Reducing water sorption of injection‐molded polyamide 6 bars by polymerization‐induced diffusion of styrene and grafting with polystyrene

An innovative method for reducing water sorption of injection‐molded polyamide 6 (PA6) bars by polymerization‐induced diffusion of styrene and grafting with polystyrene (PS) is reported. The process involves diffusion of styrene into PA6 bar in aqueous medium, addition of benzoyl peroxide to initiate polymerization of styrene, and further diffusion of styrene into the bar during polymerization. A hydrophobic PS‐rich shell consisting mainly of PS‐g‐PA6 can be formed in the surface layer of the PA6 bar, and as a result, the water sorption and dimensional change of PS‐modified PA6 bars reduce significantly. An incorporation of only 1.2% PS is sufficient, showing the advantage of this method over conventional melt mixing. The tensile modulus and strength of 1.2% PS‐modified PA6 bar increase slightly compared to those of neat PA6 bar due to reinforcement effect of rigid PS and reduced level of water‐caused plasticization, while maintaining the good ductility. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46243.     

Tough polyamide 6/core–shell blends prepared via in situ anionic polymerization of ε‐caprolactam by reactive extrusion

In this study, the molten ε‐caprolactam (CL) solution of maleated styrene‐ethylene/butylene‐styrene block copolymer (SEBS‐g‐MA) and polystyrene (PS) containing catalyst and activator were introduced into a twin screw extruder, and polyamide 6 (PA6)/SEBS/PS blends were successfully prepared via anionic polymerization of CL by reactive extrusion. The mechanical properties measurements indicated that both the elongation at break and notched Izod impact strength of PA6/SEBS/PS (85/10/5) blends were improved distinctly with slight loss of tensile and flexural strength as compared to that of pure PA6. The images of transmission electron microscopy showed that a core–shell structure with PS core and poly (ethene‐co‐1‐butene) (PEB) shell was formed within the PA6 matrix. Fourier transform infrared was used to investigate the formation mechanisms of the core–shell structure. POLYM. ENG. SCI., 53:2705–2710, 2013. © 2013 Society of Plastics Engineers     

Anionic polymerization of lactams: A comparative study on various methods of measuring the conversion of ε‐caprolactam to polyamide 6

Anionic ring‐opening polymerization of lactams leads to the formation of poly(lactams) or polyamides. This work aimed at comparing the performance of four methods for measuring the conversion of ε‐caprolactam (CL) to polyamide 6. The latter was either a homopolymer (PA6) or grafts onto polystyrene (PS‐g‐PA6 graft copolymer). Those four methods were mass balance based on solvent extraction (methanol, water, THF, or acetone), mass balance based on vacuum drying at 140°C, thermogravimetric analysis (TGA), and elemental analysis based on nitrogen. The mass balances based on methanol extraction and vacuum drying at 140°C and TGA were all suitable for measuring the conversion of CL, whether the resulting polymer was the PA6 or PS‐g‐PA6. The mass balance based on water extraction was good for the PA6 and not good for the PS‐g‐PA6. The elemental analysis based on nitrogen was not suitable for the PA6 nor for the PS‐g‐PA6. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1972–1981, 2006     

Effect of in situ synthesized macroactivator on morphology of PA6/PS blends via successive polymerization

In situ polymerization and in situ compatibilization was adopted for preparation of ternary PA6/PS‐g‐PA6/PS blends by means of successive polymerization of styrene, with TMI and ε‐caprolactam, via free radical copolymerization and anionic ring‐opening polymerization, respectively. Copolymer poly(St‐g‐TMI), the chain of which bears isocyanate (? NCO), acts as a macroactivator to initiate PA6 chain growth from the PS chain and graft copolymer of PS‐g‐PA6 and pure PA6 form, simultaneously. The effect of the macroactivator poly(St‐g‐TMI) on the phase morphology was investigated in detail, using scanning electron microscopy. In case of blends with higher content of PS‐g‐PA6 copolymer, copolymer nanoparticles coexisting with the PS formed the matrix, in which PA6 microspheres were dispersed evenly as minor phase. The content of the compositions (homopolystyrene, homopolyamide 6, and PS‐g‐PA6) of the blends were determined by selective solvent extraction technique. The mechanical properties of PA6/PS‐g‐PA6/PS blends were better than that of PA6/PS blends. Especially for the blends T10 with lower PS‐g‐PA6 copolymer content, both the flexural strength and flexural modulus showed significantly improving because of the improved interfacial adhesion between PS and PA6. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical properties of polystyrene/polyamide 6 blends compatibilized with the ionomer poly(styrene‐co‐sodium acrylate)

The compatibilizing effect of the ionomer, poly(styrene‐co‐sodium acrylate) (PSSAc), on immiscible blends of polystyrene (PS)/polyamide 6 (PA6) was studied by mechanical tests and scanning electron microscopy. The PSSAc acts as an effective compatibilizer because both the deformation at break (%) obtained by tensile stress–strain tests and the impact rupture energy are larger in blends containing small amounts of PSSAc. The morphologies of the fractured surfaces produced by tensile stress–strain tests of blends with or without the ionomer confirm that PSSAc increases the interfacial adhesion between PS and PA6 phases. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2545–2551, 2004     

Preparation of isotactic polypropylene/polystyrene blends by diffusion and subsequent polymerization of styrene in isotactic polypropylene pellets

Isotactic polypropylene (iPP) pellets were used to prepare isotactic polypropylene/polystyrene (iPP/PS) blends by diffusion and subsequent polymerization of styrene in water medium, with initiator benzoyl peroxide (BPO) added after diffusion of styrene. Two methods, differencing in whether the excess monomer was removed after diffusion, were used and parameters influencing PS contents were investigated. Diffusion kinetic study showed that the diffusion coefficient at 90 °C is 2.8 times that at 80 °C due to the α relaxation of iPP segments. Investigation on the distribution state of styrene in the mixture before diffusion revealed that most styrene adsorbed on the surface of iPP pellets, and thus the diffusion behavior of styrene into iPP pellets in water medium is similar to that in bulk styrene. Phase morphology of a typical iPP/PS blend showed an average particle size of about 90 nm in the inner part of the iPP pellets. The diametrical distributions of PS showed that styrene can diffuse up to the center of the pellets at 90 °C. It is important to note that the depth of styrene is limited when the initiator BPO is added along with styrene, providing a good explanation for the previously reported ineffective solid-state modification of melt-extruded iPP pellets.     

Anionic polymerization and properties of graft copolymers consisting of alternating styrene/maleimide copolymer main chains and polyamide 6 grafts

This article is focused on the synthesis of a new type of graft PA6, which contained alternating styrene/maleimide copolymer main chains and PA6 grafts, by anionic polymerization. The preprepared styrene/maleimide copolymers with acylated caprolactam (ACL) pendants were used as macroactivators for the polymerization of molten ε‐caprolactam (CL). Because of the low activating energy for the initial nucleophilic attack of CL anion on the N‐ACL, the polymerization took place in a few minutes. The macroactivators were characterized by ¹H‐NMR. And the thermal properties, dimensional stability, crystallinity, and solvent resistance ability of the graft PA6 were studied, using DSC, TGA, XRD, water absorption measurement, and solubility experiment. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Relationship between structure and properties in high‐performance PA6/SEBS‐g‐MA/(PPO/PS) blends: The role of PPO and PS

This work aimed at studying the role of poly(phenylene oxide) (PPO) and polystyrene (PS) in toughening polyamide‐6 (PA6)/styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (SEBS‐g‐MA) blends. The effects of weight ratio and content of PPO/PS on the morphology and mechanical behaviors of PA6/SEBS‐g‐MA/(PPO/PS) blends were studied by scanning electron microscope and mechanical tests. Driving by the interfacial tension and the spreading coefficient, the “core–shell” particles formed by PPO/PS (core) and SEBS‐g‐MA (shell) played the key role in toughening the PA6 blends. As PS improved the distribution of the “core–shell” particles due to its low viscosity, and PPO guaranteed the entanglement density of the PPO/PS phase, the 3/1 weight ratio of PPO/PS supplied the blends optimal mechanical properties. Within certain range, the increased content of PPO/PS could supply more efficient toughening particles and bring better mechanical properties. Thus, by adjusting the weight ratio and content of PPO and PS, the PA6/SEBS‐g‐MA/(PPO/PS) blends with excellent impact strength, high tensile strength, and good heat deflection temperature were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45281.     

Toughening of polyamide 6 with a maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer

Maleic anhydride functionalized acrylonitrile–butadiene–styrene (ABS‐g‐MA) copolymers were prepared via an emulsion polymerization process. The ABS‐g‐MA copolymers were used to toughen polyamide 6 (PA‐6). Fourier transform infrared results show that the maleic anhydride (MA) grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Rheological testing identified chemical reactions between PA‐6 and ABS‐g‐MA. Transmission electron microscopy and scanning electron microscopy displayed the compatibilization reactions between MA of ABS‐g‐MA and the amine and/or amide groups of PA‐6 chain ends, which improved the disperse morphology of the ABS‐g‐MA copolymers in the PA‐6 matrix. The blends compatibilized with ABS‐g‐MA exhibited notched impact strengths of more than 900 J/m. A 1 wt % concentration of MA in ABS‐g‐MA appeared sufficient to improve the impact properties and decreased the brittle–ductile transition temperature from 50 to 10°C. Scanning electron microscopy results show that the shear yielding of the PA‐6 matrix was the major toughening mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 toughened by maleated polystyrene‐based copolymers: Mechanical properties,morphology, and rheology

Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6 30/70) blends were impact modified by addition of three kinds of maleated polystyrene‐based copolymers, i.e., maleated styrene‐ethylene‐butylene‐styrene copolymer (SEBS‐g‐MA), maleated methyl methacrylate‐butadiene‐styrene copolymer (MBS‐g‐MA), and maleated acrylonitrile‐butadiene‐styrene copolymer (ABS‐g‐MA). The mechanical properties, morphology and rheological behavior of the impact modified PPO/PA6 blends were investigated. The selective location of the maleated copolymers in one phase or at interface accounted for the different toughening effects of the maleated copolymer, which is closely related to their molecular structure and composition. SEBS‐g‐MA was uniformly dispersed in PPO phase and greatly toughened PPO/PA6 blends even at low temperature. MBS‐g‐MA particles were mainly dispersed in the PA6 phase and around the PPO phase, resulting in a significant enhancement of the notched Izod impact strength of PPO/PA6 blends from 45 J/m to 281 J/m at the MBS‐g‐MA content of 20 phr. In comparison, the ABS‐g‐MA was mainly dispersed in PA6 phase without much influencing the original mechanical properties of the PPO/PA6 blend. The different molecule structure and selective location of the maleated copolymers in the blends were reflected by the change of rheological behavior as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymerization kinetics of styrene in isotactic polypropylene pellets and evolution of phase morphology during polymerization

Polymerization kinetics of styrene (St) in commercially available isotactic polypropylene (iPP) pellets and the phase morphology evolution during polymerization are investigated. The polymerization rate of St in iPP pellets is slightly faster than in the corresponding bulk and suspension polymerizations carried out under similar reaction conditions due to the existence of two reaction sites: amorphous PP and polystyrene (PS), which are formed by polymerization‐induced phase separation. Two mechanisms are proposed for the phase morphology evolution: nucleation and growth, and St‐assisted coarsening of phase structure. During polymerization, the size of the dispersed PS particles increases with polymerization time no matter at which position of the pellet, but the increasing amplitude is much bigger at 200 μm distance to the edge than at the center due to much more significant occurrence of St‐assisted coarsening of phase structure which is attributed to both high values of PS/PP and St/PP resulted from polymerization‐induced diffusion of St. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43934.     

In situ control of co‐continuous phase morphology for PS/PS‐co‐TMI/PA6 blend

The emulsification efficiency of PS‐co‐TMI, a copolymer polymerized by styrene and 3‐isopropenyl‐α,α‐dimethylbenzene isocyanate (TMI), for polystyrene (PS)/polyamide 6 (PA6) blend was studied. During the mixing process, an effective emulsifier PS‐g‐PA6 was generated, which was demonstrated by differential scanning calorimetry (DSC) and fourier transform infrared spectroscopy. PS‐g‐PA6 generated by PS‐co‐TMI with high TMI content was found to contain some unreacted isocyanate active groups which reduced using efficiency of PS‐co‐TMI. Irrespective of TMI content in PS‐co‐TMI, the dosage of PS‐co‐TMI reached 20 wt %, unreacted PS‐co‐TMI was detected. These results indicated that reactive emulsification limits for both active groups' content and reactive precursors' dosage. After the rational addition of PS‐co‐TMI into PS/PA6 system, phase sizes of co‐continuous structure were reduced conspicuously. However, co‐continuous structure was evolved into matrix‐dispersed structure while the dosage of PS‐co‐TMI reached 20 wt %. Emulsification efficiencies of PS‐co‐TMI with different TMI contents, 2.2, 4.1, and 7.5 wt %, were compared. The results revealed PS‐co‐TMI with 2.2 wt % TMI content had the highest reactive emulsification efficiency because of the block‐copolymer‐inclined emulsifier generated in the mixing process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39972.     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

The reactive compatibilization effect of copolymer macroactivator for immiscible anionic polyamide 6/polystyrene blends via in situ polymerization

In this article, a novel method has been successfully developed to prepare the anionic polyamide 6/polystyrene (APA6/PS) blends. The macroactivator P(St‐co‐IEM) was synthesized by the free radical polymerization of 2‐isocyanatoethyl methacrylate and styrene (St), then the graft copolymer of PS and APA6 (PS‐g‐APA6) can be obtained by the anionic polymerization of ɛ‐caprolactam activated by the macroactivator P(St‐co‐IEM). The X‐ray diffraction analysis, differential scanning calorimetry, scanning electron microscopy analysis, contact angle measurement, water absorption measurement, molau test, thermogravimetric analysis, and mechanical properties test were performed separately to study the effects of P(St‐co‐IEM) on crystallinity, morphology, water resistance, thermal stability, and mechanical properties. The results indicate the synthesis of macroactivator can promote the formation of the γ‐phase. Moreover, it can improve the interfacial compatibility, water resistance, thermal stability, and toughness. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46302.     

Water absorption behavior of different types of organophilic montmorillonite‐filled polyamide 6/polypropylene nanocomposites

The water absorption behavior of different types of organophilic montmorillonite (OMMT)‐filled polyamide 6/polypropylene nanocomposites with and without compatibilizers (maleated PP or PP‐g‐MA and maleated styrene‐ethylene/butylene‐styrene or SEBS‐g‐MA) was evaluated. Four different types of OMMT, i.e., dodecylamine‐modified MMT (D‐MMT), 12 aminolauric acid‐modified MMT (A‐MMT), stearylamine‐modified MMT (S‐MMT), and commercial organo‐MMT (C‐MMT) were used as reinforcement. The water absorption response of the nanocomposites was studied and analyzed by tensile test and morphology assessment by scanning electron microscopy (SEM). The kinetics of water absorption of the nanocomposites conforms to Fick's law. The M_m and D are dependent on the types of OMMT and compatibilizers. The equilibrium water content and diffusivity of PA6/PP blend were increased by the addition of OMMT but decreased in the presence of compatibilizers. On water absorption, both strength and stiffness of the nanocomposites were drastically decreased, but the ductility was remarkably increased. Both PP‐g‐MA and SEBS‐g‐MA played an effective role as compatibilizers for the nanocomposites. This was manifested by their higher retention ability in strength and stiffness (in the wet and re‐dried states), reduced the equilibrium water content, and diffusivity of the nanocomposites. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Gasoline permeation behavior and mechanical properties of polyamide 6/nanoclay,polyamide 6/PE‐g‐maleic anhydride blend,and polyamide 6/PE‐g‐maleic anhydride/clay nanocomposite

In this article, polyamide 6 (PA6)/clay nanocomposites, PA6/polyethylene grafted maleic anhydride (PE‐g‐MA) blends, and PA6/PE‐g‐MA/clay nanocomposites were prepared and their gasoline permeation behavior and some mechanical properties were investigated. In PA6/clay nanocomposites, cloisite 30B was used as nanoparticles, with weight percentages of 1, 3, and 5. The blends of PA6/PE‐g‐MA were prepared with PE‐g‐MA weight percents of 10, 20, and 30. All samples were prepared via melt mixing technique using a twin screw extruder. The results showed that the lowest gasoline permeation occurred when using 3 wt % of nanoclay in PA6/clay nanocomposites, and 10 wt % of PE‐g‐MA in PA6/PE‐g‐MA blends. Therefore, a sample of PA6/PE‐g‐MA/clay nanocomposite containing 3 wt % of nanoclay and 10 wt % of PE‐g‐MA was prepared and its gasoline permeation behavior was investigated. The results showed that the permeation amount of PA6/PE‐g‐MA/nanoclay was 0.41 g m^?2 day^?1, while this value was 0.46 g m^?2 day^?1 for both of PA6/3wt % clay nanocomposite and PA6/10 wt % PE‐g‐MA blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40150.     

Effects of maleated styrene–(ethylene‐co‐butene)–styrene on the morphology and mechanical and thermal properties of polystyrene/polyamide 1212 blends

Polystyrene (PS)/polyamide 1212 (PA 1212) blends were compatibilized with a maleated triblock copolymer of styrene–(ethylene‐co‐butene)–styrene (SEBS‐g‐MA). Scanning electron microscopy revealed that the addition of SEBS‐g‐MA was beneficial to the dispersion of PA 1212 in the PS matrix because of the reaction between them. The variation of the fraction of SEBS‐g‐MA in the blends allowed the manipulation of the phase structure, which first formed a sheetlike structure and then formed a cocontinuous phase containing PA 1212/SEBS‐g‐MA core–shell morphologies. As a result, the mechanical properties, especially the Charpy notched impact resistance, were significantly improved with the addition of SEBS‐g‐MA. Differential scanning calorimetry (DSC) data indicated that the strong interaction between SEBS‐g‐MA and PA 1212 in the blends retarded the crystallization of PA 1212. The heat distortion temperature of the compatibilized blends was improved in comparison with that of the unmodified blend, probably because of the apparent increase in the glass‐transition temperature with an increasing concentration of SEBS‐g‐MA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1354–1360, 2005     

Synthesis of poly(styrene‐co‐4‐vinylpyridine) microspheres via dispersion polymerization: Effect of the concentration of 4‐vinylpyridine

Amphiphilic copolymer microspheres of poly(styrene‐co‐4‐vinylpyridine) were prepared by dispersion polymerization in an alcohol/water medium. The synthesis of poly(styrene‐co‐4‐vinylpyridine) microparticles was successfully carried out, and the latexes had a spherical morphology with good monodispersity. The degree of conversion in the early stage of polymerization decreased with increasing 4‐vinylpyridine (4VP) monomer content, but the final conversions were similar (>95%). The copolymerization rate decreased with increasing 4VP content, and a broad particle size distribution was observed with 20 wt % 4VP because of the prolonged nucleation time. With the 4VP concentration increasing, the molecular weight of the copolymer microspheres decreased, and the glass‐transition temperature of the copolymers increased; this indicated that all the copolymers were random and homogeneous. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compatibilization of polystyrene and polyamide 6 mixtures with poly(styrene‐co‐sodium acrylate)

In this work, the compatibilization of polystyrene‐and‐nylon 6 mixtures with the ionomer, poly(styrene‐co‐sodium acrylate), is investigated. The ionomer was synthesized by emulsion polymerization. Scanning electron microscopy reveals that an appreciable size reduction of the dispersed phase is achieved in the whole composition range, when small amounts of the ionomer were added. IR spectroscopy and water absorption tests disclose that a chemical reaction occurs between the carboxylic group of the ionomer and the terminal amine group of the polyamide 6, which allows the compatibilization process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:1736–1745, 2004     

Water absorption and hygrothermal aging study on organomontmorillonite reinforced polyamide 6/polypropylene nanocomposites

The water absorption and hygrothermal aging behavior of organomontmorillonite (OMMT) reinforced polyamide 6/polypropylene (PA6/PP ratio = 70/30), with and without maleated PP (MAH‐g‐PP), was studied at three different temperatures (30, 60, and 90°C). The water absorption and hygrothermal aging response of the composites was studied and analyzed by tensile tests and morphology assessment (scanning electron microscopy and transmission electron microscopy), indicating the effect of the immersion temperature, OMMT, and MAH‐g‐PP compatibilizer. The mathematical treatment used in analyzing the data was the single free phase model of diffusion, which assumed Fickian diffusion and utilized Fick's second law of diffusion. The kinetics of water absorption of the PA6/PP nanocomposites conformed to Fickian law behavior, whereby the initial moisture absorption follows a linear relationship between the percentage gain at any time t and t^1/2 (the square root of time), followed by saturation. It was found that the equilibrium moisture content and the diffusion coefficient are dependent on the OMMT loading, MAH‐g‐PP concentration, and immersion temperatures. Both the tensile modulus and strength of the PA6/PP nanocomposites deteriorated after being exposed to hygrothermal aging. MAH‐g‐PP acted as a good compatibilizer for PA6/PP/OMMT nanocomposites, which was attributed to its higher retention ability in modulus and strength (in the wet and redried states), lower equilibrium moisture content, and reduced water diffusivity of the nanocomposites. Morphological sketches for both uncompatibilized and MAH‐g‐PP compatibilized PA6/PP/OMMT nanocomposites, toward water uptake are proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 780–790, 2005