Kinetic studies of the polymerization of nylon-6 block copolymers

The kinetics of the activated anionic polymerization of caprolactam to nylon-6 and its copolymers has been studied. Nylon-6 block copolymer and nylon-6 were prepared at various initial reaction temperatures (140°C to 165°C) by anionic polymerization in an adiabatic dewar flask. Different concentrations of poly(ethylene oxide) (PEO) in 4,4′-diphenyl methane diisocyanate (MDI)-capped PEO and 1 mole percent MDI, in a caprolactam solution, were used as the activators with the catalyst, the sodium salt of caprolactam. The kinetics of the reaction were analyzed from an adiabatic temperature rise. A new method was applied to determine the rate parameters. The activation energy, E_a, of nylon-6 and nylon-6 block copolymers were found to be 22 kcal/mole. The collision frequency factor, A_o, steadily decreased and the autocatalytic constant, B_o, decreased to a constant value of 16 with the introduction of PEO. However, it was found that the order of reaction, n, was almost a constant value at the second order for all experiments.     

Binary blends of nylons with ethylene vinyl alcohol copolymers: Morphological,thermal, rheological,and mechanical behavior

Binary blends of ethylene vinyl alcohol copolymers, containing 62 (EVOH-62) and 71 (EVOH-71) mole percent vinyl alcohols, with nylons (nylon-6, nylon-6/12, and nylon-12) have been prepared from melt mixing in a twin screw compounding machine. Morphological, thermal, rheological, and mechanical properties were determined. EVOH-62/nylon-6 and EVOH-71/nylon-6 blends showed homogeneous phase morphologies in the nylon-6-rich region, and fine phase separations (c.a. 2 × 10^?7 m) in the EVOH-rich region. Melting point depression, positive deviations in viscosity and flexural modulus, and negative deviation in impact strength from the simple additive rule were generally observed. And the results were possibly interpreted in terms of compatibility and increased nylon/EVOH interactions over the nylon/nylon interactions. On the contrary, clean phase separations in large domains were observed from EVOH-71/nylon-6/12 and EVOH-71 /nylon-12 blends. Fibrillation was also obtained from EVOH rich blends. Probably due to the incompatible nature of these blends, yield at low rate of shear and a mechanical property drop were also observed.     

Liquid natural rubber (LNR) as a compatibilizer in NR/LLDPE blends

The effects of molecular weight of LNR, as a compatibilizer in NR/LLDPE blends, were studied. Rheological studies and mechanical properties of the blends showed that the molecular weight of LNR played a very important role in determining their performance. The blends that contained 15–25% LNR with an M_w of 4.8 × 10⁵ and an M_n of 1.66 × 10⁵ showed the highest mechanical properties. Outside this range of molecular weight, the compatibilizing property of LNR is no longer effective due to inhomogeneous blends. Improvements in the mechanical properties were in consonance with the increase in gel contents of the blends. The additions of LNR in the blends were able to reduce the interfacial tension; therefore, they improved the interaction between the phases of the blends. The studies also confirmed that, within the concentration range investigated, the LNR solvent did not influence the blend properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1776–1782, 2000     

Preparation and characterization of polyamide 6/liquid natural rubber blends

This study presents a new approach to toughen Polyamide 6 (PA6) by using a low‐molecular weight liquid natural rubber (LNR). The LNR is prepared by mastication of pale latex crepe in the presence of 0.5 phr Peptizol 7. The PA6/LNR blend samples are characterized in terms melt flow index, hardness, abrasion resistance, impact strength, flexural strength, tensile strength, and thermal properties. The impact strength of PA6 increases by about 67% upon addition of 10% LNR. The percolation model is applied to study of brittle to ductile transition. The percolation threshold for the brittle to ductile transition of the blend was found to be 14.5 wt % LNR, corresponding to the critical volume fraction of the stress volume, V_sc = 0.58, which is consistent with the calculated value of ≈ π/6. The PA6/LNR blends exhibit cavitation and matrix shear yielding, which would be the main contribution to the increases impact strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39750.     

Phase morphology and mechanical properties of blends of poly(p-phenylene sulfide) and polyamides

An experimental study of the blending, thermal transitions, phase morphology, and mechanical properties of poly(p-phenylene sulfide) (PPS)/polyamide blends is presented. Nylon-6, rubber modified nylon-6, nylon-66, nylon-11, nylon-12, and two partially aromatic amorphous polyamides were included in the study. Generally, blends of PPS with aromatic amorphous polyamides exhibit better mechanical properties than those with aliphatic polyamides. The blends with nylon-12 exhibit the best characteristics among the aliphatic polyamides.     

Effect of lipid type on water‐in‐oil‐emulsions stabilized by phosphatidylcholine‐depleted lecithin and polyglycerol polyricinoleate

Water‐in‐oil (W/O, 30:70) emulsions were prepared with phosphatidylcholine‐depleted lecithin [PC/(PI,PE) = 0.16] or polyglycerol polyricinoleate (PGPR) as emulsifying agents by means of pressure homogenization. The effect of lipid type (medium‐chain triacylglycerols, sunflower, olive, butter oil, or MCT‐oil/vegetable fat blends) was investigated in relation to particle size distribution, coalescence stability and the sedimentation of the water droplets. A significant correlation (p <0.05) was observed between the interfacial pressure caused by the addition of lecithin to the pure lipids and the specific surface area of the emulsion droplets (r_s = 0.700), and between the viscosity of the lipids used as the continuous phase (reflecting the fatty acid composition) and the specific surface area of the emulsion droplets (r_s = 0.8459) on the other hand. Blends of vegetable fat and MCT‐oil led to reduced coalescence stability due to the attachment of fat crystals to the emulsion droplets. Lecithin‐stabilized W/O emulsions showed significantly higher viscosities compared to those stabilized with PGPR. It was possible to adjust the rheological properties of lecithin‐stabilized emulsions by varying the lipid phase.     

Water permeation properties of SiO2-RSiO3/2 (R = methyl,vinyl, phenyl) thin films prepared by the sol-gel method on nylon-6 substrate

Nylon-6 substrates were coated with SiO₂-RSiO_3/2 (R = methyl, vinyl, phenyl) thin films by the sol-gel method, and their water permeability was evaluated Tetraethoxysilane (TEOS) and trifunctional alkoxides such as methyltriethoxysilane (MTES), vinyltriethoxysilane (VTES), and phenyltriethoxysilane (PhTES) were used as starting materials. Water permeability coefficients of the nylon-6 substrates coated with these SiO₂-RSiO_3/2 thin films were increased with an increase in the content of these trialkoxysilanes in the films. The water permeability coefficients of these coated nylon-6 substrates were smaller in the order of the systems TEOS-PhTES < TEOS-VTES < TEOS-MTES in the relatively low content of the trialkoxysilanes. © 1996 John Wiley & Sons, Inc.     

Effects of Thermal and UV-induced Grafting of Bismaleimide on Mechanical Performance of Reclaimed Rubber/Natural Rubber Blends

The scrap rubber powder (SRP) could be compression moulded to form elastomer via in situ interfacial reactions. In this study, SRP/NR (85/15) blends with good performance could be prepared by incorporating a little amount (lower than 5 phr of SRP and NR) of m-phenyl bismaleimide (BMI) in the compositions. The mechanical properties and the interface of SRP/NR (85/15, w/w) blends (base blend) were investigated. The results showed that the processing temperature, time, and BMI content have significant effects on the mechanical properties of the blends. The optimum BMI content and processing condition were determined as 5 wt.% and 180 ^○C/10 min. The mechanical properties, especially the elongation at break, of the elastomers could be improved further by ultraviolet (UV) exposure. With UV exposure, the tensile strength, elongation at break and tear strength of the modified base blend were determined as 10.4 MPa, 260% and 24 KN/m respectively. The FTIR results indicated that the BMI could be grafted onto the SRP surface under UV exposure. The composition with UV exposure had more uniform dispersion of the BMI and improved interfacial adhesion. The glass transition temperature (T_g) of the blends was increased by increasing the processing temperature, processing time or the introduction of UV exposure.     

Thermal and mechanical behavior of polyamide 6/polyamide 6I/6T blends

The thermal and mechanical properties of blends, obtained by mixing polyamide 6 (PA6) and an amorphous aromatic copolyamide G21 (ISO nomenclature PA 6I/6T), were investigated by differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. Quenched blends show a single glass transition temperature; the T_g-composition trend was interpreted by means of the Gordon–Taylor equation. The half-time of crystal-lization decreases by increasing the G21 content and this indicates a depression of the overall crystallization rate. A small decrease in the equilibrium melting temperature of PA6 in the blends was observed; this finding suggests that the interaction parameter in PA6/G21 blends is probably very small. The dynamic mechanical analysis of crystallized blends suggests the presence of a homogeneous amorphous phase even if the crystallization of PA6 occurred. The tensile mechanical properties reveal that G21 acts as stiffener of PA6. The collected experimental data suggest that PA6 and G21 are miscible in the composition range investigated. © 1996 John Wiley & Sons, Inc.     

Synthesis of polypyrrole nanoparticles in natural rubber–polystyrene blend via emulsion polymerization

Nanoparticles of polypyrrole (PPy) in 40/60 wt % natural rubber (NR)–polystyrene (PS) blends were synthesized by emulsion polymerization using ferric sulfate [Fe₂ (SO₄)₃], sodium dodecyl sulfate (SDS), and n‐amyl alcohol as the oxidant, surfactant, and cosurfactant, respectively. The NR/PS/PPy blends were characterized by Fourier transform infrared spectroscopy (FTIR), elemental analysis, thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FESEM). FESEM micrographs showed that NR/PS/PPy blends were homogeneous, and PPy nanoparticles were well distributed throughout the binary matrix of NR/PS. The size of PPy particles in the blends was in the range of 26–80 nm. The electrical conductivities of the pellets prepared from NR/PS/PPy blends increased as the composition of PPy nanoparticles was increased, which were in the range of 8.9 × 10^?8 – 2.89 × 10^?4 S/cm. Thermal stability of the blends increased as the content of PPy was increased, as shown by TGA thermograms. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Reactive blends of polyamide 6 with polyester elastomer using coupling agents

In situ compatibilized melt blends of polyamide 6 (PA‐6) with polyester elastomer (PEL) were prepared in a corotating twin‐screw extruder using two types of coupling agent (CA): diglycidyl ether of bisphenol A (DGEBA) and 1,4‐phenylene bis(2‐oxazoline) (PBO). The notched impact strength of PA‐6 and PA‐6/PEL blends increased with the addition of coupling agent, especially DGEBA, and the maximum impact toughening of the blend was obtained with 0.6 mol % DGEBA, the composition of minimum domain size observed from SEM. Viscosities of the untreated blends increased over those of the base resins at low frequencies. Viscosities of both the base resins and the blends increased with the addition of CA, and the effect was much more pronounced with DGEBA, especially for PA‐6 and PA‐6–rich blends. The crystallization temperature (T_c) of PEL increased over 10°C, whereas the T_c of PA‐6 decreased by 2–3°C in the blends. With the addition of coupling agents, the crystallization melting temperature (T_m) and T_c of PA‐6 decreased by up to 5°C with DGEBA, implying that the crystallization of PA‐6 is disturbed by the in situ formed PA‐6–CA–PEL or PA‐6–CA–PA‐6 type copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3966–3973, 2004     

Influence of nonsolvents on dissolution characteristics of nylon-6

The dissolution of nylon-6 has been made effective by adding a nonsolvent to the primary solvents that in turn created potential combined contact sites and enhanced the process of dissolution. It is found that 50% of a primary solvent like m-cresol or phenol could be replaced by solvents that are relatively economical and safe to handle. Nylon-6 is found to get dissolved at a faster rate and with ease in a blend of 45 : 55 phenol-toluene compared to other solvent blends. The dependence of limiting viscosity on solute-binary solvent interactions is used as a measure of the solvency power of solvent blends for nylon. The lowering of temperature is found to favour the dissolution of nylon-6 in m-cresol. Its dissolution is found to be optimum in phenol at 55°C and further increase in temperature has adverse effects on it.     

A fourier transform infrared spectroscopy study of the effect of temperature on soy lecithin-stabilized emulsions

The effect of temperature on soy lecithin-stabilized emulsions was studied using Fourier transform infrared spectroscopy (FTIR). Oil-in-water (o/w) 4% (wt/vol) soy lecithin emulsions were prepared in 6% (vol/vol) medium-chain triglycerides and 94% (vol/vol) water using a two-stage homogenizer set at a pressure of 3000 psig. Three types of emulsions were used in this study: emulsions containing Lecigran and Lecimulthin as emulsifiers and a control emulsion, with no emulsifier added. After preparation, the emulsions were cooled to 4°C, held at this temperature, and spectra were collected after 1 h. The emulsions and reference water were raised to room temperature (22°C) and held at that temperature for 1 h and the spectra collected. The temperature was raised 15°C over the temperature range of 22 to 82°C, and spectral data were collected similarly. The four regions used for this determination in the subtracted spectra of the emulsion were those contributing to -OH vibration, -CH₂ stretching, H-O-H bending vibrations, and P=O, C-O-C, and P-O-C vibrations. The control emulsion was greatly affected at temperatures other than room temperature. This was due to the lack of lecithin as an emulsifier, resulting in a destabilization of the emulsion with temperature increases. The vibrational peaks for the emulsion containing Lecimulthin were found to be lower than those for the emulsion made with Lecigran due to greater water bonding. The control had the highest peaks at the -OH regions because of reduced interaction at the oil-water interface. Both of the emulsions with phospholipids remained stable throughout the temperature range. FTIR is a potentially powerful tool that could be used in the rapid determination of emulsion stability in food systems by measuring emulsifier-water interactions.     

Crystallization,morphology, structure and thermal behaviour of nylon-6/rubber blends

An experimental study was carried out in order to investigate the morphological, kinetic, structural and thermodynamic properties of nylon-6/rubber (namely ethylene-propylene copolymer (EPM) and ethylene-propylene copolymer functionalized by inserting along its backbone succinic anhydride groups (EPM-g-SA)) blends. The morphology and the overall kinetics of crystallization of the blends strongly depend on the type of copolymer added to nylon and on the blend composition. The EPM-g-SA acts as a nucleating agent for the Ny spherulites and at the same time causes a drastic depression of the overall kinetic rate constant. This decrease is related to the increase of the melt viscosity observed in Ny/EPM-g-SA blends. The crystalline lamella thickness of the Ny phase in the blends is lower than that of pure Ny crystallized at the same T_c suggesting that the presence in the melt of an elastomeric phase disturbs the growth of the Ny crystals. The rubber does not influence the thermal behaviour of the nylon. The results found lead to the conclusion that in the melt nylon-6 is incompatible with both EPM and EPM-g-SA copolymers.     

Natural rubber–HDPE blends with liquid natural rubber as a compatibilizer. I. Thermal and mechanical properties

The measurement of physical properties of thermoplastic natural rubber (TPNR) of NR–HDPE blends have been made at various compositions of high-density polyethylene (HDPE). The tensile properties and hardness of TPNR improve significantly with the addition of liquid natural rubber (LNR) to the blend. The degree of cross-linking also increases with increasing amount of LNR added. The LNR with molecular weight (M_w) of 50,000 and reactive terminals promotes cross-linking within the rubber phase and grafting of the polyethylene chains onto the rubber matrix system. The maximum stress and strain of the blends measured are about 7.5 MPa and 1000%, respectively. Dynamic mechanical analysis results indicate a single T_g on a tan δ trace at about ?50 and ?55°C for the two types of blends, respectively. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of nylon 6/66/510 used as hot melt adhesives for metal plate with low-surface-energy coating

In this work, nylon 6/66 and nylon 6/66/510 containing 5?～?20?mol % nylon-510 were synthesized to be used as hot melt adhesive for metal plate with low-surface-energy coating. The effects of mole fraction of nylon-510 (X_m) on the thermal and mechanical properties of nylon 6/66/510 were systematically studied. The results demonstrated that: (1) the melting point of the copolyamide decreases and the glass transition temperature decreases when the X_m value increases; (2) the tensile strength of nylon 6/66/510 remains almost unchanged and is almost equal to that of nylon 6/66; (3) the elongation at break of nylon 6/66/510 is significantly higher than that of nylon 6/66. The crystal structure of the copolyamide was also investigated by wide-angle X-ray diffraction (WAXD). The hot-melt adhesives (HMAs) were prepared from nylon 6/66/510, and the adhesive experiments of HMAs to aluminum sheet with low-surface-energy coating were carried out. The results showed that the peeling strength of HMAs based on nylon 6/66/510 reaches a maximum value when X_m = 15?mol %.     

Influence of Copolymer Composition and Curing on Toughness of Isotactic Polypropene Blended Together with Metallocene‐EPDM and Ethene/Propene/Vinylcyclohexane Terpolymers

Ethene/propene terpolymers containing either 1‐vinylcylohexene‐4 (VCHen) or vinylcyclohexane (VCHan) as termonomer component were prepared using MAO‐activated rac‐Me₂Si(2‐MeBenz[e]Ind)₂ZrCl₂ (MBI). Propene content was varied between 26 and 72 wt.‐% with less than 1 mol‐% termonomer incorporation. Blends containing 85 vol.‐% isotactic polypropene (i‐PP) and 15 vol.‐% of the two EP terpolymer families were prepared by melt‐compounding in a twin‐screw kneader at 200°C to examine the role of sulfur‐mediated crosslinking of the unsaturated EPDM terpolymer phase in comparison to the corresponding blends containing non‐crosslinked saturated EP/VCHan terpolymers. The observed glass temperature (T_g) depression of the T_g of EP(D)M phases with respect to the T_g of the corresponding bulk EP(D)M was attributed to the presence of thermally induced stresses in both blend systems. Blends of i‐PP with crosslinked EPDM showed smaller T_g depression with respect to those of iPP/EPM blends containing non‐crosslinked EP and EPM dispersed phases. Morphology differences were detected for i‐PP/EPM and dynamically vulcanized i‐PP/EPDM blends by means of atomic force microscopy (AFM). The crosslinked i‐PP/EPDM blends exhibited significantly improved low temperature toughness as compared to the corresponding non‐crosslinked i‐PP/EPM blends. Curing of the EPDM elastomer phase in i‐PP/EPDM (85 vol.‐%/15 vol.‐%) blends afforded significantly improved toughness/stiffness balance and a wider toughness window with respect to the corresponding i‐PP/EPM and i‐PP/EP blends without sulfur‐cured rubber phases.     

Grafting of methyl methacrylate on EPR and EPDR: Impact properties of polyvinyl chloride grafted polymer blends

EPDM rubber can be brought into water suspension after swelling in n-heptane containing proper emulsifiers and in shear stress; particles reach dimensions as low as 150 Å. Methyl methacrylate in emulsion can be grafted easily with Bz₂O₂ on the rubber. Grafting yields depend particularly on the monomer/rubber ratio. The grafted polymer can be recovered by precipitating the emulsion with acetone, which eliminates the homopolymer. The grafting mechanism is discussed in terms of different initiators (AIBN and Bz₂O₂) and unsaturated (EPDM) and saturated rubber (EPR); AIBN and PMMA radicals were inactive in abstracting hydrogen atoms from rubber chains. Mechanical properties of the blends with PVC of the raw graft product are discussed on the basis of the grafted polymer composition and synthesis conditions. Very high impact strength can be reached at 15% rubber content in the blend for a grafted polymer obtained from a monomer/rubber ratio equal to 0.75.     

Effect of poly(styrene-co-maleic anhydride) on physical properties and crystalline behavior of nylon-6/PEBA blends

This study investigated the effect of blending poly(styrene-co-maleic anhydride) (SMA) on the mechanical and thermal properties of nylon-6/polyether block amide (PEBA) blend. In these blends, nylon-6 was toughened with PEBA using SMA as the compatibilizer. All the blends were prepared via direct melt compounding using a co-rotating twin screw extruder. The amount of PEBA added affected the crystallization characteristics and the relative ratio of γ and α crystalline phases of Nylon 6. The crystallization rate of Nylon 6 was also affected by the cooling rate and the amount of PEBA added. The results of mechanical tests showed that the tensile properties, flexural properties, and impact strengths of the nylon-6/PEBA were all increased when blended with 1 wt% of SMA, at both 23 and ?20 °C. However, for neat nylon-6, the impact strength was not affected despite that both tensile and flexural properties were increased by the blending of SMA. The results indicated that SMA can increase the compatibility between nylon-6 and PEBA, thus expanding the usage of nylon-6/PEBA blend in low-temperature applications.     

Structure and Tribological Performance of Monomer Casting Nylon-6/Colloidal Graphite Composites Synthesized through in Situ Polymerization

A series of monomer casting nylon-6/colloidal graphite composites were synthesized through in situ anionic ring-opening polymerization. It was found that colloidal graphite layers modified with titanate coupling agent had a uniform distribution in the matrix, and the molecular weight of monomer casting nylon-6 decreased slightly below 5?wt% titanate coupling agent-colloidal graphite content. The crystallizing ability was much improved at lower titanate coupling agent-colloidal graphite content, indicating the nucleation effect of titanate coupling agent-colloidal graphite on monomer casting nylon-6. The notched charpy impact strength of the composites increased by addition of 0.5–1?wt% titanate coupling agent-colloidal graphite, and the obvious ductile fracture characteristics was presented. Meanwhile the storage modulus and the glass transition temperature (T_g) increased, and the loss factor (tan δ) decreased by addition of titanate coupling agent-colloidal graphite, indicating the toughening effect of titanate coupling agent-colloidal graphite on monomer casting nylon-6 matrix and improvement of the stiffness of the composites. Compared with neat monomer casting nylon-6 specimen, the composites presented a remarkable lower friction coefficient at the initial friction stage, and the wear resistance of monomer casting nylon-6/4?wt% titanate coupling agent-colloidal graphite specimen was enhanced by more than 10-fold. For neat monomer casting nylon-6, the melting and crystallization temperature, and crystallinity of the worn surface were obviously higher than that of the bulk part, indicating that the surface was fully annealed and the crystallizing ability was improved under produced friction heat, resulting in a poor anti-wear performance with abrasive wear form. For monomer casting nylon-6/titanate coupling agent-colloidal graphite composite, the annealing degree of the surfaces exhibited much lower than that of neat monomer casting nylon-6, due to the protective effect and suppression effect of titanate coupling agent-colloidal graphite layers and reduction of friction heat, resulting in the formation of uniform transfer film and a significant improvement of the wear resistance of the composites with the adhesive wear form.