Flame retardant polyamide 6 by in situ polymerization of ε-caprolactam in the presence of melamine derivatives

An improved method for preparing melamine cyanurate （MCA） based flame retardant polyamide 6 （FRPA6） materials has been proposed. This processing method, i.e., improved in situ polymerization, was used to synthesize flame retardant PA6. In situ formed MCA nanoparticles were supposed to be linked to PA6 chains in the ε-caprolactam hydrolytic polymerization system to obtain startype polymers for the first time. Through TEM photographs, it can be found that the in situ formed MCA nanoparticles with diametric size of less than 50 nm, are nanoscaled, highly uniformly dispersed in the PA6 matrix. Synthesized flame retardant PA6 have good fire performance which can achieve UL-94 V-0 rating at 1.6 mm thickness with the presence of 7.34 wt.% MCA in the matrix.

Depolymerization of polyamide 6 in hydrophilic ionic liquids

Polyamide 6 underwent an efficient depolymerization in hydrophilic ionic liquids under microwave irradiation at 300C. The depolymerization completed within 60 min. Caprolactam was readily separated by simple extraction procedure and the ionic liquids were recovered and reused for several times. Addition of catalytic amounts of DMAP(N,N-dimethylaminopyridine) promoted the depolymerization effectively.The present improved procedure provides a method to avoid direct distillation procedure, which consumes energy for the separation of caprolactam from ionic liquids. Although some contamination of ionic liquids was observed, the present procedure provides a new possibility for the use of ionic liquids for plastic chemical recycling from the viewpoint of development of an energy-saving methodology. Use of solubility switchable ionic liquids is also examined to explore a possibility for better separation although depolymerization did not work well.

HEAT-RESISTANT,PYRIDINE-BASED POLYAMIDES CONTAINING ETHER AND ESTER UNITS WITH IMPROVED SOLUBILITY

A diamine containing ether and ester units, as basic monomer for the preparation of polyamides, was prepared via three consecutive reactions. Nucleophilic substitution reaction of 1,4-dihydroxy benzene with 4-nitrobenzoyl chloride produced 4-hydroxyphenyl 4-nitrobenzoate （HPNB）. Reduction of nitro groups to amino groups using Fe and HC1 resulted in preparation of 4-hydroxyphenyl 4-aminobenzoate （HPAB）. The diamine was synthesized through nucleophilic substitution reaction of HPAB with 2,6-dichloropyridine. The precursors and diamine were fully characterized by common methods, and the diamine was polycondensed with different diacid chlorides in the presence of an acid scavenger to prepare new polyamides. The polyamides were characterized, and their physical properties including thermal stability and behavior, inherent viscosity and solubility were studied.

Synthesis and Characterization of Long Chain Semiaromatic Polyamides based on Undecanediamine

Long chain semiaromatic polyamides with high molecular weight were synthesized by the reactions of undecanediamine with various aromatic diacids,and characterized by fourier transform infrared spectra（FT-IR） and nuclear magnetic resonance（1H-NMR）.The thermal behaviors were determined by differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA）.The solubility,dynamic mechanical,physical and mechanical properties of the polyamides were also investigated.The experimental results show that the polyamides with high molecular weights are obtained only the PH value of the polyamides salt are in the range of 7.2-7.4.The melting temperatures and the glass transition temperatures of the polyamides increase with the increase of the rigidity of aromatic diacids,and are near to those of poly（nonamethylenetere-phthalamide）（PA9T）.

Miscibility of Semi-flexible Thermotropic Liquid Crystalline Copolyesteramide with Polyamide 66

Liquid crystalline polymer-polyamide 66 (LCP/PA66) blends were compounded by using a Brabender mixing followed by compression moulding. The LCP employed was a semi-flexible liquid crystalline copolyesteramide based on 30% (molar fraction ) of p-amino benzoic acid (ABA ) and 70% (molar fraction) of poly (ethylene terephthalate) (PET). The LCP/PA66 blends were investigated in terms of the thermal and dynamic mechanical properties. It was found that PA66 and LCP components of the blends are miscible in the molten state, but are partially miscible in the solid state. The inclusion of the semi-flexible LCP into PA66 retards the crystallization rate of PA66. Furthermore, the melting temperature and the degree of crystallinity of PA66 are reduced considerably due to the LCP addition.

In-situ Composite Based on Poly (ethylene terephthalate),Polyamide and Polyethylene with Microfibres Formed through Extrusion and Hot Stretching

In-situ composites based on dispersed poly (ethylene terephthalate) (PET) or polyamide (PA), and continuous polyethylene (PE) were prepared through a single screw extruder of Haake rheometer system with a rod-die relatively small in diameter. The extrudate was drawn at a drawing ratio of 3.1, and then quickly cooled in cold water. The specimens were obtained by injection molding at processing temperatures less than 190℃, far below the melting temperature of PET (265℃) and PA (230℃), which can maintain the solid state of PET and PA microfiber phase in the composites. Morphological observation with scanning electron microscopy (SEM) indicated that PET and PA can more or less form in-situ microfibers at compositions studied (0~20 wt pct PET or PA), and especially, PET and PA were almost deformed into fibers at the concentration of 15 wt pct. Tensile strength and modulus of the blends reinforced by PET or PA microfibers showed to be increased from the tensile test results. The most noticeable improvement of the tensile properties occurred at 15 wt pct of PET in PET/PE system, corresponding to the highest microfiber content, where the tensile strength reached 32.5 MPa, whereas only 19.5 MPa for the pure PE.

Synthesis of a hypocrellin B-polyamide conjugate as DNA-targeting photosensitizer

A new hypocrellin B （HB） derivative bearing a bispyrrolecarboxamide-containing side chain was synthesized, which presents improved absorptivity in phototherapeufic window than HB and affinity feature towards dsDNA.

PREPARATION AND CHARACTERIZATION OF POLYAMIDE 11/CLAY NANOCOMPOSITES

Polyamide 11 (PA 11) is a widely used polyamide resin, but its application is limited since the impact properties, tensile strength, and thermal properties are not very satisfactory for industrial application. In order to improve the mechanical properties of PA 11, in this paper, the preparation of polyamide 11/clay nanocomposites (PACN) via in-situ intercalated polymerization was reported. SEM, TEM and XRD were employed to investigate the dispersion of clay sheet in the matrix. The results indicate that clay layers were homogeneously dispersed in PA11 matrix on a nano-scale, and an exfoliated and intercalated structure co-existed in the composites. The mechanical and thermal properties of the obtained nanocomposites were improved to certain extent by the addition of clay.

Non-isothermal Crystallization Kinetics of Polyamide 6/Diaminemodified MWNTs Nanocomposite

The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.

Microstructure of Selective Laser Sintered Polyamide

The selective laser sintering (SLS) was used to prepare components from modified polyamide (PA) powder.The behaviour of the sintering process was analyzed.The influences of the fill laser power,powder bed temperature and powder thickness were discussed in detail.By means of SEM,the morphology and the heat influence were analyzed.Results show that the powders were fused thoroughly which allowed a more dense structure to be built at a powder bed temperature of 98℃,fill laser power of 12W,slice thickness of 0.10mm and a default scanning speed of 1700mm/s.

Synthesis of organosoluble polyamides with bulky triaryl imidazole pendent group

New unsymmetrical diamine monomer containing triaryl imidazole pendent group, 4-[4-（4,5-diphenyl-1H-imidazol-2-y1）phe- noxy]-1,3-benzenediamine, was synthesized via aromatic substitution reaction of 1-chloro-2,4-dinitrobenzene with 4-（4,5- diphenyl-1H-imidazol-2-y1）pbenol, followed by palladium-catalyzed hydrazine reduction. This new monomer was further confirmed by FT-IR, IH NMR and ^13C NMR. Novel polyamides having pendant triaryl imidazole group were prepared by the phosphorylation polycondensation of four commercially aromatic dicarboxylic acids with the prepared diamine. Inherent viscosities of polyamides were in the range 0.42-0.53 dL/g indicating formation of medium molecular weight polymers. Polyamides exhibited glass-transition temperature （Tg） in the range 236-265 ℃. These polymers are essentially amorphous and were soluble in polar aprotic solvents such as DMF, NMP, DMAc. The 10% weight loss temperatures in air atmosphere, measured by TGA were in the range 350-373 ℃ indicating their good thermal stabilities. ？2009 Mousa Ghaemy. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Development of Clinical Cement of Nanoapatite and Polyamide Composite

A new type of inorganic organic biomimetic bone cement consisting of nano hydroxyapatite and polyamide 66 composite was investigated. This cement can be handled as paste and easily shaped into any contour. Nanoapatite and polyamide composite cement has a reasonable setting time, excellent washout resistance, high mechanical strength and bioactivity, and it is easily handled and shaped, which can be developed as a clinical cement. It can be predicted that nanoapatite/polymer composite cement would be a new trend of biomedical material, showing a promising prospect.

COMPARISON OF POLYAMIDE 66/MONTMORILLONITE NANOCOMPOSITES PREPARED FROM POLYAMIDE 6 AND POLYAMIDE 66 BASED MASTER-BATCHES

Two master-batches,polyamide 66 (PA66)/organo-montmorillonite (OMMT) and polyamide 6 (PA6)/OMMT, prepared by melt compounding with methyl methacrylate (MMA) as co-intercalation agent,have been used to prepare nearly exfoliated PA661montmorillonite (MMT) nanocomposites.The resulting nanocomposites are compared in view of their morphology and properties.Nano-scale dispersion of OMMT is realized in both types of nanocomposites,as revealed by XRD,TEM and Molau tests.PA66/MMT nanocomposites having superior mecha...

INTERFACIAL MOLECULAR DESIGN OF A RIGID- PARTICLE TOUGHENED POLYAMIDE 6 COMPOSITE

The effects of interfacial modifier on the mechanical properties of kaolin-filled polyamide 6 (PA6) have been studied. The interracial interaction between polyamide 6 and kaolin has been character ized by means of infrared spectroscopy (IR) and scanning electron microscopy (SEM). The results show that the role of the interracial modifier lies in forming an elastic interlayer with good adhesion between kaolin and PA 6. A composite with high impact strength, high tensile strength and high elastic modulus can be obtained by inserting the elastic interfacial modifier into the rigid-particle-filled polymer system.

Effect of Magnetic Field on the Friction and Wear of Polyamide Sliding against Steel

The present work discusses the friction and wear of polyamide sliding against steel in the presence of magnetic field. Tests were carried out at dry and oil lubricated steel surfaces. Paraffin and vegetable oils such as almond, castor, corn, glycerine, jasmine, olive and sun flower oils were used as lubricants. The friction coefficient and wear were investigated using pin on disc wear tester. Based on the experimental results, it was found that application of magnetic field on the contact area affected both friction coefficient and wear of polyamide sliding against steel at dry and oil lubricated conditions. Magnetic field decreased friction coefficient. Lubricating the sliding surface by paraffin oil as well as almond, castor, corn, glycerine, jasmine, olive and sun flower oils significantly decreased friction coefficient. Generally, friction coefficient increased with increasing applied load. Dry sliding of polyamide against steel surface showed increased wear with increasing load. The lowest wear values at no magnetic field were displayed by jasmine oil followed by sun flower, almond, olive, castor, corn, glycerine and paraffin oils. Under the application of magnetic field, the lowest wear values were displayed by sun flower oil followed by jasmine, castor, glycerine, olive, paraffin, almond and corn oils. It can be concluded that friction and wear decrease observed at dry sliding can be explained on the basis that presence of magnetic field around the contact area decreased the adherence and transfer of polyamide into the steel surface. For oil lubricated sliding, the polar molecules of the tested lubricating oils were much affected by the magnetic field, where they oriented themselves to the polar end directed towards the sliding surface making a close packed multi-molecular layered surface film that could protect the sliding surfaces from excessive wear.

EFFECTS OF COUPLING AGENTS ON THE RHEOLOGICAL BEHAVIOR OF KAOLIN FILLED POLYAMIDE 6

An experimental study was carried out to investigate the effects of coupling agents on the rheological properties of kaolin filled polyamide 6(PA6). We have investigated the state of dispersion and interfacial interaction of the filled systems, using 'h:anning electron microscopy (SEM) and Molau test, respectively. It is found that the addition of the coupling agents to the PA6/ kaolin (20 wt percent) significantly decreases the melt viscosity and the melt elasticity (first normal stress difference). Moreover, the states of dispersion and the polymer/filler interactions have significant influences on the rheological properties of kaolin/PA6 systems. The rheological behavior of KH550 kaolin /PA6 system is different from that of KH560 kaolin/PA6 system, although chemical reactions have taken place between the surface of KH550 kaolin (or KH560 kaolin) and PA6 matrix during melt processing. This is attributable, in part, to the differences in the state of dispersion of kaolins in PA6 matrix and, to a great extent, to the differences in the extent of chemical reactions that have taken place between the filler and polymer matrix.

Flame Retardant and Pyrolytic Behaviors of Polyamide 6/Montmorillonite Nanocomposite

Na +-montmorillonite(Na +-MMT) was converted to organic montmorillonite(OMMT) using modifier which was synthesized at authors’ laboratory. PA6/OMMT nanocomposite was prepared via in situ intercalative polymerization. The limiting oxygen index (LOI), UL 94V flame retardancy and thermal stability of PA6/OMMT using thermal gravity analysis (TGA) were measured. The Fourier transform infrared (FTIR) technique was used to analyze the pyrolytic residuum and the cone calorimeter (CONE) was applied to determine a number of combustion parameters which were closely related to fire safety, including heat release rate, mass loss rate, effective combustion heat, total heat release, specific extinction area and the time of ignition. In addition, the elemental composition of the surface pyrolytic residuum and the corresponding X-ray photoelectron spectroscopy (XPS) data were obtained, and the morphology of the residuum from CONE measurement was examined by scanning electron microscope (SEM).

Synthesis and Magnetic Properties of Polyamide Complex Containing Bithiazole Moieties

A new polyamide containing bithiazole moieties （PTA） was synthesized by the polycondensation of 2, 2＇-diamino-4, 4＇-bithiazole （DABT） and oxalyl chloride. The polymer complex was prepared from PTA and NdC13 in DMSO. They were characterized through IR and elemental analysis. The preliminary magnetic properties of the complex PTA-Nd^3＋ was investigated, it was found that the material is a ferromagnet at low temperature.

Synthesis and Characterization of Polyamide-Containing 2, 6-(Substituded) pyridine Derivatives

A new series of acyelic aromatic polyamide pyridine derivatives a-h and a new macrocyclic polyamide containing pyridine ring i were synthesized by the reaction of N^2, N^6-his（2-aminoethyl） pyridine-2, 6-dicarboxamide or N^2 , N^6-bis （3-aminopropyl） pyridine-2,6-dicarboxamide with various acyl chloride. The compounds were characterized by MS, ^1H NMR, IR and elemental analysis. The single-crystal structure of g confirmed that the crystal is of triclinic, space group P-1 with Mr = 487.55, α=9.3031（19）, b=12.167（2） , c=126.50（3） nm, α=108.91（3）°, β= 97. 57（3）°, γ=102.07（3）°, Ⅴ= 1 293.5 nm, Z=2, Dc=1. 252 kg/m^3, μ=0. 086 mm^-1, F（000）=516, X-ray analysis reveals that there exist hydrogen bonding and network structure in the crystal.

Crystalline Morphology and Crystallization Characteristics of In-situ Blends of Anionic Polyamide 6 with Noncrystallizable Semiaromatic Polyamide Copolymer

A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of a single loss tangent（tanS） peak measured by means of dynamic mechanical analysis（DMA） proves the miscibility between PA6 and NSAP in the blends. It was found that there existed drastic changes in the crystallographic form and crystallization kinetics for the in-situ blends, e.g. , when 20% NSAP was added, nearly all crystallites existed in the ,y form and the crystallization could hardly occur upon cooling even at a rate of 2.5 ℃/min. Moreover, cold crystallization appears during the subsequent heating, and its melting point is 40 ℃ lower than that of the virgin system. On the other hand, the size of the spherulites only decreases modestly. It is suggested that the introduction of irregular stiff segments originated from NSAP into PA6 macromolecule chain, which resulted from transamidation during the polymerization play a dominant role in the drastic change of crystallization kinetics and the resultant morphology of the in-situ blends.