Relating the molecular structure and crystallization behavior of polypropylene

The crystallization behavior of two polypropylene (PP) resins as used for biaxially oriented polypropylene (BOPP) and general injection mold applications, respectively, has been intensively investigated and compared by means of polarized light optical micrography (POM), differential scanning calorimetry (DSC), conventional transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM). It is found that both molecular weight distribution and isotacticity of polypropylene strongly affect its crystallization characteristics, e.g., the number of crystal nuclei at the initial stage, crystallization dynamics, the morphology, size and perfection of crystals in the final product, and so on. The results indicate an appropriate molecular structure is vital in producing high-quality BOPP film.

Copolymers derived from bismaleimide oligomer with active solvent

An oligomer from 4, 4'-bis(maleimido)diphenyl methane and methylenedianiline were dissolved in active solvent N,N-dimethyl acrylamide in a solid content up to 50-70%; the solution was poured in a sheet-shaped module and irradiated b y Co-60 with the dose from 20 to 350 kGy at room temperature. The polymerized sheet was postcured at 180degreesC to obtain a transparent red-orange sheet with tensile strength above 100 MPa. The glass transition temperature before and after postcuring was around 100degreesC and 150-180degreesC, respectively. Styrene was used along with DMAA to decrease the water absorption for the copolymers.

Adsorption of heavy rare earth(III) with extraction resin containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid

In the present paper, the adsorption of thulium(Ill) from chloride medium on an extraction resin containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid (CL302, HL) has been studied. The results show that 1.5 h is enough for the adsorption equilibrium. The distribution coefficients are determined as a function of the acidity of the aqueous phase and the data are analyzed both graphically and numerically. The plots of log D versus pH give a straight line with a slope of about 3, indicating that 3 protons are released in the adsorption reaction of thulium(III). The content of Cyanex302 in the resin is determined to be 48.21%. The total amount of Tm3+ adsorbed up to resin saturation is determined to be 82.46 mg Tm3+/g resin. Therefore, the sorption reactions of Tm3+ from chloride medium with CL302 can be described as: Tm3+ + 3HL((r)) <----> TmL3(r) + 3H(+) The Freundlich's isothermal adsorption equation is also determined as: log Q = 0.73 log C + 3.05 The amounts (Q) of Tm3+ adsorbed with the resin have been studied at different temperatures (15-40degreesC) at fixed concentrations of Tm3+, amounts of extraction resin, ion strength and acidities in the aqueous phase.

Polyimides from isomeric diphenylthioether dianhydrides

3,3',4,4'-Diphenylthioether dianhydride (4,4'-TDPA), 2,3,3',4'-diphenylthioether dianhydride (3,4'-TDPA), and 2,2',3,3-diphenylthioether dianhydride (3,3'TDPA) were synthesized from 3-chlorophthalic anhydride and 4-chlorophthalic anhydride. A series of polyimides derived from the isomeric diphenylthioether dianhydrides with several diamines were prepared. The properties, such as the solubility, thermal and mechanical behavior, dynamic mechanical behavior, wide-angle X-ray diffraction, and permeability to some gases, were compared among the isomeric polyimides. Both 3,3'-TDPA- and 3,4-TDPA-based polyimides had good solubility in polar aprotic solvents and phenols. The 5% weight loss temperatures of all the obtained polyimides was near 500 degrees C in nitrogen. The glass-transition temperatures decreased according to the order of the polyimides based on 3,3'-TDPA, 3,4'-TDPA, and 4,4'-TDPA. The 3,4'-TDPA-based polyimides had the best permeability and lowest permselectivity, whereas the 4,4'-TDPA-based polyimides had the highest permselectivity and the lowest permeability of the three isomers. Furthermore, the rheological properties of thermoplastic polyimide resins based on the isomeric dipbenylthioether dianhydrides were investigated, and they showed that polyimide 3,4'-TDPA/4,4-oxydianiline had the lowest melt viscosity among the isomers; this indicated that the melt processibility had been greatly improved.

Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Characterization of the microstructure of biaxially oriented polypropylene using preparative temperature-rising elution fractionation

Two commercial biaxially oriented polypropylene (BOPP) resins, resin A and resin B, having different processing properties, were fractionated by preparative temperature-rising elution fractionation (TREF). The TREF fractions were further characterized by gel permeation chromatography (GPC), gel permeation chromatography coupled with light scattering (GPC-LS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). GPC-LS did not find visible long-chain branching in either resin A or B. The results from TREF and DSC indicate that the fractional melting parameter f(T) may be used to predict the profile of the TREF cumulative weight distribution curve. GPC results show that the molecular weights of the fractions tend to increase with elution temperature. WAXD and DSC data show that the crystallinity of fractions does not increase monotonically with increase of elution temperature. There appears to be a maximum in the plot of crystallinity versus elution temperature. The high-speed BOPP resin A has a lower isotacticity but a homogeneous isotacticity distribution and a higher molecular weight but a broader molecular weight distribution than resin B.

Adsorption studies of divalent metal ions with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid

Equilibrium distributions of cobalt(II), nickel(II), zinc(II), cadmium(II), and copper(II) have been studied in the adsorption with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HEOPPA) as an extractant from chloride medium. The distribution coefficients are determined as a function of pH. The data are analyzed both graphically and numerically. The extraction of the metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML2(HL)(q). The adsorbed species of the metal ions are proposed to be ML2 and the equilibrium constants are calculated. The efficiency of the resin in the separation of the metal ions is provided according to the separation factors values. The separation of Zn from Ni, Cd, Cu, Co, and Co from Ni, Cd, Cu with the resin is determined to be available. Furthermore, Freundlich's isothermal adsorption equations and thermodynamic quantities, i.e., DeltaG, DeltaH, and DeltaS are determined.

Multiple melting behavior of isotactic polypropylene and poly(propylene-co-ethylene) after stepwise isothermal crystallization

The multiple melting behavior of several commercial resins of isotactic polypropylene (iPP) and random copolymer, poly(propylene-co-ethylene) (PPE), after stepwise isothermal crystallization (SIC) were studied by differential scanning calorimeter and wide-angle X-ray diffraction (WAXD). For iPP samples, three typical melting endotherms appeared after SIC process when heating rate was lower than 10 degreesC/min. The WAXD experiments proved that only alpha-form crystal was formed during SIC process and no transition from alpha1- to alpha2-form occurred during heating process. Heating rate dependence for each endotherm was discussed and it was concluded that there were only,two major crystals with different thermal stability. For the PPE sample, more melting endotherms appeared after stepwise isothermal crystallization. The introduction of ethylene comonomer in isotactic propylene backbone further decreased the regularity of molecular chain, and the short isotactic propylene sequences could crystallize into gamma-form crystal having a low melting temperature whereas the long sequences crystallized into alpha-form crystal having high melting temperature.

Novel polyimides derived from 2,3,3 ',4 '-benzophenonetetracarboxylic dianhydride

A series of polyimides (PIs) based on 2,3,3',4'-benzophenonetetracarboxylic dianhydride (2,3,3',4'-BTDA) and 3,3',4,4'-BTDA were prepared by the conventional two-step process. The properties of the 2,3,3',4'-BTDA based polyimides were compared with those of polyimides prepared from 3,3',4,4'-BTDA. It was found that PIs from 2,3,3,4'-BTDA have higher glass transition temperature and better solubility without sacrificing their thermal properties. Furthermore the theological properties of PMR-15 type polyimide resins based on 2,3,3',4'-BTDA showed lower melt viscosity and wider melt flow region (flow window) compared with those from 3,3',4,4'-BTDA. The structure-property relations resulted from isomerism were discussed.

Liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol catalyzed by polymer resin supported palladium catalysts

Three kinds of polymer resin supported Pd catalysts were prepared by mixing PdCl2, with alkaline styrene anion exchange resins[D392 -NH2, D382, -NHCH3, D301R, -NH(CH3)(2)], strongly alkaline styrene anion exchanged resin [201 X 7DVB, -NH+ (CH3)(3)] and alkaline epoxy exchange resin (701, -NH2), and hydrogenating in liquid phase at 1.013 X 10(5) Pa. The hydrogenation of furfural was studied under the reaction conditions such as solvent, temperature. Pd content in the supported catalyst and the amount of the catalyst. The yield of hydrogenation reaction of furfural markedly increased to 100% and the selectivity to tetrahydrofurfuryl alcohol increased to over 98% by polymer (alkaline styrene anion exchange resins D392, -NH2, D382, -NHCH3) supported palladium catalysts comparing with the yield over 70% and selectivity over 97% by palladium catalyst, in 50% alcohol-50% water or pure water solution at 1.013 X 10(5) Pa. The relationship between hydrogenation and the structures of functional group in the supporting resin was examined by XPS method.

Efforts to decrease crosslinking extent of polyethylene in a reactive extrusion grafting process

Grafting of acrylic acid and glycidyl methacrylate onto low density polyethylene (LDPE) was performed by using a corotating twin-screw extruder. The effects of residence time and concentration of initiator and monomers on degree of grafting and gel content of grafting LDPE were studied systematically. Paraffin, styrene, p-benzoquinone, triphenyl phosphite, tetrachloromethane, and oleic acid were added to try to decrease the extent of crosslinking of LDPE. 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidinyloxy (4-hydroxyl-TEMPO) and dipentamethylenethiuram tetrasulfide were also tried to inhibit crosslinking reaction of LDPE during its extruding grafting process. It was found that p-benzoquinone, triphenyl phosphite and tetrachloromethane were good inhibitors for crosslinking of LDPE. (C) 2000 John Wiley & Sons, Inc.

Crosslinking of polyimides via spirodilactone unit in polymer backbone

A new approach for the crosslinking of polyimides via the lactamization of spirodilactone unit in polyimide backbone was studied by two means: model reaction and the comparison of the properties of the polyimide precursors to those of the crosslinking polymers. Polyimides 4 and 5 were soluble in N,N'dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), N'-methylpyrrolidone (NMP), and other common organic solvents, whereas their corresponding crosslinking polymers were insoluble in these solvents. The glass transition temperatures for polyimide 5 and its crosslinking polymer were 262 degrees C and 291 degrees C, whereas those for polyimide 4 and its crosslinking polymer were 265 degrees C and 360 degrees C. The weight-loss rate of the crosslinling polymers was apparently slower than that of the precursors when the temperature was >400 degrees C. The 10% weight-loss temperature for the polyimides 4 and 5 was <500 degrees C, whereas that for the crosslinking polymers was close to or above 600 degrees C. The results indicate that this type of crosslinking polymer has good thermal properties. The temperature for the formation of lactam was above 180 degrees C. (C) 1999 John Wiley & Sons, Inc.

Extraction and separation of heavy rare earth (III) with Extraction Resin containing di(2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272)

Extraction resins, of the type of;levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50 degrees C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm2O3 >99.97%, >80%, Er2O3 >99.9%, >94% and Yb2O3 >99.8%, >80% respectively, have been obtained from a feed having the composition Tm2O3 60%, Er2O3 10%, and Yb2O3 3%, the others 27%. The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .1. DSC characterization of curing reaction

The curing reaction process of epoxy-terminated poly(phenylene ether ketone) (E-PEK) with 4,4'-diaminodiphenyl sulfone (DDS) and hexahydrophthalic acid anhydride (Nadic) as curing agents was investigated using isothermal differential scanning calorimetry (IDSC) and nonisothermal differential scanning calorimetry (DDSC) techniques. It was found that the curing reactions of E-PEK/DDS and E-PEK/Nadic are nth-order reactions but not autoaccelerating. The experimental results revealed that the curing reaction kinetics parameters measured from IDSC and DDSC are not equivalent. This means that, in the curing reaction kinetics model for our E-PEK system, both isothermal and nonisothermal reaction kinetics parameters are needed to describe isothermal and nonisothermal curing processes, The isothermal and nonisothermal curing processes were successfully simulated using this model. A new extrapolation method was suggested. On the basis of this method the maximum extent of the curing reaction (A(ult)) that is able to reach a certain temperature can be predicted. The A(ult) for the E-PEK system estimated by the new method agrees well with the results obtained from another procedure reported in the literature. (C) 1997 John Wiley & Sons, Inc.

TEMPERATURE AND STRAIN-RATE DEPENDENCE OF FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

A strong strain-rate and temperature dependence was observed for the fracture toughness of phenolphthalein polyether ketone (PEK-C). Two separate crack-blunting mechanisms have been proposed to account for the fracture-toughness data. The first mechanism involves thermal blunting due to adiabatic heating at the crack tip for the high temperatures studied. In the high-temperature range, thermal blunting increases the fracture toughness corresponding to an effectively higher test temperature. However, in the low-temperature range, the adiabatic temperature rise is insufficient to cause softening and Jic increases with increasing temperature owing to viscoelastic losses associated with the p-relaxation there. The second mechanism involves plastic blunting due to shear yield/flow processes at the crack tip and this takes place at slow strain testing of the single-edge notched bending (SENB) samples. The temperature and strain-rate dependence of the plastic zone size may also be responsible for the temperature and strain-rate dependence of fracture toughness.