible gel. The dielectric constants of the developed PBT‐co‐PAGT/DBA gels are much higher than those of PBT‐co‐PAGT films at low frequency. We believe that these PBT‐co‐PAGT/DBA gels could be used as photovoltaic, dielectric, and actuator materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 829–832     

Flame retardancy mechanisms of poly(1,4‐butylene terephthalate) containing microencapsulated ammonium polyphosphate and melamine cyanurate

The flame retardancy mechanisms of poly(1,4‐butylene terephthalate) (PBT) containing microencapsulated ammonium polyphosphate (MAPP) and melamine cyanurate (MC) were investigated via pyrolysis analysis (thermogravimetric analysis (TGA), real‐time Fourier transform infrared (FTIR), TG‐IR), cone calorimeter test, combustion tests (limited oxygen index (LOI), UL‐94), and residue analysis (scanning electron microscopy (SEM)). A loading of 20 wt% MC to PBT gave the PBT composites an LOI of 26%, V‐2 classification in UL‐94 test and a high peak heat release rate (HRR) in cone calorimeter test. Adding APP to PBT/MC composites did not improve their flame retardancy. In comparison with the addition of ammonium polyphosphate (APP) to PBT, MAPP with silica gel shell and MAPP with polyurethane shell both promoted the intumescent char‐forming and improved the flame retardancy of PBT through different mechanisms in the presence of MC. These two halogen‐free PBT composites with V‐0 classification according to UL‐94 test were obtained; their LOI were 32 and 33%, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Poly(butylene terephthalate)/clay nanocomposite compatibilized with poly(ethylene‐co‐glycidyl methacrylate). II. Nonisothermal crystallization

Melting behaviors and nonisothermal crystallization of poly(butylene terephthalate)/poly(ethylene‐co‐glycidyl methacrylate) (PBT/PEGMA), PBT/commercial modified montmorillonite clays (PBT/Clay), and PBT/exfoliated silicates (PBT/PEGMA/Clay) nanocomposites were studied by wide‐angle X‐ray diffraction and differential scanning calorimeter. PEGMA is used as a compatibilizer. For both isothermally and nonisothermally crystallized samples, PEGMA facilitates the recrystallization of PBT during the heating scans, and leads to a less degree of perfection of the crystals. However, the clay hinders the recrystallization growth during heating scans, and increases perfection of the crystals. Nonisothermal crystallization kinetics was described by kinetic models and undercooling was taken into account. The PEGMA would lead to an increase of the blend viscosity, rendering the chains less mobile and lower the crystallizability of PBT in PBT/PEGMA. The well‐dispersed exfoliated silicates in PBT/PEGMA/Clay cause a large number of nuclei to precede crystallization. The fold surface free energy (σ_e) and activation energy also supported the interpretation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 564–576, 2008     

Poly(butylene terephthalate)–polyarylate blends

In this paper we focus on miscible blends of two engineering polymers: poly(butylene terephthalate) (PBT) and a polyarylate (PAr). The issue of transesterification in these blends will be addressed, followed by a discussion of the crystallization kinetics of PBT, poly(ethylene terephthalate) and several PBT/PAr blends. The ability to estimate polymer–polymer interaction parameters in blends from melting point depression will also be discussed. The amorphous phase behavior of the PBT/PAr blends has been explored primarily using dielectric spectroscopy. For blends in which PBT has crystallized, we observe two relaxations associated with T_g-like motion, and this behavior is interpreted in light of our recent work on order–disorder interphases in crystalline blends.     

Characterization of PBT/POSS nanocomposites prepared by in situ polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS

Novel poly(butylene terephthalate) (PBT)/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized by ring‐opening polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS with various feed ratios. The impact of POSS incorporation on melting and crystallization behaviors of PBT/POSS nanocomposites was investigated by means of X‐ray diffraction and differential scanning calorimetry. It was found that the novel organic–inorganic association result in the significant alterations in the melting and crystallization behavior of PBT. Thermal studies confirmed that the incorporation of POSS can enhance the thermal stability of the polymers, and the copolymer glass transition temperature increased with the increasing of POSS macromonomer content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1853–1859, 2010     

Preparation of Long Glass Fiber Reinforced Poly(butylene terephthalate) Composites with Chemical Bonding Interphase

Long glass fiber reinforced poly(butylene terephthalate) composites (LGF/PBT) were prepared by a new process. PBT oligomers with low melt viscosity were impregnated into the reinforcing glass fiber and then grafted to the reinforcing glass fiber surface treated with a silane coupling agent during solid‐state polymerization. The reinforcing glass fiber, after removing ungrafted PBT from LGF/PBT, was investigated with the result showing the presence of a grafted PBT layer on the surface of treated glass fiber. The mechanical properties of the composites were significantly improved owing to the grafting of the PBT macromolecules. The fiber length distribution and fiber arrangement in the injection molded composites were also studied and the results showed that a small amount long glass fiber could be connected at junction points in the composites, which were of benefit to the mechanical properties of the composites.     

High‐pressure DTA of poly(butylene terephthalate), poly(hexamethylene terephthalate), and poly(ethylene terephthalate)

Pressure effect on the melting behavior of poly(butylene terephthalate) (PBT) and poly(hexamethylene terephthalate) (PHT) was studied by high‐pressure DTA (HP‐DTA) up to 320 and 530 MPa, respectively. Cooling rate dependence on the DSC melting curves of the samples cooled from the melt was shown at atmospheric pressure. Stable and metastable samples were prepared by cooling from the melt at low and normal cooling rates, respectively. DTA melting curves for the stable samples showed a single peak, and the peak profile did not change up to high pressure. Phase diagrams for PBT and PHT were newly determined. Fitting curves of melting temperature (T_m) versus pressure expressed by quadratic equation were obtained. Pressure coefficients of T_m at atmospheric pressure, dT_m/dp, of PBT and PHT were 37 and 33 K/100 MPa, respectively. HP‐DTA curves of the metastable PBT showed double melting peaks up to about 70 MPa. In contrast, PHT showed them over the whole pressure region. HP‐DTA of stable poly(ethylene terephthalate) (PET) was also carried out up to 200 MPa, and the phase diagram for PET was determined. dT_m/dp for PET was 49 K/100 MPa. dT_m/dp increased linearly with reciprocal number of ethylene unit. The decrease of dT_m/dp for poly(alkylene terephthalate) with increasing a segmental fraction of an alkyl group in a whole molecule is explained by the increase of entropy of fusion. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 262–272, 2000     

Preparation and characterization of poly(butylene terephthalate)/poly(ethylene terephthalate) copolymers via solid‐state and melt polymerization

To increase the T_g in combination with a retained crystallization rate, bis(2‐hydroxyethyl)terephthalate (BHET) was incorporated into poly(butylene terephthalate) (PBT) via solid‐state copolymerization (SSP). The incorporated BHET fraction depends on the miscibility of BHET in the amorphous phase of PBT prior to SSP. DSC measurements showed that BHET is only partially miscible. During SSP, the miscible BHET fraction reacts via transesterification reactions with the mobile amorphous PBT segments. The immiscible BHET fraction reacts by self‐condensation, resulting in the formation of poly(ethylene terephthalate) (PET) homopolymer. ¹H‐NMR sequence distribution analysis showed that self‐condensation of BHET proceeded faster than the transesterification with PBT. SAXS measurements showed an increase in the long period with increasing fraction BHET present in the mixtures used for SSP followed by a decrease due to the formation of small PET crystals. DSC confirmed the presence of separate PET crystals. Furthermore, the incorporation of BHET via SSP resulted in PBT‐PET copolymers with an increased T_g compared to PBT. However, these copolymers showed a poorer crystallization behavior. The modified copolymer chain segments are apparently fully miscible with the unmodified PBT chains in the molten state. Consequently, the crystal growth process is retarded resulting in a decreased crystallization rate and crystallinity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 882–899, 2007.     

Supertoughness and critical interparticle distance dependence in poly(butylene terephthalate) and poly(ethylene‐co‐glycidyl methacrylate) blends

Supertough poly(butylene terephthalate) (PBT)‐based blends were obtained by the melt blending of PBT with 0–30 wt % poly(ethylene‐co‐glycidyl methacrylate) (EGMA). The reaction between PBT and EGMA was detected by torque measurements. The particle size was almost constant with increasing EGMA content, and this indicated that compatibilization occurred. The minimum EGMA content for achieving supertoughness (i.e., an impact strength 16 times greater than that of PBT) was 20 wt %. The interparticle distance was the parameter controlling toughness in these PBT/EGMA blends. The dependence of the critical interparticle distance (τ_c) on the modulus of the dispersed phase appeared only at low τ_c values, and the primary dependence of τ_c on the ratio of the modulus of the matrix to the modulus of the rubbery dispersed phase was proposed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2236–2247, 2003     

Polymeric Nanocomposites of Polyurethane Block Copolymers and Functionalized Multi‐Walled Carbon Nanotubes as Crosslinkers

Summary: We report on a new route to synthesize polymeric carbon nanotube‐polyurethane (PU) nanocomposites. Multi‐walled carbon nanotubes (MWNTs) functionalized by chemical modification were incorporated as a crosslinker in prepolymer, which was prepared from a reaction of 4,4′‐methylene bis(phenylisocyanate) and poly(ε‐caprolactone)diol. The reinforcing effect of carbon nanotubes in crosslinked MWNT‐PU nanocomposites was more pronounced as compared to that in conventional MWNT‐PU nanocomposites. The optimum content of chemically modified MWNTs for crosslinking with polyurethane was determined to be approximately 4 wt.‐% in our samples, based on observation of a NCO peak in FT‐IR spectroscopy. MWNT‐crosslinked polyurethane containing 4 wt.‐% modified MWNTs showed the highest modulus and tensile strength among the composites and pure PU. The presence of functionalized MWNTs in the polymeric nanocomposite yielded enhancement in the thermal stability due to crosslinking of the MWNTs with PU.

Possible configuration for MWNT‐PU nanocomposite molecules and FT‐IR spectra of samples obtained during reaction of prepolymer with functionalized MWNTs (second step).     

Isothermal crystallization kinetics of poly(butylene terephthalate)/attapulgite nanocomposites

Poly(butylene terephthalate) (PBT)/organo‐attapulgite (ATT) nanocomposites containing 2.5 and 5 wt % nanoparticles loadings were fabricated via a simple melt‐compounding approach. The crystal structure and isothermal crystallization behaviors of PBT composites were studied by wide‐angle X‐ray diffraction and differential scanning calorimetry, respectively. The X‐ray diffraction results indicated that the addition of ATT did not alter the crystal structure of PBT and the crystallites in all the samples were triclinic α‐crystals. During the isothermal crystallization, the PBT nanocomposites exhibited higher crystallization rates than the neat PBT and the varied Avrami exponents when compared with the neat PBT. At the same time, the regime II/III transition was also observed in all the samples on the basis of Hoffman‐Laurizten theory, but the transition temperature increased with increasing ATT loadings. The fold surface free energy (σ_e) of polymer chains in the nanocomposites was lower than that in the neat PBT. It should be reasonable to treat ATT as a good nucleating agent for the crystallization of PBT, which plays a determinant effect on the reduction in σ_e during the isothermal crystallization of the nanocomposites, even if the existence of ATT could restrict the segmental motion of PBT. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2112–2121, 2006     

Partially renewable copolyesters prepared from acetalized d‐glucitol by solid‐state modification of poly(butylene terephthalate)

The backbone of poly(butylene terephthalate) (PBT) was modified with 2,4:3,5‐di‐O‐methylene‐D ‐glucitol (Glux) using solid‐state modification (SSM). The obtained copolyesters proved to have a non‐random overall chemical microstructure. The thermal properties of these semicrystalline, block‐like, Glux‐based materials were extraordinary, showing higher melting points, and glass transition temperatures compared with other sugar‐based copolyesters prepared by SSM. These remarkable thermal properties were a direct result of the inherently rigid structure of Glux and the relatively slow randomization of the block‐like chemical microstructure of the Glux‐based copolyesters in the melt. SSM proved to be a versatile tool for preparing partially biobased copolyesters with superior thermal properties. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 164–177     

Surface modification of poly(butylene terephthalate) nonwoven by photochemistry and biofunctionalization with peptides for blood filtration

The surface of meltblown poly(butylene terephthalate) (PBT) nonwoven was modified by photochemistry using the photolinker O‐succinimidyl 4‐azido‐2,3,5,6‐tetrafluorobenzoate for the introduction of activated ester functions and then coupling of molecular probes or biomolecules. Approximately 4000 pmol of (L )‐4,5‐[³H]‐lysine was fixed per PBT sample (1.13 cm²) and measured by liquid scintillation counting. The method consisted in a two‐step process: (a) coating of the clip (0.05 mg/sample) on the fibrous surface of the PBT followed by UV irradiation (30 min, 254 nm) and (b) coupling of amine‐terminated molecules (10^?3 M in phosphate buffer–CH₃CN [1/1, v/v], 20 h). Moreover, about 2000 pmol of ³H‐lysine can be immobilized on the PBT surface after UV irradiation (without clip) by aminolysis reactions with the created oxygenated functions. The derivatizations (via the clip and UV irradiation only) were stable after long‐term heating at 100 °C in water or under steam‐sterilization conditions. They induce neither modifications of the nonwoven morphology nor cytotoxicity. This method was applied for the grafting of peptides Gly‐Arg‐Gly‐Asp‐Ser and Gly‐Gly‐Gly‐Gly‐Gly to perform blood filtration experiments and to retain the leukocytes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Rheological and thermal study of delayed crystallization in poly(butylene terephthalate)/ethylene‐co‐ethyl acrylate blends

The effects of the composition and resulting morphology on the crystallization and rheology of blends containing poly(butylene terephthalate) (PBT) and an ethylene‐co‐ethyl acrylate (EEA) copolymer, two immiscible polymers, were studied over the entire range of volume fractions. Differential scanning calorimetry (DSC) thermograms recorded during cooling showed important differences, mainly in terms of the PBT crystallization temperatures, depending on the blend composition. In addition to the classical crystallization peaks of PBT and EEA, a third crystallization peak appeared for blends containing less than 60% PBT. This peak was attributed to a delayed crystallization of PBT. This phenomenon was examined in terms of homogeneous crystallization. Linear viscoelastic measurements allowed the delayed crystallization behavior in these polymer blends to be displayed. Indeed, the variation of the storage modulus with the temperature showed increasing steps during cooling. These sudden increases appeared at temperatures very close to those at which the crystallization peaks were observed in the DSC experiments. This behavior was verified for different blend compositions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 714–721, 2004     

Effect of organo‐modified montmorillonite on flame retardant poly(1,4‐butylene terephthalate) composites

In this paper, the effect of organo‐modified montmorillonite (OMMT) on a novel intumescent flame retardant (IFR) system was studied in poly(1,4‐butylene terephthalate) (PBT) composites containing microencapsulated ammonium polyphosphate (MAPP) and melamine cyanurate (MC). Nanocomposite morphology was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal decomposition analysis was studied via thermogravimetric analysis (TGA). Combustion behavior was investigated by microcombustion calorimeter (MCC), limited oxygen index (LOI), and UL‐94 test. Residues obtained after samples treated in muffle furnace at 500°C under air condition for 10 min were analyzed through X‐ray powder diffraction (XRD) and scanning electron microscopy (SEM). It was found that the addition of OMMT improved the flame retardancy of PBT/IFR composites significantly. A mass of microcomposite structure particles formed in the heating or combustion process of PBT/IFR/OMMT nanocomposites were found for the first time in the SEM images, which is strong evidence to confirm the migration or accumulation of montmorillonite and carbonaceous‐silicate materials during the heating or combustion process. Copyright © 2010 John Wiley & Sons, Ltd.     

Transesterification and crystallization behavior of poly(butylene succinate)/poly(butylene terephthalate) block copolymers

The block copolymers of poly(butylene succinate) (PBS) and poly(butylene terephthalate) (PBT) were synthesized by melt processing for different times. The sequence distribution, thermal properties, and crystallization behavior were investigated over a wide range of compositions. For PBS/PBT block copolymers it was confirmed by statistical analysis from ¹H-NMR data that the degree of randomness (B) was below 1. The melting peak (T_m) gradually moved to lower temperature with increasing melt processing time. It can be seen that the transesterification between PBS and PBT leads to a random copolymer. From the X-ray diffraction diagrams, only the crystal structure of PBS appeared in the M1 copolymer (PBS 80 wt %) and that of PBT appeared in the M3 (PBS 50 wt %) to M5 (PBS 20 wt %) copolymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 147–156, 1998