A facile synthesis of aliphatic polybenzoxazoles from a bis(o-aminophenol) or its hydrochloride and aliphatic dinitriles

A facile one-step method for the synthesis of aliphatic polybenzoxazoles has been developed. Thus, a series of aliphatic polybenzoxazoles having inherent viscosities of 0.2–0.7 dL/g in concentrated sulfuric acid were successfully synthesized by the melt polycondensation of alipatic dinitriles with 4,4′-diamino-3,3′-dihydroxybiphenyl (AHB) or its hydrochloride (AHB–HCl) with the elimination of ammonia or ammonium chloride, respectively. Monomer AHB–HCl was more reactive than the parent AHB, thereby affording higher molecular weight polybenzoxazoles in a shorter reaction time. The aliphatic polybenzoxazoles having 6–10 methylene units were highly crystalline with melting temperatures in the range of 187–308°C, which were stable up to 400°C in a melt state in nitrogen. © 1994 John Wiley & Sons, Inc.     

Purification by solid layer melt crystallization

The application of solid layer crystallization techniques in industry is arousing ever more interest. One reason is the increasing demand for ultrapure products, and another is the energysaving potential of this separation technology.This article examines solid layer melt crystallization as concerns its purification efficiency. The crystallization process was carried out in two different modes, whereby the process parameters were varied and post-crystallization treatments were additionally applied. The experimental results were used as the basis for a mathematical fit of a semi-empirical expression which predicts the purification efficiency. It was used for a design of different multistage plants, which operate with different crystallization strategies. One result is that a comparable product quality is attainable with a simple process technique in combination with post-crystallization treatments, instead of a more complicated and therefore more expensive process technique.The authors wish to acknowledge support by the EU (JOULE program), which helped attainment of some results presented here.     

Formation of Iron Macro-Spheres in Plasma

In this paper the formation mechanism of iron macro-spheres in a plasma medium is dealt with, including the conditions under which such spheres are formed. The geometry of the spheres referred to above depends on the main technological parameters involved in the production of pores. Conditions under which pores occur within macro-spheres are also established. The radii of these pores are sensitive to the velocity distribution within the plasma jet section     

Studies on the thermotropic liquid crystalline polycarbonates. III. Synthesis and properties of fully aromatic liquid crystalline polycarbonates

Four series of fully aromatic thermotropic liquid crystalline polycarbonates were prepared by melt polycondensation from various novel phenylene diphenyl dicarbonates with monomers, such as hydroquinone, methylhydroquinone, chlorohydroquinone, resorcinol, bisphenol A, 4,4′-dihydroxydiphenylsulfone, or phenylhydroquinone, respectively. The thermotropic liquid crystalline properties were studied by polarizing microscope with a heating stage, differential scanning calorimeter (DSC), and wide-angle x-ray diffraction (WAXD). It was found that the nonlinearity of the carbonate group was compensated by resorcinol (1,3-phenylene unit), a bent shape unit. Nematic melts were found for the resulting polycarbonates. © 1993 John Wiley & Sons, Inc.     

Development in the area of UV-crosslinkable solvent-based pressure-sensitive adhesives with excellent shrinkage resistance

Solvent-based UV-crosslinkable pressure-sensitive adhesives (PSA) present a new class of products that offers the potential to produce a novel generation of ultraviolet cured self-adhesive products with excellent shrinkage resistance. A variety of solvent-based pressure-sensitive adhesives were prepared by synthesis in ethyl acetate with solid content on 50 wt.% with 2-ethylhexyl acrylate, methyl acrylate, acrylic acid, N-vinyl caprolactam and unsaturated photoinitiators: 4-acryloyloxy benzophenone, allyl benzoine and phenyl-(1-acryloyloxy)-cyclohexyl ketone. The main emphasis is given to the influence of viscosity and molecular mass of synthesized adhesive on their shrinkage. Further trials show the effect of the UV-crosslinking process with UV-lamp and comparison with acrylics PSA crosslinked with metal chelates aluminium acetylacetonate and titanium acetylacetonate on shrinkage. Further examinations describe the influence of various factors such as UV exposure time and UV dose on very relevant PSA performance such as shrinkage on coated PVC carrier.     

Description of the Structure and Properties of Atactic Polystyrene Melt Using Integral Equation Theory

The polymer reference interaction site model （PRISM） integral equation theory was used to describe the structure and thermodynamic properties of atactic polystyrene （aPS） melt, in which the monomer of aPS is represented with an eight-site model to characterize its microstructure. The intramolecular structure factors needed in the PRISM calculations were obtained from single chain MD simulations. The calculated results indicate that the results by the integral equation method agrees well with experiments, and can reflect the fine microscopic structure of real aPS melt. This work shows that the PRISM theory is a powerful tool for investigating the structure and properties of complex polymers.     

EFFECTS OF COUPLING AGENTS ON THE CRYSTALLIZATION BEHAVIOR OF PP/T-ZnOw COMPOSITES

The objectives of this paper are to understand the crystallization behavior of polypropylene(PP)composites with surface modified tetra-needle-shaped zinc oxide whisker(T-ZnOw).T-ZnOw was surface modified with different coupling agents,such as silane coupling agents(KH-550,KH-560)and titanate coupling agent(NDZ-105),in order to improve the compatibility between PP and T-ZnOw.DSC and POM were used to characterize the melt and crystallization behavior and the crystalline structures of the composites,respectively.The results show that the surface modified T-ZnOw acts as a nucleating agent of PP crystallization,depending on the coupling agent used for modification.KH-550 and KH-560 have more apparent role in improving the interfacial interaction than NDZ-105 and induce PP crystallization at higher temperature and with smaller spherulites size.The results also suggest that the crystallization behavior depends on not only the content of coupling agent,but also the content of the surface modified T-ZnOw used in the composites.     

新型尼龙214,414,614,814,1014和1214的合成与表征

用熔融缩聚法基于十四碳二酸合成了一系列偶偶尼龙，包括尼龙2 14，4 14， 6 14，8 14，10 14，12 14。用红外光谱、元素分析、核磁共振、差示扫描热分析 、热失重分析、热机械分析、粘度法对合成尼龙的结构与性能进行了表征。同时还 初步研究了尼龙12 14的物理性能，发现其物理性能介于尼龙66和聚乙烯之间。     

Exchange reactions occurring through active chain ends: Melt mixing of nylon 6 and polycarbonate

The chemical reactions occurring in the melt mixing of nylon6/polycarbonate (Ny6/PC) at 240°C were investigated. The reaction of equimolar Ny6/PC blends can be reconciled within the overall scheme of an exchange reaction occurring with the attack of active amino terminals on the inner carbonate groups. We have performed the synthesis of low molecular weight amino-terminated nylon 6 and the effect of the active amino terminal groups on the exchange kinetics was investigated. The exchange reaction yields sizeable amounts of copolymer, in fact after 75 min of melt mixing the (initially equimolar) blend contains 30 mol of unreacted PC and 70 mol of Ny6/PC copolymer (all the Ny6 was therefore incorporated in the copolymer). Trifluoroacetylation of nylon 6 was used to produce CHCl₃-soluble Ny6/PC copolymers, that could be analyzed by NMR. The NMR analysis yielded, beside the copolymer composition, evidence of the presence of urethane units interconnecting the Ny6 and PC blocks. The amount of urethane units increased with the reaction time, indicating a reduction of the block size as a function of the extent of exchange. Our study established the structure of the products formed, provided the materials balance of the process, and investigated some salient kinetic aspects. A thermal degradation study was also performed by thermogravimetry and direct pyrolysis mass spectrometry, to identify the products formed in the thermal treatment of the blends and to investigate the possible role of the inner amide groups in the intermolecular exchange reactions occurring between Ny6 and PC. Our results prove that these reactions occur above 300°C, and that only the cleavage of carbonate groups, by means of Ny6 amino end groups, is actually occurring at 240°C. © 1994 John Wiley & Sons, Inc.     

Stereoblock poly(lactic acid): synthesis via solid-state polycondensation of a stereocomplexed mixture of poly(L-lactic acid) and poly(D-lactic acid)

Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time.