TRANSESTERIFICATION OF POLY(ETHYLENE TEREPHTHALATE) WITH POLY(ε-CAPROLACTONE)*

Transesterification of poly(ethylene terephthalate) (PET) with poly(ε-caprolactone) (PCL) was investigated bymeans of NMR spectroscopy, extraction experiments, differential scanning calorimetry (DSC) and phase contrast microscopy(PCM). The ~1H-NMR results show that transesterification takes place in the melt blends and leads to the formation of thePET-PCL copolyester with a chemical structure similar to ethylene terephthalate-ε-caprolactonc copolycster (TCL)synthesized directly from monomers. However, even in the blend that has been transesterified for 8 h, the random PET-PCLcopolyester, PET-PCL copolyester with long PET or long PCL segments and the unreacted PET and PCL homopolymersmay coexist. Due to the low mobility of PET and PCL chains and the high viscosity of the two macromolecules, thetransesterification proceeds with difficulty. Furthermore, PET is incompatible with PCL, the transesterification can onlyoccur at the interface or in the interfacial region between two phases, and finally the reaction can only reach a localequilibrium. These results indicate that in fact the transesterification in the melt blend between two incompatiblehomopolymers could not lead to the formation of completely random or typical block copolyesters.     

MOLECULAR WEIGHT DEPENDENCE OF THE MELTING BEHAVIOR OF POLY(ε-CAPROLACTONE)

Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found thatthe equilibrium melting points (T_m~0) of PCL samples depend on their molecular weights. Wide angle X-ray diffractionmeasurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were moreperfect than those of the low molecular weigh ones. These results demonstrate that the concentration of the end groups ofPCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (ΔH_u) wasdetermined to be 11.3 kJ/mol for PCL.     

STUDIES ON MISCIBILITY AND MORPHOLOGICAL FEATURES OF BLENDS OF LC COPOLYESTER AND PET

The morphology of a special blend system composed of liquid crystalline aromatic random copolyester (LCP) and semiflexible polyester PET over the whole composition range has been studied by means of polarized microscope, density measurement, DSC, FTIR and SEM. Based on the microscopic observation, it is found that under suitable mechanical mixing condition, LCP may be rather homogeneously dispersed in the PET matrix, with the middle composition range of the contents of LCP at 30--70 wt % the anisotropic and isotropic phase segregation appears, while with LCP contents over 80 wt% the blends exhibit wholly anisotropie. The DSC thermographs of the melt-pressed and quenched films show single T_(?), T_(cc) and T_m. T_(?) increases with increasing content of LCP and ap, proaches to the T_(?) of pure LCP. The experimental results indicate that the two components of this blend system are miscible, there exist some specific interactions between them.     

RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE BY LANTHANOCENE CATALYSIS*

Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C_2H_4C_5H_3CH_3)_2YCl (Cat-YCl) and Me_2Si[(CH_3)_3SiC_5H_3]_2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization tem-perature is found to be the most important factor affecting the polymerization. The bulkpolymerization gives higher molecular weight PCL and higher conversion than that in solu-tion polymerization. NaBPh_4 was found to promote the polymerization of ε-caprolactone,and thus to increase both the polymerization conversion and MW of poly (ε- caprolactone ).     

STUDIES ON THE POLYMERIZATION OF β-CYCLODEXTRIN WITH EPICHLOROHYDRIN*

Different proportions of β-cydodextrin and epichlorohydrin were used to prepare a group of β-cyclodextrin polymers. The relationship between the reaction extent and the molar ratios of reactants was discussed according to the results of ~1H-NMR, ~(13) C-NMR spectra and elemental analysis. Especially, high resolution ~1H-NMR spectra were usd for studying the reaction active sites and the extent of reaction. The solubility of oil soluble drugs in water was largely improved in the presence of water-soluble β-cyclodextrin polymer.     

SYNTHESIS OF γ-SUBSTITUTED-PROPYLCYCLOTETRASILOXANES AND THEIR EMULSION COPOLYMERIZATION WITH OCTAMETHYLCYCLOTETRASILOXANE*

Four γ-substituted-propylcyclotetrasiloxanes have been synthesized. Emulsion copolymerizations of these cyclosiloxanes with octamethylcyclotetrasiloxane have been carried out both in cationic and anionic emulsion systems. By way of these reactions, stable emulsions of organosilicon polymers which contain carbonfuctional groups such as γ-hydroxypropyl, γ-acetoxypropyl and γ-chloropropyi have been obtained.The effects of temperature, catalyst and the amount of γ-substituted-propylcyclotetrasiloxanes in emulsion copolymerizations have been studied.     

STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLY(ETHER-URETHANE)

A new method of graft copolymerization of acrylamide (AAM) on poly(ether-urethane) (PEU) which was prepared from poly(tetramethylene ether) glycol (PTMG), 4,4'-diphenylmethane diisocyanate (MDI) and ethylene diamine or butanediol extender was investigated. Hydroperoxide group was first introduced onto the surface of PEU through photo-oxidation in the presence of hydrogen peroxide, then it was reacted with ferrous ion or N,N-dimethyl toluidine (DMT) to initiate AAM graft copolymerization on PEU surface. The graft reaction could be carried out effectively at low temperature. The formation of graft copolymer has been verified by its water absorption % and the scanning electron microscopy photographs. Some model compounds of PEU soft segment and hard segment were synthesized in order to clarify the site of graft reaction. The results of oxida-tion and graft copolymerization of model compounds showed that this graft copolymerization possesses higher selectivity, and it takes place predominately at the polyether segments, because the ether linkage in soft segment is very sensitive to oxidation and can form hydroperoxide easily. Thus, the grafting site appears to be at α-carbon of the ether linkage.     

EFFECTS OF ω-ACRYLOYL POLY (ETHYLENE OXIDE) MACROMONOMER ON EMULSIFIER-FREE EMULSI0N COPOLYMERIZATION OF METHYL METHACRYLATE AND n-BUTYL ACRYLATE*

Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.     

THERMAL PROPERTY, MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY(3-HYDROXYBUTYRATE-co-3-YDROXYHEXANOATE) AND POLY(BUTYLENE SUCCINATE-ADIPATE) (PHBHHX/PBSA) BLENDS

1. INTRODUCTION Biodegradable polymers have received considerable attention in the last two decades due to their potential applications in the fields related to human life such as environmental protection and ecology. According to the difference in the preparation methods, biodegradable polymers can be classified into two types. One is the biosynthetic polymers, such as bacterialpolyhydroxyalkanoates (PHAs). Among them, the most extensively studied biodegradable thermoplastic polymers ar…     

PIEZOEIECTRICITY AND MOLECULAR MOTION OF POLY(VINYLIDENE-FLUORIDE)BLENDS

In the last few years,the piezoelectricity of PVDF has attracted much attention,andvarious transducers using PVDF have been widely used.With the purpose to clarify the influence of the second component of PVDF blend onits film piezoelectric property and to search for new piezoelectric materials,this paperreports the investigation on the piezoelectricity and the molecular motion of three types     

COMPATIBILITY OF POLY (STYRENE-B-2-VINYL PYRIDINE)/IONOMER BLENDS BASED ON ION-LIGAND INTERACTION

1. INTRODUCTION The blending of polymers is an economically viable and versatile way in which new materials can be produced to have a wide range of properties. The majority of polymers are immiscible at the molecular level as given by laws of thermodynami…     

STUDIES ON ULTRASONIC ABSORPTION AND VISCO-RELAXATION OF POLY (ETHYLENE GLYCOL) AQUEOUS SOLUTIONS

Ultrasonic absorption and velocity measurements were made on aqueous solutions of poly (ethylene glycol)(PEG)of different molecular weights and concentrations, using a pulse sender-receiver ultrasonic generator, Measurements were obtained at a frequency of 2MHz. , and a temperature of 293 K. The results show a linear increase of the Values of velocity, density and viscosity with increase of molecu lar weight and concentration of PEG. On the contrary, the attenuation values decreased with increase of molecular weight and concentration of PEG. A mathematical equation correlating relaxation amplitude and molecular weight of the polymer is suggested. This was applied to calculate the molecular weights of unknown samples of PEG from their measured relaxation amplitude. The results obtained were in good agreement with those obtained from osmometry.     

SYNTHESIS OF POLYACRYLAMIDE WITH PENDANT POLY(BUTYL ACRYLATE) CHAINS USING THE MACROMER TECHNIQUE AND STUDIES ON THEIR PROPERTIES

INTRODUCTIONSince Milkovich and Chiang[1] developed a method of preparing copolymers with uniform side chains by usingthe macromer technique, the synthesis of copolymers with uniform side chains from different macromers hasbeen studied extensively. Milkovich et al. reported the synthesis of polystyrene macromer through termination ofliving polystyrene anions with methacryloyl chloride and its copolymerization with butyl acrylate to formthermoplastic elastomer[2]. Rempp[3] obtained polyoxy…     

MISCIBILITY AND MORPHOLOGICAL STRUCTURE OF BIODEGRADABLE BLEND OF POLY(β—HYDROXYBUTYRATE)AND POLY(D,L—LACTIDE)

The poly(β-hydroxybutyrate)/poly(d,1-lactide)(PHB/PLA)blend was foundto be immiscible,the melting point and the phase crystallinity of PHB were independent of theblend composition.Comparing with plain PHB,the blend exhibited the crystallization changeand a certain improvement of the mechanical property.     

STUDIES ON ULTRASONIC GRAFTING OF POLY(VINYL ACETATE) WITH POLY(ETHYLENE OXIDE)

The ultrasonic degradation of poly(ethylene oxide) and poly(vinyl acetate) in benzene solution, and grafting reaction of poly(vinyl acetate) with poly(ethylene oxide) were studied. It is found that the chain-scission reactions follow the course suggested by D. W. Ovenall. The structure of the copolymer was identified by IR, NMR and DTA, showing that the copolymer prepared is a graft copolymer mainly. The copolymer formed by irradiating 1% PEO/PVAc solution (PEO/PVAc:1/1 by weight) for a period of 10 rain at 18.2 kHZ, with 2.0 A input current on reversed main circuit, amounts to 10.5%.     

AROMATIC AND HETEROCYCLIC DINITRILES AND THEIR POLYMERS ⅪⅤ. STUDY ON THE CATALYSTS OF THE POLYMERIZATION OF AROMATIC NITRILES*

Various catalysts for the polymerization ot aromatic nitriles were investigated. It was found that Lewis acid-metal is a preferable catalyst system for the polymerization of aromatic nitriles, and the polymerization rate is about 10 times faster than Lewis acid alone. The polymerization rate of benzonitrile catalyzed by Lewis acid and different metals was measured, and the activity of metals was in the following decreasing order ,magnesium, zinc, sodium, calcium. Furthermore, the polymerization of benzonitrile catalyzed by different Lewis acid and zinc was also investigated.     

SURFACE STRUCTURE AND BULK PROPERTIES OF FLUORINATED POLY(ETHER URETHANE)S AND POLY(ETHER URETHANE) BLENDS

INTRODUCTIONPolyurethanes (PU) have been widely used for manufacturing medical devices because of their excellentmechanical properties and moderate biocompatibility[1]. Although polyurethanes used in applications requiringall of the above properties have been successful for short-term use, the problems of long-term thromboresistanceand biostability in a biological environment still remain unsolved[2,3]. A legitimate approach to improving theproperties of polyurethanes is introduction of f…     

STUDIES OF ACTIVE DIACYLAMIDES OF BENZOTRIAZOLE Ⅰ. SYNTHESIS OF POLYAMIDES AND POLYESTERS*

Two new routes to polyamides and polyesters were established, based on the polycondensationof new typical active diacylamide of benzotriazole, such as 1, 1'-(isophthaloyl) bisbenzotriazole(IPBBT) and 1, 1'-(terephthaloyl)bisbenzotriazole (PBBT) with diamines, diols and diphenol underdifferent mild conditions. The N-acylation of polycondensation occurred at room temperaturewithout added catalyst, the O-acylation of polycondensation had to complete in the presence oftriethylamine as a catalyst at 60℃.     

CONFORMATION AND CHAIN PACKING STRUCTURES OF POLY (ρ-PHENYLEN BENZOBISTHIAZOLE) BY MOLECULAR SIMULATION*

The conformation, the chain packing stabilization and the unit cell modeling of poly(p-phenylene benzobisthiazole) have been investigated by using molecular simulation techniquein the present work. A coupling behaviour of σ-bond rotations at either side of the pheny-lene ring or the heterocyclic ring was found surely to exceed a length of the repeat unit ofthe polymer chain. For a single chain model, the stable torsion angle of the repeat resultedat 14°. In the crystalline cell minimization, the dihedral angle along the polymer chaincould even be stabilized in various values. It therefore indicates that the intermolecularinteraction does play a considerable role for this polymer forming the conformation. Ac-cording to cohesive energies calculated for these unit cell models, the torsion angle in themost stable crystalline cell is 0°. When the chains packing together, there exist so manyenergy stable wells along the chain axis 0.35--0.36nm apart from neighbouring chains.Most of the unit cells have quite closed cohesive energies. These factors thus cause thedifficulty of forming an unique perfect crystalline structure of the polymer. The presentstudy suggested a number of reasonable unit cells, and the most stable crystalline structurefor this polymer that is monoclinic, non-primitive unit cell.     

STUDIES OF THE CRYSTALLIZATION BEHAVIOR IN THE CRYSTALLINE/AMORPHOUS POLYMER BLENDS: POLY(ETHYLENE OXIDE)/POLY(METHYL METHACRYLATE) AND POLY(ETHYLENE OXIDE)/POLY(VINYL ACETATE)

The crystallization process of poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)and PEO/poly(vinyl acetate) (PVAc) blends has been characterized by Fourier Transform Infrared(FTIR) spectra in conjunction with Differential Scanning Calorimeter (DSC) measurements. Thecrystallinity of PEO varies consistently with PEO content in PEO/PVAc blends and the PEO/PMMAblends containing 50 wt% or less PMMA. For the PEO/PMMA blends containing 60 wt% ormore PMMA, the crystallinity of PEO decreases more than PEO content but develops with crystal-lization time. These results can be explained in terms of difference between the crystallization tem-perature (T_c) and glass transition temperature (T_g) of the blends as a function of content of amorphouscomponent.