Starlike Nylon 6/polyurethane block copolymers by reaction injection‐molding process (RIM)

Starlike block copolymers of Nylon‐6 and polyurethane were synthesized using ε‐caprolactam as a monomer, caprolactam magnesium bromide as a catalyst, and a star prepolymer of polyurethane. These copolymers were compared with the linear block copolymers of Nylon‐6 and polyurethane. Such copolymers were obtained using the reaction injection‐molding process (RIM) of ε‐caprolactam at different contents of polyurethane (5–30 wt %). In increasing the content of the soft phase, in FTIR, a displacement was observed in the band at 1637 cm^?1, assigned to the amide I of the Nylon 6, to a higher wavenumber. This suggests a bigger interaction between the urethane group of the polyurethane and the amide group of the Nylon 6. Star block copolymers showed better mechanical properties compared with the linear ones. This behavior is attributed to the higher crystallinity and ramifications present in the materials. The structure and the thermal properties of the copolymers were studied using different techniques such as DSC, WAXS, DMA, and SEM. A decrease in the crystallinity when increasing the soft phase was also observed. Finally, physical tensile, impact, and hardness tests of the copolymers were carried out. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2483–2494, 2001     

Preparation and characterization of polyimide‐g‐nylon 6 copolymers from nonfunctionalized polyimides

In this research, the anionic polymerization of ?‐caprolactam was carried out in the presence of small amounts of several different polyimides to generate polyimide‐g‐nylon 6 copolymers. The polyimides, which were prepared from 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and commercially available diamines with a one‐step method, were first dissolved in molten ?‐caprolactam. Phenylmagnesium bromide was then added at 120°C. Under these conditions, caprolactam anions were formed that attacked the five‐membered imide rings to form N‐acyllactam moieties, which activated the anionic polymerization of caprolactam. In essence, nylon 6 chains grew from the polyimide backbones. Probably because of a high activation energy, the process was relatively slow, requiring 1 h at 120°C. The introduction of 5 wt % polyimide into the graft copolymers produced significant increases in the tensile modulus and tensile strength in comparison with those of low‐ and high‐molecular‐weight nylon 6. The elongation to break, however, was reduced. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 292–299, 2006     

Gas‐sorption properties of 6FDA–durene/1,4‐phenylenediamine (pPDA) and 6FDA–durene/1,3‐phenylenediamine (mPDA) copolyimides

We investigated the sorption isotherms of O₂, N₂, CH₄, and CO₂ gases in 6FDA–durene, 6FDA–1,4‐phenylenediamine (6FDA–pPDA), and 6FDA–1,3‐phenylenediamine (6FDA–mPDA) homopolymers and 6FDA–durene/pPDA and 6FDA–durene/mPDA copolyimides. The solubilities decrease in the order of the inherent condensabilities of the penetrant gases, namely, CO₂, CH₄, O₂, and N₂. The chemical structures of the polymer, as well as the chain packing, determine the sorption properties of these homopolymers and copolymers. The FDA–durene homopolymer has the highest solubility for all gases because of its high specific free volume and fractional free volume. The solubilities of the copolymers increase with an increasing 6FDA–durene content, while the solubility selectivities of the copolymers only vary slightly. The values of K_D (Henry's law constant) and C_H′ (Langmuir site capacity) of these copolyimides decrease with a decreasing 6FDA–durene content. To our surprise, contradictory to the previous known fact that the meta‐connected materials tend to have denser molecular packing than that of the para‐linked materials for homopolymers, the 6FDA–durene/mPDA 80/20 copolymer has higher gas solubilities than those of the 6FDA–durene/pPDA 80/20 copolymer. The random moiety sequence within the copolymer may be the main cause for the abnormal phenomenon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2187–2193, 2003     

Crystallization Controlled by Silicate Surfaces in Nylon 6‐Clay Nanocomposites

The crystallization behavior of pure nylon 6 (N6) and its nanocomposite with montmorillonite has been studied in detail. The crystallization rate of N6 is faster in the presence of clay compared to pure N6, as revealed by light scattering experiments. Nylon 6 crystallizes exclusively in the γ‐form in the nanocomposite because of the epitaxial crystallization, which is also revealed from the transmission electron microscopic images (sandwiched structure) of the crystallized sample. The storage modulus of the nanocomposite is always higher than the pure nylon 6, irrespective of crystallization temperatures. Much higher increment of storage modulus for pure nylon 6 with increasing crystallization temperature is explained by the higher amount of the thermally stable α‐form at higher temperature. A unique mechanism has been proposed to illustrate the crystallization behavior of nylon 6 in the presence of the clay particles.

Transmission electron micrograph of N6C3.7 crystallized at 210 °C, showing the typical shish‐kebab type of structure.     

Poly(ethylene terephthalate) copolymers that contain 5‐tert‐butylisophthalic acid and 1‐3/1‐4‐cyclohexanedimethanol: Synthesis,characterization, and properties

The effects of incorporating 5‐tert‐butylisophthalic acid (^tBI) and 1‐3/1‐4 cyclohexanedimethanol (CHDM) in the polymer chain of poly(ethylene terephthalate) (PET) on the crystallization behavior and thermal, optical and tensile properties of this polyester (PETGB) were evaluated. These random copolyesters that contained between 0 and 20 mol % of CHDM and between 0 and 10 mol % of ^tBI units were prepared by esterification followed by melt copolycondensation. The compositions and molecular weights of the copolyesters were determined by ¹H‐NMR spectroscopy and viscometry, respectively. The composition of the polyester was consistent with the composition of the feed. The intrinsic viscosities of the copolymers ranged between 0.62 and 0.74 dL/g. The thermal behaviors were investigated over the entire range of copolymer compositions, using DSC under the heating and cooling rate of 20°C/min and TGA. The copolyesters with ^tBI and CHDM of < 20 mol % were crystallizable, whereas the copolyesters with ^tBI and CHDM of ≥ 20 mol % were amorphous. They appeared to be stable up to 395°C. The optical transmissions of the amorphous polyesters were more than 88% in the visible region. The mechanical behavior was investigated by performing a tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 279–285, 2007     

Synthesis of polypropylene‐graft‐maleic anhydride compatibilizer and evaluation of nylon 6/polypropylene blend properties

Polymer blends based on polyolefins are of a great interest owing to their broad spectrum of properties and practical applications. However, because of poor compatibilities of components, most of these systems generally exhibit high interfacial tension, a low degree of dispersion and poor mechanical properties. It is generally accepted that polypropylene (PP) and nylon 6 (N6) are not compatible and that their blending results in poor materials. The compatibility can be improved by the addition of a compatibilizer, and in this study PP was functionalized by maleic anhydride (MAH) in the presence of an optimized amount of dicumyl peroxide (DCP). The reaction was carried out in the molten state using an internal mixer. Then, once the compatibilizer polypropylene‐graft‐maleic anhydride (PP‐g‐MAH) was prepared, it was added at various concentrations (2.5–10 wt%) to 30/70 glass fibre reinforced N6 (GFRN6) PP, and the mechanical properties were evaluated. It was found that the incorporation of the compatibilizer enhanced the tensile properties (tensile strength and modulus) as well as the Izod impact properties of the notched samples. This was attributed to better interfacial adhesion as evidenced by scanning electron microscopy (SEM). The optimum in these properties was achieved at a critical PP‐g‐MAH concentration. Copyright © 2005 Society of Chemical Industry     

MCPA6/改性聚硅氧烷复合材料的摩擦磨损性能

采用阴离子聚合法制备了浇铸尼龙6(MCPA6)/改性羟基封端聚二甲基硅氧烷(MHPDMS)原位复合材料,研究了不同MHPDMS含量对复合材料在水润滑及干摩擦条件下的摩擦磨损性能影响。结果表明,在干摩擦条件下,复合材料的摩擦系数随滑动时间增加先增大后减小最后达到平衡,随着MHPDMS含量的增加,复合材料在稳定阶段的摩擦系数变化不大,但是磨损量逐渐减小,MHPDMS质量分数为4%的复合材料磨损量仅为MCPA6的25%;在水润滑条件下,复合材料的摩擦系数随滑动时间增加先增大后平衡,随着MHPDMS含量的增加,复合材料的稳定摩擦系数基本没有变化,磨损量先减小后增大,当MHPDMS质量分数为2%时,磨损量最小,为MCPA6的50%左右。复合材料在水润滑条件下的稳定摩擦系数比干摩擦条件下的小,但磨损量比干摩擦条件下的大很多。复合材料在干摩擦条件下的磨损机理主要是粘着磨损和疲劳磨损,而在水润滑条件下主要为犁削磨损和磨粒磨损。     

Nanostructuration of Unsaturated Polyester by All‐Acrylic Block Copolymers, 1 ‐ Use of High‐Molecular‐Weight Block Copolymers

Nanostructuration of maleate and orthophthalic unsaturated polyester (UP) resins was achieved by the use of high molecular weight amphiphilic PBA‐b‐P(MMA‐co‐DMA)₂ triblock copolymers. PBA is fully immiscible in cured UP resins, and the miscibility of P(MMA‐co‐DMA) random copolymers can be ensured with a minimum DMA content of 12 mol‐%. When using the triblock copolymers, fully transparent and nanostructured thermosets are obtained with a minimum DMA content in the outer blocks; the value of which is higher than 12 mol‐% and depends on the UP chemical structure. Finally, the fracture toughness of nanostructured thermoset was evaluated: for a triblock copolymer content as low as 5 wt.‐%, a 50% increase of K_Ic was obtained, as compared to the neat thermoset.

     

PA6/蒙脱土复合材料结构与性能的研究

采用熔融插层法制备了尼龙6(PA6)／蒙脱土插层复合材料,通过X射线衍射仪、透射电镜等表征手段研究了该复合材料的微观结构,采用锥形量热仪、拉伸测试仪等测试了材料的阻燃性能、力学性能以及热变形温度。结果表明,有机蒙脱土片层的间距扩大了,PA6插入了有机蒙脱土片层之间。PA6／蒙脱土插层复合材料具有较低的热释放速率和质量损失,并且当有机蒙脱土质量分数为5％～7％时,该复合材料的综合性能最好。     

High‐Impact Polyamide Composites with Linear Ethylene–Norbornene Anhydride Copolymers from Insertion Polymerization

Toughening of polyamide 66 with novel linear norbornene anhydride functionalized polyethylenes leads to an impact performance in the Charpy‐notch impact testing at 23 °C and ?30 °C as high as a_CN = 18.0 ± 1.0 and 13.7 ± 0.8 kJ m^?2, respectively, which compares favorably to a state of the art functional low density polyethylene (LDPE) from high‐pressure copolymerization with a Charpy‐notch impact strength of a_CN = 16.8 ± 0.0 and 13.8 ± 2.1 kJ m^?2 at 23 and ?30 °C, respectively. The linear copolymers are obtained by insertion polymerization at mild ethylene pressures of 5 to 15 bars with phosphinesulfonato Pd (II) catalysts, to yield linear copolymers with norbornene anhydride incorporations as high as 4.8 mol% along with a polymer molecular weight of >10⁵ g mol^?1. Furthermore, the norbornene anhydride functionality serves as a reaction site for postpolymerization functionalization with alcohols to obtain the respective half‐ and diesters of the anhydride functionality. Notably, the impact performance is improved with the increase of the alkyl chain length and degree of branching of the ester functionality in the order methanol < n‐butanol < 2‐ethyl hexanol from 10.0 to 13.8 kJ m^?2.     

Preparation of biodegradable polyesters/high‐amylose‐starch composites by reactive blending and their characterization

Two different biodegradable polyesters [polycaprolactone (PCL) and poly(3‐hydroxybutyrate‐co‐valerate) (PHBV)] were blended with a maize starch that had high amylose content through the use different reactive approaches. The compatibilization of both systems was obtained. PCL/starch composites were obtained by the addition of a third reactive component that was able to act as a coupling agent, and the reactive interface of PHBV/starch composites was improved during blending with an organic peroxide. Thermal, morphological, and mechanical characterization showed that the compatibilized composite materials had better final proprieties than neat materials or composites prepared without compatibilization. Finally, the degradation of all prepared materials by a compost simulation test was investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1432–1442, 2002     

Synthesis and characterization of conducting copolymer of Trans‐1‐(4‐methyl‐3′‐thienyl)‐2‐(ferrocenyl)ethene with EDOT

Ferrocene‐substituted conducting polymer namely poly(trans‐1‐(4‐methyl‐3′‐thienyl)‐2‐(ferrocenyl)ethene‐co‐3,4‐ethylenedioxythiophene) [P(MTFE‐co‐EDOT)] was synthesized and its electrochromic properties were studied. Monomer, MTFE, was obtained using 2‐(ferrocenyl)ethene and 3‐methyl‐4‐bromothiophene. The structure of monomer was determined via Fourier transform infrared spectroscopy (FTIR), ¹H‐NMR, and ¹³C‐NMR techniques. The copolymer was synthesized using this monomer and EDOT. The resulting copolymer P(MTFE‐co‐EDOT) was characterized by cyclic voltammetry, FTIR, scanning electron microscopy, atomic force microscopy, and UV–vis spectroscopy. The conductivity measurements of copolymer and PEDOT were accomplished by the four‐probe technique. Although poly(trans‐1‐(4‐methyl‐3′‐thienyl)‐2‐(ferrocenyl)ethene) [P(MTFE)] reveals no electrochromic activity, its copolymer with EDOT has two different colors (violet and gray). Band gap (E_g) and λ_max of P(MTFE‐co‐EDOT) were determined. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nylon 6/ethylene propylene rubber (EPM) blends: Phase morphology development during processing and comparison with literature data

The morphology of immiscible blends of nylon 6 and ethylene propylene rubber blends (EPM) was studied. The blends were prepared by melt blending in a twin‐screw miniextruder and a Haake Rheocord mixer. The influence of the blend ratio, time of mixing, rotation speed of the rotors, mixing temperature, and quenching of the extruded melt at low temperature on the phase morphology of the blends was quantitatively analyzed. The morphology was examined by scanning electron microscopy (SEM) after preferential extraction of the minor phase. The SEM micrographs were quantitatively analyzed for domain‐size measurements. The morphology of the blends indicated that the EPM phase was preferentially dispersed as domains in the continuous nylon matrix up to 40 wt % of its concentration. A cocontinuous morphology was observed at 50 and 60 wt % EPM content followed by a phase inversion beyond 60 wt % of EPM where the nylon phase was dispersed as domains in the continuous EPM phase. The size, shape, and distribution of the domains were evaluated by image analysis as a function of the blend composition. The effect of the time of mixing on the phase morphology was studied up to 20 min for the 30/70 EPM/nylon blend. The most significant domain breakup was observed within the first 3 min of mixing followed by a leveling off up to 15 min. This may be associated with the equilibrium between the domain breakup and coalescence. The influence of rotor speed on the morphology was insignificant at a high rotor speed although a significant effect was observed by changing the rotor speed from 9 to 20 rpm. The influence of high‐temperature annealing, repeated cycles of extrusion, the molecular weight of the nylon matrix, and the nature of the mixer type (twin‐screw miniextruder versus Haake Rheocord mixer) on the morphology was also investigated in detail. The experimental results were compared with literature data. Finally, the extent of interface adhesion in these blends was analyzed by examination of the fracture‐surface morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1405–1429, 1999     

Control and development of crystallinity and morphology in poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(propylene carbonate) blends

Two different methodologies (reactive blending and mechanical blending) for preparing blends of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and poly(propylene carbonate) (PPC) were used. The miscibility, chemical structure, thermal behavior, crystallinity, morphology, and mechanical properties of the blends were investigated with Fourier transform infrared spectroscopy, differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and tensile tests. A certain extent of hydrogen‐bonding interactions between PHBV and PPC took place in the blends. The graft copolymerization was confirmed in the reactive system. The incorporation of PPC hampered the crystallization process of PHBV and evidently altered the morphology, and the effect was enhanced in the reactive blend. The mechanical properties of PHBV could be changed by 1–2 orders of magnitude by blending modification. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1427–1436, 2005     

PP-g-MAH对尼龙6/炭黑复合材料性能和形貌的影响

以炭黑(CB)为导电填料,马来酸酐接枝聚丙烯(PP-g-MAH)为增韧剂,通过双螺杆挤出机和注射成型机制备了尼龙(PA)6/PP-g-MAH/CB复合材料,研究了PP-g-MAH含量对7.5%CB填充PA6力学性能、抗静电性能、热稳定性能和形貌的影响。结果表明,添加质量分数20%的PP-g-MAH可提高PA6/CB复合材料的拉伸强度、韧性、抗静电性能和热稳定性。PA6/PP-g-MAH/CB复合材料力学强度和热稳定性的提高源于PP-g-MAH产生的能量耗散以及CB,PP-g-MAH与PA6之间较好的界面粘附和PP-g-MAH均匀细化分散在PA6/CB中。PP-g-MAH改变了CB在共混物中的选择性分布,使PA6/CB的表面电阻率和体积电阻率分别下降5个和3个数量级。     

Effect of the type of nylon chain‐end on the compatibilization of PP/PP‐GMA/nylon 6 blends

Polyamide and polypropylene (PP) are two important classes of commercial polymers; however, their direct mixing leads to incompatible blends with poor properties. Polypropylene functionalized with glycidyl methacrylate (PP‐GMA) was used as a compatibilizer in blends of PP and nylon 6, because of the possible reaction of ? NH₂ and ? COOH groups with the epoxide group of GMA. Two types of nylon 6 with different ratios between ? NH₂ and ? COOH groups were used. The one with higher concentration of ? COOH groups was less compatible with PP in a binary blend. When PP‐GMA was used as a compatibilizer, a better dispersion of nylon in the PP matrix was obtained together with better mechanical properties for both nylons used in this work. © 2001 Society of Chemical Industry     

Nylon 6 induced morphological developments and electrical conductivity improvements of polypropylene/carbon black composites

In this study, a polar conductive filler [carbon black (CB)], a nonpolar polymer [polypropylene (PP)], and a polar polymer [nylon 6 (PA6)] were chosen to fabricate electrically conductive polymer composites by melt blending and compression molding. The morphological developments of these composites were studied. Scanning electron microscopy results showed that in a CB‐filled PP/PA6 (CPA) composite, CB particles were selectively dispersed in PA6 phases and could make the dispersed particles exist as microfiber particles, which could greatly improve the electrical conductivity. The PA6 and CB contents both could affect the morphologies of these composites. The results of electrical resistivity measurements of these composites proved the formation of conductive networks. The resistivity–temperature behaviors of these composites were also studied. For CB‐filled PP (CP) composites, there were apparent positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects and an unrepeatable resistivity–temperature characteristic. However, for CPA composites, there were no PTC or NTC effects from room temperature to 180°C, and the resistivity–temperature behavior showed a repeatable characteristic; this proved that CB particles were selectively dispersed in the PA6 phase from another point of view. All experimental results indicated that the addition of PA6 to a CP composite could lead to an expected morphological structure and improve the electrical conductivity of the CP composite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization of 1‐oxo‐2,6,7‐trioxa‐1‐phorsphabicyclo[2,2,2]oct‐4‐yl methyl acrylate and (10‐oxo‐10‐hydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐yl) methyl acrylate with styrene and their thermal degradation characteristics

Two phosphorus‐containing acrylates of 1‐oxo‐2,6,7‐trioxa‐1‐phorsphabicyclo[2,2,2]oct‐4‐yl methyl acrylate and (10‐oxo‐10‐hydro‐9‐oxa‐10λ⁵‐phosphaphenanthrene‐10‐yl) methyl acrylate were free‐radical‐copolymerized with styrene (St). The r₁ reactivity ratio values (related to the novel acrylates) were 0.342 and 0.225, respectively, and the r₂ reactivity ratio values (related to St) were 0.432 and 0.503, respectively. The thermal stability of the copolymers was tested by thermogravimetric analysis (TGA) in N₂ or air, and the ignitability was tested by measurements of UL‐94 vertical combustion tests and the limiting oxygen index. The results of TGA and combustion tests indicated that the effect of flame retardancy was determined by the nature of the phosphorus‐containing substituent. Compared with the 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide based group, the 1‐oxo‐2,6,7‐trioxa‐1‐phorsphabicyclo[2,2,2]oct‐4‐yl methol based group could enhance the ability of char formation with an antidripping effect. It is concluded that phosphorus‐containing acrylates are potential flame‐retarding monomers for styrenic polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ethylene/1‐octadecene copolymerization using [η5:η1‐C5Me4‐4‐R1‐6‐R‐C6H2O]TiCl2 catalysts

Copolymerization of ethylene with 1‐octadecene was studied using [η⁵:η¹‐C₅Me₄‐4‐R₁‐6‐R‐C₆H₂O]TiCl₂ [R₁ = ^tBu (1), H (2, 3, 4); R = ^tBu (1, 2), Me (3), Ph (4)] as catalysts in the presence of Al(i‐Bu)₃ and [Ph₃C][B(C₆F₅)₄]. The effect of the concentration of comonomer in the feed and Al/Ti molar ratio on the catalytic activity and molecular weight of the resultant copolymer were investigated. The substituents on the phenyl ring of the ligand affect considerably both the catalytic activity and comonomer incorporation. The 1 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system exhibits the highest catalytic activity and produces copolymers with the highest molecular weight, while the 2 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system gives copolymers with the highest comonomer incorporation under similar conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011