Polyamide 6/ethylene‐butylene elastomer blends generated via anionic polymerization of ε‐caprolactam: Phase morphology and dynamic mechanical behavior

This paper reports about the polymerization of ε‐caprolactam monomer in the presence of low molecular weight hydroxyl or isocyanate end‐capped ethylene‐butylene elastomer (EB) elastomers as a new concept for the development of a submicron phase morphology in polyamide 6 (PA6)/EB blends. The phase morphology, viscoelastic behavior, and impact strength of the polymerization‐designed blends are compared to those of similar blends prepared via melt‐extrusion of PA6 homopolymer and EB elastomer. Polyamide 6 and EB elastomer were compatibilized using a premade triblock copolymer PA6‐b‐EB‐b‐PA6 or a pure EB‐b‐PA6 diblock reactively generated during melt‐blending (extrusion‐prepared blends) or built‐up via anionic polymerization of ε‐caprolactam on initiating ? NCO groups attached to EB chain ends (polymerization‐prepared blends). Two compatibilization approaches were considered for the polymerization‐prepared blends: (i) the addition of a premade PA6‐b‐EB‐b‐PA6 triblock copolymer to the ε‐caprolactam monomer containing nonreactive EB? OH elastomer and (ii) generation in situ of a PA6‐b‐EB diblock using EB? NCO precursor on which polyamide 6 blocks are built‐up via anionic polymerization of ε‐caprolactam. The noncompatibilized blends exhibit a coarse phase morphology, either in the extruded or the polymerization prepared blends. Addition of premade triblock copolymer (PA6‐b‐EB‐b‐PA6) to a EB? OH /ε‐caprolactam dispersion led to a fine EB phase (0.14 μm) in the PA6 matrix after ε‐caprolactam polymerization. The average particle size of the in situ reactively compatibilized polymerization‐prepared blend is about 1 μm. The notched Izod impact strength of the blend compatibilized with premade triblock copolymer was much higher than that of the neat PA6, the noncompatibilized, and the in situ reactively compatibilized polymerization blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2538–2544, 2004     

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     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

A new macroinitiator for the synthesis of triblock copolymers PA12‐b‐PDMS‐b‐PA12

A new PDMS macroinitiator is proposed for the anionic ring‐opening polymerization of lactams. This α,ω‐dicarbamoyloxy caprolactam PDMS macroinitiator was readily obtained in quantitative yield, by an original synthesis scheme in two steps, which involved the scarcely reported reaction of isocyanates with silanol groups. It was then shown that this bifunctional macroinitiator enabled to synthesize triblock copolymers PA12‐b‐PDMS‐b‐PA12 by polymerization of lauryl lactam (LL) at high temperature (200°C) in inert atmosphere under conditions compatible with reactive extrusion processes. Another related high molar weight α,ω‐diacyllactam PDMS macroinitiator was also successfully used in the polymerization of LL under the same conditions, therefore overcoming the limitations formerly reported for this type of macroinitiators during the polymerization ε‐caprolactam (ε‐CL) at a much lower temperature (80°C). Triblock copolymers with a wide range of PA12 /molar weights (M_n: ～ 10,800–250,000 Da) were eventually obtained by using both types of macroinitiators. DMTA and DSC analyses showed that their thermal properties were strongly dependent upon their respective contents in soft and hard blocks. Such triblock copolymers already appear very promising for the highly effective in situ compatibilization of PA12/PDMS blends as shown by recent complementary results obtained in our laboratory. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2818–2831, 2006     

Properties of anionic polymerized ε‐caprolactam in the presence of carbon nanotubes

The results of the investigations of the relations between structure, physical and usage properties of polyamide 6 (PA6) reinforced with multiwall carbon nanotubes (MWNTs) are presented. A method of in situ anionic bulk polymerization of ε‐caprolactam in the presence of MWNTs was used for the preparation of reinforced PA6. The polymerization product was crushed, and the pellets of PA6 and PA6/MWNTs composites were injection molded to produce the standard test specimens for various measurements. The surface morphology (SEM), thermal (DSC, TGA, DMTA), and mechanical properties (tensile strength, Charpy's notched impact strength) of these materials were examined. Some differences between our specimens and those obtained by hydrolytic polymerization of ε‐caprolactam (CL) were found. It was found that a small amount of carbon nanotube decreases the crystallinity degree of PA6 matrix in the composites. The thermal stability was higher than that for neat PA6. DMTA results showed that the magnitudes of the storage modulus are higher for the PA6/MWNTs composites than for the unmodified PA6 in the temperature range between ?90 and 200°C. The tensile strength and tensile modulus are higher compared with the neat PA6. The elongation at break showed no noticeable change in the range of MWNTs loading considered, while the Charpy's notched impact strength slightly decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization and thermal dissociation of 2‐butoxyethanol‐blocked diisocyanates and their use in the synthesis of isocyanate‐terminated prepolymers

A series of blocked diisocyanates has been synthesized from toluene diisocyante (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′‐diphenylmethane diisocyanate (MDI) and 2‐butoxyethanol. The synthesis of blocked diisocyanate adducts was confirmed by Fourier transform infrared, ¹H NMR, electron impact mass spectrometry and nitrogen analysis. Differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and carbon dioxide evolution were used to determine the minimum de‐blocking temperatures. De‐blocking temperatures determined by these three techniques were found to be in the order DSC > TGA > CO₂ evolution. The effect of different metal catalysts on thermal de‐blocking reaction of the blocked diisocyanates was studied, using the carbon dioxide evolution method. It was found that iron(III) oxide has the maximum catalytic activity on de‐blocking. The solubility of the blocked diisocyanate adducts was determined in different solvents. The study revealed that at 30 °C blocked IPDI and HDI adducts show better solubility than adducts based on TDI and MDI. Isocyanate‐terminated prepolymers of blocked diisocyanates and hydroxyl‐terminated polybutadiene (HTPB) were prepared. The storage stability and gelation times of the prepolymers were studied. Results showed that all the diisocyanate‐HTPB compositions are stable at 50 °C for more than three months. However, aliphatic diisocyanate‐HTPB compositions require greater gelation time than aromatic diisocyanate‐HTPB compositions at their respective de‐blocking temperatures. Copyright © 2007 Society of Chemical Industry     

Effects of the polybutadiene/poly(styrene‐co‐acrylonitrile) ratio in a polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) impact modifier on the morphology and mechanical behavior of acrylonitrile–butadiene–styrene blends

Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005     

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     

Synthesis of sub‐micrometer core–shell rubber particles with 1,2‐azobisisobutyronitrile as initiator and deformation mechanisms of modified polystyrene under various conditions

BACKGROUND: Sub‐micrometer core‐shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) copolymers with various ratios of polybutadiene (PB) core to polystyrene (PS) shell were synthesized by emulsion grafting polymerization with 1,2‐azobisisobutyronitrile (AIBN) as initiator. These graft copolymers were blended with PS to prepare PS/PB‐g‐PS with a rubber content of 20 wt%. The mechanical properties, morphologies of the core‐shell rubber particles and deformation mechanisms under various conditions were investigated. RESULTS: Infrared spectroscopic analysis confirmed that PS could be grafted onto the PB rubber particles. The experimental results showed that a specimen with a ‘cluster’ dispersion state of rubber particles in the PS matrix displayed better mechanical properties. Transmission electron micrographs suggested that crazing only occurred from rubber particles and extended in a bridge‐like manner to neighboring rubber particles parallel to the equatorial plane at a high speed for failure specimens, while the interaction between crazing and shear yielding stabilized the growing crazes at a low speed in tensile tests. CONCLUSION: AIBN can be used as an initiator in the graft polymerization of styrene onto PB. The dispersion of rubber particles in a ‘cluster’ state leads to better impact resistance. The deformation mechanism in impact tests was multi‐crazing, and crazing and shear yielding absorbed the energy in tensile experiments. Copyright © 2009 Society of Chemical Industry     

Micro‐ and macrophase separation of thermosetting systems modified with epoxidized styrene‐block‐butadiene‐ block‐styrene linear triblock copolymers and their influence on final mechanical properties

BACKGROUND: The goal of this work was to establish the minimum degree of epoxidation needed to develop nanostructured epoxy systems by modification with poly(styrene‐block‐butadiene‐block‐styrene) (SBS) triblock copolymers epoxidized to several degrees, and also to investigate the effect of polystyrene (PS) content on the final morphologies. By using two SBS copolymers, the influence of the weight ratio of the two blocks on the generated morphologies and mechanical properties was also analysed. RESULTS: Nanostructured thermosets were effectively obtained through reaction‐induced microphase separation of PS blocks from the matrix. A minimum of 27 mol% of epoxidation, which corresponds to 4.8 wt% of epoxidized polybutadiene (PB) units in the overall mixture, was needed to ensure nanostructuring of final mixtures and thus their transparency. Hexagonally ordered nanostructures were achieved for PS contents of around 16–20 wt%, which agrees with our previous results for mixtures with other SBS copolymers with different ratios between blocks. The fracture toughness of the epoxy matrix was improved or at least retained with mixing. CONCLUSION: The degree of epoxidation of PB blocks needed to switch epoxy/SBS mixtures from a macrophase‐separated to a nanostructured state has been established. The generated morphologies in the epoxy systems are mainly dependent on the PS content in the mixture. Copyright © 2008 Society of Chemical Industry     

Effect of maleic anhydride grafted polybutadiene on the compatibility of polyamide 66/acrylonitrile‐butadiene‐styrene copolymer blend

The addition of maleic anhydride grafted polybutadiene (PB‐g‐MAH) can greatly improve the compatibility of polyamide 66 (PA66)/acrylonitrile‐butadiene‐styrene copolymer (ABS) blends. Unlike the commonly used compatibilizers in polyamide/ABS blends, PB‐g‐MAH is compatible with the ABS particles' core phase polybutadiene (PB), rather than the shell styrene‐acrylonitrile (SAN). The compatibility and interaction of the components in the blends were characterized by Fourier transform‐infrared spectra (FTIR), Molau tests, melt flow index (MFI), dynamic mechanical analyses (DMA), and scanning electron microscopic (SEM) observations. The results show that PB‐g‐MAH can react with the amino end groups in PA66 while entangle with the PB phase in ABS. In this way, the compatibilizer anchors at the interface of PA66/ABS blend. The morphology study of the fracture sections before and after tensile test reveals that the ABS particles were dispersed uniformly in the PA66 matrix and the interfacial adhesion between PA66 and ABS was increased significantly. The mechanical properties of the blends thus were enhanced with the improving of the compatibility. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Polyurethane ionomer dispersions from a blocked aromatic‐diisocyanate prepolymer

Aqueous anionic blocked aromatic polyurethane prepolymers were synthesized by a prepolymer mixing process and their dispersions were obtained by adding water to the blocked prepolymer solutions. A series of prepolymers were prepared by using toluene 2,4‐diisocyanate, 4,4′‐diphenylmethane diisocyanate, polytetramethylene glycol, dimethylol propionic acid, methyl ethyl ketoxime and ε‐caprolactam. The aqueous dispersions were characterized by Fourier‐transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The particle sizes, viscosities, pH and storage stabilities of the dispersions were studied and compared. Some mechanical properties of the cast films obtained from the aqueous dispersions and the adhesive properties of the dispersions were also evaluated. Copyright © 2004 Society of Chemical Industry     

Effects of molecular weight on the dynamic mechanical and rheological properties of anionically polymerized polyamide 6 containing nanofiber

Anionic ring‐opening polymerization of ε‐caprolactam leads to the formation of polyamide 6 (PA6). This reaction takes place at a significantly faster rate and gives a narrower molecular‐weight distribution than those obtained with other techniques. Because of this advantage, anionic polymerization of PA6 during melting was investigated in this work. In an internal mixer, PA6 was prepared via the melt polymerization of ε‐caprolactam as monomer with sodium caprolactam as a catalyst and hexamethylene diisocyanate as an activator. The effects of various concentrations of catalyst and activator on the rate of reaction and the amount of residual monomer were determined. Also, the physical and mechanical properties of PA6 prepared in this way and commercial PA6 prepared via hydrolytic processing were determined by differential scanning calorimetry and dynamic mechanical thermal analysis, as well as tensile, impact, and rheological tests. The experimental results showed that the composition which included 3% of catalyst and 3% of activator gave better properties than the other formulations. These conditions led to the lowest residual monomer content and better mechanical properties, as well. Another novel aspect of this investigation was nanofiber formation during the melt polymerization. The nanofibers had lower molecular weights than the matrix and thus created a special crystal structure different from that of the matrix. Mechanical property measurements showed that PA6 prepared by using this technique and the aforementioned formulation was similar to the commercial PA6. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Preparation and properties of polyamide‐6‐based thermoplastic laminate composites by a novel in‐mold polymerization technique

In this work, a method for preparation of polyamide‐6 (PA6) based laminates reinforced by glass fiber‐ (GFL) or polyamide‐66 (PA66) textile structures (PL) via reactive injection molding is disclosed. It is based on in‐mold anionic polymerization of ε‐caprolactam carried out at 165°C in the presence of the respective reinforcements performed in newly developed prototype equipment whose design concept and operation are described. Both composite types were produced for reaction times of 20 min, with conversion degrees of 97–99%. Initial mechanical tests in tension of GFL samples displayed almost twofold increase of the Young's modulus and stress at break values when compared with the neat anionic PA6. The improvement was proportional to the volume fraction V_f of glass fiber fabric that was varied in the 0.16–0.25 range. A 300% growth of the impact strength was registered in PL composites with V_f of PA66 textile of 0.1. Removing the surface finish of the latter was found to be a factor for improving the adhesion at the matrix–fiber interface. The mechanical behavior of GFL and PL composites was discussed in conjunction with the morphology of the samples studied by optical and electron microscopy and the matrix crystalline structure as revealed by synchrotron X‐ray diffraction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40083.     

Preparation and characterization of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring‐opening polymerization of ϵ‐caprolactam

The blends of thermoplastic polyether‐based urethane elastomer (TPEU) and monomer casting polyamide 6 (MCPA6) were prepared using ε‐caprolactam (CL) as a reactive solvent, and CL sodium as a catalyst at various TPEU contents (2.5–15 phr by weight). In situ anionic ring‐opening polymerization and in situ compatibilization of TPEU/MCPA6 blends were realized in one step. The dissociated TPEU chains acted as macroactivator to initiate MCPA6 chain growth from the TPEU chains. The formed block copolymers (TPEU‐co‐MCPA6), which have been confirmed by Fourier transform infrared spectroscopy and ¹H‐NMR analysis, improved the compatibility between TPEU and MCPA6. In addition, both differential scanning calorimetry and dynamic mechanical analysis studies revealed that the crystallinity temperature, melting temperature, the degree of crystallization, and the glass‐transition temperature of MCPA6 component remarkably shifted to a low temperature with increasing TPEU content. Mechanical properties demonstrated that the impact strength and the elongation‐at‐break of the blends significantly increased with the content of TPEU, whereas a progressive decrease occurred in tensile strength, flexural strength, and flexural modulus. WAXD spectra showed that only α‐form crystal of PA6 component existed in the TPEU/MCPA6 blends. Furthermore, scanning electron microscopes (SEM) of the cryo‐fractured surfaces confirmed a substantially improved compatibility, and reflected a seemly single‐phase morphology. POLYM. ENG. SCI., 46: 1196–1203, 2006. © 2006 Society of Plastics Engineers     

Synthesis of polyamide 6/11 copolymers and their use as matrix polymer in wood‐plastic composites

The goal of this study was to investigate the synthesis and the resulting thermal, rheological, and mechanical properties of polyamide 6/11 copolymers (PA 6/11) as a function of their composition and to further investigate their usability as matrix polymers for wood‐plastic composites (WPC). A significant composition dependency of the melting temperature was found due to the hindered crystallization of the PA 6/11 copolymers with increasing content of the minor component. In result, the lowest melting temperature of the copolymers was measured at 120 °C for 40 wt % of ?‐caprolactam (PA 6/11‐40/60) by DSC analysis. Due to its low melting point and feasible mechanical properties, a copolyamide with 70 wt % of ?‐caprolactam (PA 6/11‐70/30) was chosen as matrix material for the processing of WPC. Incorporation of 30 wt % of wood fibers into PA 6/11‐70/30 caused a significant increase in tensile modulus and a decrease in tensile strength and strain at break. However, the processed WPC still showed an exceptional ductility with a strain at break of 15 to 20%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44155.     

Rapid FTIR method for quantification of styrene‐butadiene type copolymers in bitumen

The mid‐IR molar absorptivity for polystyrene (PS) and polybutadiene (PB) blocks were obtained for five styrene‐butadiene‐styrene (SBS) and SB copolymers, including linear, branched, and star copolymers, and their blends with bitumen. The average absorptivity for PS and PB blocks was 277 and 69 L mol⁻¹ cm⁻¹ and it was little affected by the S/B ratio or the copolymer architecture. In the presence of bitumen, Beer's law was obeyed but the respective PS and PB absorptivity was 242 and 68 L mol⁻¹ cm⁻¹, possibly because of weak interactions between the copolymer and bitumen. The absorptivity values were used to calculate the concentration of SB‐type copolymers in blends with bitumen with an accuracy of 10% or better. The method can be used to probe the stability of bitumen–copolymer blends in storage at 165°C, to determine the copolymer concentration in commercial polymer modified bitumen (PMB), and to assess the resistance of PMB to weathering. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1034–1041, 2001     

Dually reinforced all‐polyamide laminate composites via microencapsulation strategy

A new two‐stage strategy is disclosed for the preparation of all‐polyamide laminate composites based on polyamide 6 (PA6) matrices reinforced by high volume fractions of polyamide 66 (PA66) textile structures and three different types of nanoclays. In the first stage, PA6 microcapsules (MC) loaded with montmorillonite nanoclays (MMT) are synthesized by activated anionic ring‐opening polymerization of ε‐caprolactam in solution in the presence of three different organically treated MMT brands. In the second stage, the MMT‐loaded MC obtained with controlled molecular weight, composition and granulometry are compression molded in the presence of PA66 textile structures to produce the final dually reinforced laminate composites. Mechanical tests in tension, flexion, and impact for selected composites in this study showed up to 73% increase of the Young's modulus, up to 142% increase of the stress at break, and more than a fivefold increase of the notched impact resistance. The mechanical behavior of the dually reinforced composites was discussed in conjunction with the morphology of the samples studied by optical and electron microscopy, and the matrix crystalline structure as revealed by DSC and microfocus synchrotron X‐ray diffraction. POLYM. ENG. SCI., 57:806–820, 2017. © 2016 Society of Plastics Engineers     

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     

Tracer‐compatibilizer: Synthesis and applications in polymer blending processes

This article reports on a route to synthesizing fluorescent labeled graft copolymers, on the one hand; and on a concept of tracer‐compatibilizer for facile build‐up of emulsification curves of polymer blends, on the other hand. For these purposes, blends composed of polystyrene (PS) and polyamide 6 (PA6) are chosen. The synthesis of the corresponding tracer‐compatibilizer consists of three steps: (1) copolymerization of styrene with 3‐isopropenyl‐α,α'‐dimethybenzyl isocyanate (TMI); (2) conversion of a fraction of the isocyanate moieties of the resulting copolymer into anthracene ones upon reacting with 9‐(methylamino‐methyl)anthracene (MAMA); and (3) polymerization of ε‐caprolactam (CL) from the remaining isocyanate moieties. The resulting fluorescent labeled graft copolymer, denoted as PS‐g‐PA6‐Ant, is used to build up emulsification curves of PS/PA6 blends in a twin screw extruder (TSE), showing great usefulness of the concept of tracer‐compatibilizer. POLYM. ENG. SCI. 2012. © 2011 Society of Plastics Engineers