Heterogeneous polyamide 66/syndiotactic polystyrene blends: Phase structure and thermal and mechanical properties

The structural and physical properties of polyamide 66 (PA66)/syndiotactic polystyrene (sPS) blends were studied with electron microscopy, wide‐angle X‐ray scattering (WAXS), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis, and tensile creep, stress–strain, and impact measurements. Attention was primarily concentrated on blends with sPS weight fractions (w₂) in the range of 0 < w₂ ≤ 0.50. DSC and WAXS showed that the integral crystallinity of the PA66 and sPS components in the blends was virtually unaffected by the blend composition. Polymorphism of sPS was observed for blends with w₂ ≥ 0.50. Blends with 0.40 ≤ w₂ ≤ 0.60 consisted of partially cocontinuous components; otherwise, particles of the minority component were dispersed in the continuous majority component. The compatibilizer enhanced interfacial adhesion so that no debonding of the components in the fractured blends was observed. The compliance and creep rate of the blends at room temperature decreased proportionally to the sPS fraction; a corresponding increase in the storage modulus (E′) was observed in the 25–100°C interval. However, E′ (125°C) noticeably declined with w₂ and thus showed that sPS did not improve the dimensional stability of the blends at elevated temperatures. The yield strength consistently grew with w₂, whereas the yield strain dropped markedly; blends with w₂ ≥ 0.60 were brittle, showing very low values of the ultimate properties. The stress at break, strain at break, and tensile energy to break displayed some local maxima at 0.25 ≤ w₂ ≤ 0.30, whereas the tensile impact strength steeply decreased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 673–684, 2005     

Properties of polyamide 6,10/poly(vinyl alcohol) blends and impact on oxygen barrier performance

The oxygen transmission rate, average volume of free‐volume cavities (V_f) and fractional free volume (F_v) of polyamide 6,10 (PA610)/poly(vinyl alcohol) (PVA) (i.e. PA610_xPVA⁰⁵_y, PA610_xPVA⁰⁸_y and PA610_xPVA¹⁴_y) blend films reduced to minimum values when their PVA contents reached corresponding optimal values. Oxygen transmission rate, V_f and F_v values obtained for optimal PA610_xPVA^z_y blown films were reduced considerably with decreasing PVA degrees of polymerization. The oxygen transmission rate of the optimal bio‐based PA610₈₀PVA⁰⁵₂₀ blown film was only 2.4 cm³ (m²·day·atm)^?1, which is about the same as that of the most often used high‐barrier polymer, ethylene–vinyl alcohol copolymer. Experimental findings from dynamic mechanical analysis, differential scanning calorimetry, wide‐angle X‐ray diffraction and Fourier transform infrared spectroscopy of the PA610_xPVA^z_y blends indicate that PA610 and PVA in the blends are miscible to some extent at the molecular level when the PVA contents are less than or equal to the corresponding optimal values. The considerably enhanced oxygen barrier properties of the PA610_xPVA^z_y blend films with optimized compositions are attributed to the significantly reduced local free‐volume characteristics. © 2017 Society of Chemical Industry     

Highly fluorinated poly(ether‐imide)s derived from 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether and aromatic dianhydrides

A new diamine, 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether (FPAPE) was synthesized through the Suzuki coupling reaction of 2,2′‐diiodo‐4,4′‐dinitrodiphenyl ether with 3,4,5‐trifluorophenylboronic acid to produce 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐dinitrodiphenyl ether (FPNPE), followed by palladium‐catalyzed hydrazine reduction of FPNPE. FPAPE was then utilized to prepare a novel class of highly fluorinated all‐aromatic poly(ether‐imide)s. The chemical structure of the resulting polymers is well confirmed by infrared and nuclear magnetic resonance spectroscopic methods. Limiting viscosity numbers of the polymer solutions at 25 °C were measured through the extrapolation of the concentrations used to zero. M_n and M_w of these polymers were about 10 000 and 25 000 g mol^?1, respectively. The polymers showed a good film‐forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. An excellent solubility in polar organic solvents was observed. X‐ray diffraction measurements showed that the fluoro‐containing polymers have a nearly amorphous nature. The resulting polymers had T_g values higher than 340 °C and were thermally stable, with 10% weight loss temperatures being recorded above 550 °C. Based on the results obtained, FPAPE can be considered as a promising design to prepare the related high performance polymeric materials. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of organo‐soluble fluorinated polyimides

A novel fluorinated diamine monomer with a keto group, 4‐[4‐amino‐2‐trifluoromethyl phenoxy]‐4′‐[4‐aminophenoxy]benzophenone (ATAB) was prepared by reacting dihydroxybenzophenone with 4‐chloronitrobenzene and 2‐chloro‐5‐nitrotrifluoromethylbenzene in the presence of potassium carbonate followed by catalytic reduction with palladized carbon (10%). Fluorinated polyimides IVa–e were synthesized from the diamine mentioned above via a two‐step method (thermal and chemical imidization). Polyimides IVa–e have inherent viscosities in the range 0.65–1.06 dL g^?1 (thermal imidization) and 0.82–1.56 dL g^?1 (chemical imidization). The polyimides prepared by chemical imidization exhibit excellent solubility. Polyimide films exhibit tensile strength, elongation and tensile modulus in the ranges 96–106 MPa, 9–13% and 1.1–1.7 GPa, respectively. The T₁₀ values of the polyimides are in the range 540–598 °C in nitrogen and 545–586 °C in air, with more than 50–60% char yield. They have T_g values between 244 and 285 °C. The prepared polyimides show cut‐off wavelengths in the range 365–412 nm and transmittance at 450 nm in the range 80.9–94.2%. The dielectric constants of the polyimide films are in the range 3.10–3.77 at 1 kHz and 3.04–3.66 at 10 kHz, with moisture absorption of 0.14–0.40%. Copyright © 2006 Society of Chemical Industry     

Preparation,surface wetting properties,and protein adsorption resistance of well‐defined amphiphilic fluorinated diblock copolymers

Novel well‐defined amphiphilic fluorinated diblock copolymers P(PEGMA‐co‐MMA)‐b‐PC₆SMA were synthesized successfully by RAFT polymerization and characterized by FTIR, ¹HNMR and GPC. For copolymer coatings, static contact angles, θ, with water (θ_water ≥ 109.5^°) and n‐hexadecane (θ_hexadecane ≥ 68.9^°) pointed to the simultaneous hydrophobic and lipophobic characteristics of the copolymer surfaces. Dynamic contact angle measurements indirectly demonstrated that copolymer films underwent surface reconstruction upon contact with water, which results in a surface with surface coverage of polar PEG units. Moreover, the distinct nanoscale microphase segregation structures were proved by atomic force microscopy (AFM) images. Finally, using bovine serum albumin (BSA–FITC) as the model protein, copolymers exhibited excellent protein adsorption resistance. It is believed that the combination of surface reorganization and nanometer‐scale microphase segregation structure endows the excellent protein resistance for amphiphilic fluorinated copolymers. These results provide deeper insight of the effect of surface reconstruction and microphase segregation on the protein adsorption behaviors, and these amphiphilic fluoropolymers can expect to have potential applications as antifouling coatings in the field of marine and biomedical. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41167.     

Partially fluorinated polymer networks: Synthesis and structural characterization

Functionalizacion of epoxy‐based networks by the preferential surface enrichment of perfluorinated tails to achieve hydrophobic surface is described. The selected fluorinated epoxies (FE) were: 2,2,3,3,4,4,5,5,6,6,7,7,8,9,9,9‐hexadecafluoro‐8‐trifluoromethyl nonyloxirane (FED3) and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9‐heptadecafluoro nonyloxirane (FES3). Two series of crosslinked fluorinated epoxy‐based materials containing variable fluorine contents (from 0 to 5 wt % F) were prepared using formulations based on partially fluorinated diamine, epoxy monomer and a curing agent. The epoxy monomer was based on diglycidyl ether of bisphenol A (DGEBA) while the curing agents were either propyleneoxide diamine (JEFFAMINE) or 4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline) (MCDEA). It was found that depending on the curing agent employed, homogeneous distribution of fluorine or phase separation distinguishable at micrometer or nanometer scale was obtained when curing blends initially homogeneous. The morphology and composition of partially fluorinated networks were investigated on a micrometer scale combining scanning electron microscopy and X‐ray analysis. When curing with JEFFAMINE, samples were homogeneous for all fluorine proportions. In contrast, MCDEA‐cured blends showed fluorine‐rich zones dispersed in a continuous epoxy‐rich phase. A completely different morphology, characterized by a distribution of irregular fluorine‐rich domains dispersed in an epoxy‐rich phase, was obtained when curing blends initially immiscible. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Synthesis and characterization of novel aromatic polyamides derived from 2,2′‐bis(p‐phenoxyphenyl)‐4, 4′‐diaminodiphenyl ether

BACKGROUND: Wholly aromatic polyamides (aramids) are high‐performance polymeric materials with outstanding heat resistance and excellent chemical stabilities due to chain stiffness and intermolecular hydrogen bonding of amide groups. Synthesis of structurally well‐designed monomers is an effective strategy to prepare modified forms of these aramids to overcome lack of organo‐solubility and processability limitations. RESULTS: A novel class of wholly aromatic polyamides was prepared from a new diamine, namely 2,2′‐bis(p‐phenoxyphenyl)‐4,4′‐diaminodiphenyl ether (PPAPE), and two simple aromatic dicarboxylic acids. Two reference polyamides were also prepared by reacting 4,4′‐diaminodiphenyl ether with the same comonomers under similar conditions. M?_w and M?_n of the resultant polymers were 8.0 × 10⁴ and 5.5 × 10⁴ g mol^?1, respectively. Polymers resulting from PPAPE exhibited a nearly amorphous nature. These polyamides exhibited excellent organo‐solubility in a variety of polar solvents and possessed glass transition temperatures up to 200 °C. The 10% weight loss temperatures of these polymers were found to be up to 500 °C under a nitrogen atmosphere. The polymers obtained from PPAPE could be cast into transparent and flexible films from N,N‐dimethylacetamide solution. CONCLUSION: The results obtained show that the new PPAPE diamine can be considered as a good monomer to enhance the processability of its resultant aromatic polyamides while maintaining their high thermal stability. The observed characteristics of the polyamides obtained make them promising high‐performance polymeric materials. Copyright © 2009 Society of Chemical Industry     

Preparation and properties of polyurethane/benzyl amylose semi‐interpenetrating networks

A series of semi‐interpenetrating polymer networks (semi‐IPNs) films were prepared from 20 wt % of benzyl amylose (BA) of different M_w and castor oil‐based polyurethane (PU) in N,N‐dimethylformamide (DMF). The weight‐average molecular weight (M_w), and radii of gyration (<S²>_z^1/2) of benzyl amylose were determined by laser scattering measurement, and the results suggested BA was in a compact coil conformation in DMF. Furthermore, the properties and miscibility of the polyurethane/benzyl amylose (PUBA) films were studied by scanning electronic microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, ultraviolet–visible spectrophotometer, and tensile testing. The PUBA films possessed much higher optical transmittance and tensile strength than the pure PU film regardless of the molecular weight of BA, but lower values of elongation at break were observed. With decreasing of the BA M_w from 9.24 × 10⁵ to 2.69 × 10⁵, interestingly, the elongation at break of the films increased from 135 to 326%. This might be ascribed to the decrease of crosslinking density of PU networks and the enhancement in freedom of the molecular motion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(Vinyl chloride): Viscoelastic and fatigue properties as a function of molecular weight in ethanol vapor

Viscoelastic fatigue studies were made on poly(vinyl chloride) (PVC) films using oscillatory loading on prestressed samples in an ethanol vapor environment. Samples include unfractionated PVC, relatively narrow molecular weight distribution fractions, and blends made from the fractions. Strain, complex modulus, and tan δ were studied as a function of time until rupture occurred. A marked dependence on molecular weight was observed, for example, a fraction with M?_w = 51,000 failed in a few seconds, while one with M?_w = 228,000 did not fracture after 1600 min.     

Domain structure and miscibility studies of blends of styrene–butadiene–styrene block copolymers (SBS) and styrene–glycidyl methacrylate statistical copolymers (PS‐GMA) using SAXS and DMTA

The domain structure and miscibility in the solid state of a series of blends of styrene‐butadiene‐styrene (SBS) block copolymers and styrene‐glycidyl methacrylate (PS‐GMA) statistical copolymers with varying molecular weights and compositions were studied using small angle X‐ray scattering and dynamic mechanical thermal analysis. Depending on the molecular characteristics of each component, different types and degrees of solubilization of PS‐GMA in SBS were found which, in addition to the initially SBS phase morphology, lead to materials with multiphase domain morphologies with differences in size and structure. The degree of solubilization of PS‐GMA into the PS domains of SBS was found to be higher for blends containing PS‐GMA with lower molecular weight (M_w = 18 100 g mol^?1) and lower GMA content (1 wt%) and/or for SBS with higher PS content (39 wt%) and longer PS blocks (M_w = 19 600 g mol^?1). Localized solubilization of PS‐GMA in the middle of PS domains of SBS was found to be the most probable to occur for the systems under study, causing swelling of PS domains. However, uniform solubilization was also observed for SBS/PS‐GMA blends containing SBS with composition in the range of a morphological transition (PS block M_w = 19 600 g mol^?1 and 39 wt% of PS) causing a morphological transition in the SBS copolymer (cylinder to lamella). Copyright © 2006 Crown in the right of Canada. Published by John Wiley & Sons, Ltd     

Fracture characterization of recycled high density polyethylene/nanoclay composites using the essential work of fracture concept

The effect of nanoclay on the plane‐strain fracture behavior of pristine High density polyethylene (HDPE) and recycled HDPE blends was studied using the essential work of fracture (EWF) concept. The failure mode of EWF tested specimens was found to be associated with the specific non‐EWF (β_Bw_p,B). Adding 6‐wt% of nanoclay to pristine HDPE and 2‐wt% to recycle‐blends greatly decreased the β_Bw_p,B values and led to a transition from ductile to brittle failure mode. A fractographic study revealed that the difference in failure modes was caused by the changes in micro and macro morphologies, which could be related with the specific EWF (w_e,B). In the ductile failure, w_e,B is governed by the fibril size; adding nanoclay and recycled HDPE to pristine HDPE decreased the fibril size and subsequently lowered the w_e,B value. In the brittle failure, the w_e,B value was enhanced by creating a rough fracture surface. Adding nanoclay to pristine HDPE, a steadily decrease in w_e,B was measured until 4‐wt% after which the change was insignificant. Conversely, nanoclay content more than 2‐wt% in recycle‐blends greatly decreased the w_e,B value. A transition map was constructed to illustrate the potential failure mode and the associated fracture morphology based on the tested material compositions. POLYM. ENG. SCI., 56:222–232, 2016. © 2015 Society of Plastics Engineers     

Microstructure morphology of poly(trimethylene terephthalate)/amorphous poly(ethylene terephthalate) blends studied via small angle X‐ray scattering

The microstructure morphology of the poly(trimethylene terephthalate) (PTT) and amorphous poly(ethylene terephthalate) (aPET) blends prepared by solution precipitation has been investigated by means of optical polarized microscopy (POM) and small angle X‐ray scattering (SAXS). From the observation of POM, it was suggested that aPET was predominantly segregated into the interlamellar and/or interfibrillar regions upon PTT crystallization with the evidence that the PTT spherulitic morphologies of blends were volume filling. From results of SAXS data analysis, the maximum scattering peak (q_max) of Lorentz‐corrected SAXS profiles, amorphous layer thickness (l_a) and lamellar volume stacking fraction (?_s), the segregation morphology of PTT/aPET blends is characterized to be the interlamellar segregation morphology when the weight friction of aPET (w_aPET) ≤ 0.2 and the interlamellar and interfibrillar segregation coexisted when w_aPET > 0.2. The extent of aPET segregation was promoted by increasing aPET composition. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Lamellar morphology of poly(trimethylene terephthalate)/poly(ether imide) blends studied via small‐angle X‐ray scattering

The lamellar morphology of a melt‐miscible blend consisting of poly(trimethylene terephthalate) (PTT) and poly(ether imide) (PEI) prepared by solution precipitation has been investigated by means of optical polarized microscopy (POM) and small angle X‐ray scattering (SAXS). From the observation under POM, it was suggested that PEI was predominantly segregated into the interlamellar and/or interfibrillar regions upon PTT crystallization since the PTT spherulitic morphologies of blends were volume‐filling. From results of SAXS data analysis, a larger amorphous layer thickness was identified in the blends, showing that some PEI was incorporated inside the interlamellar regions after crystallization. Despite the swelling of the amorphous layer, the amorphous layer thickness was relatively independent of the blend composition. It was concluded that amorphous PEI was located in the interlamellar regions of PTT as the weight fraction of PEI (w_PEI) [≤] 0.1, while amorphous PEI was predominantly segregated into the interfibrillar regions of PTT as w_PEI > 0.1, and the extent of interfibrillar segregation increased with increasing w_PEI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Analysis of low‐density polyethylene‐g‐poly(vinyl chloride) copolymers formed in poly(vinyl chloride)/low‐density polyethylene melt blends with gel permeation chromatography and solid‐state 13C‐NMR

Gel permeation chromatography (GPC) and solid‐state ¹³C‐NMR techniques were used to analyze the structural changes of poly(vinyl chloride) (PVC) in blends of a low‐density polyethylene (LDPE) and PVC during melt blending. The GPC results showed that the weight‐average molecular weight (M_w) of PVC increased with LDPE content up to 13.0 wt % and then decreased at a LDPE content of 16.7 wt %, whereas the number‐average molecular weight remained unchanged for all of LDPE contents used. The ¹³C‐NMR results suggest that the increase in M_w was associated with the formation of a LDPE‐g‐PVC structure, resulting from a PVC and LDPE macroradical cross‐recombination reaction during melt blending. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3167–3172, 2004     

Metal‐solvating and self‐association of amphiphilic polyamides containing poly(oxyethylene) blocks

An amphiphilic poly(ether amide) consisting of hydrophilic poly(oxyethylene) amide blocks was prepared from the copolymerization of sebacic acid and two poly(oxyalkylene) diamines including a poly(oxyethylene) diamine (POE‐amine at 2000 M_w) and a poly(oxypropylene) diamine (POP‐amine at 230 M_w). The copolymer was estimated to have an average molecular weight of 15,000 M_w (GPC) or approximately three hydrophilic POE segments per strain. The presence of POE segments rendered polymer hydrophilicity and complexing ability for Li⁺, K⁺, Ca⁺², Ni⁺², Pd⁺², and Cu⁺² salts. In particular, lithium perchlorate affected the copolymer to the greatest extent in enhancing electrostatic dissipation or reducing surface resistivity as low as 10^5.0 Ω/sq (cross‐sectional area) at 1/180 Li⁺/EO from 10^7.2 Ω/sq (without metal ion). In such a metal complexation, the copolymer showed a new POE segmental crystalline phase at a melting temperature between ?10.4 and ?14°C, accompanied with the metal‐free original phase of ?31°C. In static toluene/water, the metal ions had no effect on the copolymer surfactancy in lowering the interfacial tension, reaching 4.4 dyn/cm at a critical micelle concentration (cmc) of 0.01 wt %. When mixing toluene and water, the lithium or nickel ions were found to be detrimental to the emulsifying process. Without the metal ion, fine droplets at average sizes of 4.5–5.0 μm were observed in the copolymer/ toluene/water emulsification. These amphiphilic behaviors of the POE‐segmented polyamide with or without metal ions were explained by the competing noncovalent bonding interactions among POE/metal ion/water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 612–621, 2002     

Porous biodegradable polyesters. I. Preparation of porous poly(L‐lactide) films by extraction of poly(ethylene oxide) from their blends

Porous poly(L ‐lactide) (PLLA) films were prepared by water extraction of poly(ethylene oxide) (PEO) from solution‐cast PLLA and PEO blend films. The dependence of blend ratio and molecular weight of PEO on the porosity and pore size of films was investigated by gravimetry and scanning electron microscopy. The film porosity and extracted weight ratio were in good agreement with the expected for porous films prepared using PEO of low molecular weight (M_w = 1 × 10³), but shifted to lower values than expected when high molecular weight PEO (M_w = 1 × 10⁵) was utilized. The maximum pore size was larger for porous films prepared from PEO having higher molecular weight, when compared at the same blending ratio of PLLA and PEO before water extraction. Differential scanning calorimetry of as‐cast PLLA and PEO blend films revealed that PLLA and PEO were phase‐separated at least after solvent evaporation. On the other hand, comparison of blend films before and after extraction suggested that a small amount of PEO was trapped in the amorphous region between PLLA crystallites even after water extraction and hindered PLLA crystallization during solvent evaporation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 629–637, 2000     

Films made from poly(vinyl alcohol‐co‐ethylene) and soluble biopolymers isolated from postharvest tomato plant

Blended films were obtained from polyvinyl alcohol‐co‐ethylene (EVOH) with 52 kDa weight average molecular weight (M_w) and three water soluble biopolymers isolated from exhausted tomato plants hydrolysates. Two biopolymers contained mainly polysaccharides and had 27 and 79 kDa M_w, respectively. The third contained mainly lignin‐like C moieties and had 392 kDa M_W. The films were fabricated with a biopolymer/EVOH w/w ratio ranging from 0.1 to 0.9. All blends had molecular weight and solubility which were substantially different from the starting materials. They were characterized for the chemical nature, and the thermal, rheological, and mechanical properties. Evidence of a chemical reaction between the biopolymers and EVOH was found. Generally, the films exhibited higher mechanical strength but lower strain at break then the neat EVOH. The best performing blended film was fabricated from the 27 kDa M_w polysaccharide. This contained less than 10% biopolymer. It exhibited 1043 MPa Young's modulus and 70% strain at break against 351 MPa modulus and 86% strain for neat EVOH. The results offer scope for investigating biopolymers sourced from other biowastes to understand more the reasons of the observed effects and exploit their full potential to modify or to replace synthetic polymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41935.     

Degradation and biodegradation of polyethylene with pro‐oxidant aditives under compost conditions establishing relationships between physicochemical and rheological parameters

In the present work, an analysis is carried out to provide a relationship between the Molecular Weight (M_w) of degraded LDPE films (containing Mn stearate as pro oxidant (MnSt‐LDPE) and changes in viscosity, elongation at break (EB %) and carbonyl index (CI) occurring during thermal degradation in the thermophilic phase of the compost process. The thermal treatment comprised various temperatures (50°C, 60°C, and 70°C) and exposure times, and was characterized through a so‐called Energy‐Time Factor (the product of thermal energy and exposure time). Changes in viscosity, EB %, and CI were correlated to this factor. A modified Mark‐Houwink equation was used to relate the zero shear‐rate viscosity and M_w of the degraded LDPE films. Results indicate that the EB %, M_w and viscosity decrease simultaneously with an increase in the CI as the Energy‐Time Factor augments, allowing the assessment of the variation of these properties with M_w. Calculations of the percentage abiotic degradation (%D) of LDPE films indicate that a M_w of 6 kg mol^?1 corresponds to a maximum abiotic degradation degree of 91.85%, which is henceforth susceptible to biodegradation. The film treated with Energy‐Time Factor of 2.79E+09 J s mol^?1 reached a 74% of biodegradation in 90 days (average time of the composting process). Results exhibit clearly the correlation between abiotic and biotic degradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42721.     

Synthesis and properties of poly(amide–imide)s based on N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide,p‐aminobenzoic acid and various aromatic diamines

A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, III_a–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only III_k–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though III_g–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g^?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry     

Interfacial slip‐stick transition induced by reactive compatibilization in ethylene‐co‐butyl acrylate elastomer dispersed polyamide 6 blend subjected to high shear flow and extensional flow

The effect of phase interaction induced by reactive compatibilization during high shear and extensional flow in polyamide (PA6) and ethylene‐co‐butyl acrylate (EBA) blends was studied using advanced dual bore capillary rheometer. The viscosity‐composition behavior of the uncompatibilized PA6/EBA blends exhibited negative deviation behavior from log‐additivity rule. The interfacial slip mechanism, operative between the matrix PA6 and dispersed EBA during shear flow was studied by the use of Lin's and Bousmina‐Palierne‐Utracki (BPU) model for viscosity for the blends under the processing conditions. On the other hand, the compatibilized PA6/EBA‐g‐MAH^0.49/EBA blends with varying dispersed phase volume fraction show positive deviation behavior. The reactive compatibilizers EBA‐g‐MAH^0.49 and EBA‐g‐MAH^0.96 increased the phase interaction with adequate reduction in the dynamic interfacial tension, which favored the particle break‐up and stabilized the morphology in the compatibilized blends. The extensional viscosity of the blends has enhanced because of the inclusion of EBA in all the uncompatibilized and compatibilized blends. The melt elasticity and elasticity function were systematically studied from first normal stress coefficient functions (ψ₁). The variation in the recoverable shear strain (γ_R), shear rate dependent relaxation time (λ) and shear compliance (J_c) under various shear rates were thoroughly analyzed for all the blend compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers