Thermally crosslinkable poly(phenylene sulfide)/poly (ether sulfone)/polymerization of monomer reactant-polyimide blends

The effects of thermally crosslinkable polymerization of monomer reactant-polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature.

Crystal structure of a noval poly(aryl ether ketone) containing meta-phenyl linkage

Crystal structure of a novel aryl ether ketone polymer poly(aryl ether ketone ether ketone ketone containing meta-phenyl linkage)(PEKEKmK) was determined by means of WAXD and ED. An orthorhombic unit cell is proposed containing two chains with a=0.772 nm, b=0.604 nm and c=2.572 nm. According to the orthorhombic system, the 10 reflections of this polymer were indexed.

Crystal structure and variation in unit cell parameters with crystallization temperatures of poly (ether ketone ether ketone ketone)s containing meta-phenyl links (PEKEKmK)

The X-ray diffraction patterns of the crystalline aromatic ketone polymer PEKEKmK (aryl ether ketone ether ketone ketone polymer containing meta-phenyl links) have been investigated (for the chemical structure, see Formula). An orthorhombic unit cell is proposed to contain two chains with a = 0.772 nm, b = 0.604 nm and c = 2.572 nm. According to the orthorhombic system, the 11 reflections of this polymer were indexed. Meanwhile, variation in unit cell parameters with crystallization temperatures of PEKEKmK was also investigated. [GRAPHICS]

Formation of a metastable phase induced by a liquid crystalline phase in a novel chloropoly(aryl ether ketone)

The phase transition behavior of a thermotropic liquid crystalline poly(aryl ether ketone) synthesized by nucleophilic substitution reactions of 4,4'-biphenol (BP), and chlorohydroquinone (CH) with 1,4-bis(4-fluorobenzoyl)benzene (BF) has been investigated by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). The copolymer exhibits multiple first order phase transitions, which are associated with crystal-to-smectic liquid crystal transition and smectic liquid crystal-to-isotropic transition. When the cooling rate is low (<10C/min), only stable crystal from I is formed. With the cooling rate being high (>20 degreesC/min), the metastable crystal form II is formed, which always coexists with form I. The liquid crystalline phase plays an important role in the formation of metastable phase form II.

Synthesis and crystallization of a novel poly(ether ketone ether ketone ketone) containing meta-phenylene linkage: PEKEKK(T/I)

Poly(ether ketone ether ketone ketone) containing meta-phenylene linkage (PEKEKK(T/I)) was synthesized by electrophilic Friedel-Crafts acylation condensation of 1, 4-diphenoxybenzophenone with terephthaloyl chloride (T) and isophthaloyl chloride (I) with a T/I ratio of 1 and characterized by LR,DSC,TGA and WAXD. PEKEKK(T/I) has two different crystal structures: a conventional Farm I structure, the same as that observed in PEEK and PEK, wich is usually developed from melt crystallization, and a new Form II structure which can be developed from cold crystallization or solvent induced crystallization (by exposing the glassy sample to methylene chloride).

A study of the crystallographic equivalence of ether and ketone groups in poly(aryl ether ketone)s

Crystallographic equivalence of ether and ketone in all para-substituted PAEKs crystallized in form I was discussed in this paper. In a word, crystallographic equivalence between ether and ketone groups is tenable when polymer contains only phenyl rings in the repeat unit. If a polymer contains a diphenyl group in the repeat unit, two cases should be distinguished. In the case of PEDEKK and PEEKDK, crystallographic equivalence between ether and ketone linkages is untenable, However, in the case of PEDK and PEDEKDK, crystallographic equivalence between ether and ketone linkages is still tenable.

Gas transport properties of novel cardo poly(aryl ether ketone)s with pendant alkyl groups

Gas transport of hydrogen, oxygen, nitrogen, carbon dioxide, and methane in four cardo poly(aryl ether ketone)s containing different alkyl substituents on the phenyl ring has been examined from 30 to 100 degrees C. The permeability, diffusivity, solubility, and their temperature dependency were studied by correlations with gas shape, size, and critical temperature as well as polymeric structural factors including glass transition, secondary transition, cohesive energy density, and free volume. The bulky, stiff cardo and alkyl groups in tetramethyl-substituted TMPEK-C resulted in increased H-2 permeability (by 55%) and H-2/N-2 permselectivity (by 106%) relative to bisphenol A polysulfone (PSF). Moreover, the weak dependence of gas transport on temperature in TMPEK-C made it maintain high permselectivities (alpha(H2/N2) in 68.3 and alpha(O2/N2) in 5.71) up to 100 degrees C, exhibiting potential for high-temperature gas separation applications.

Isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

The isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) are investigated by differential scanning calorimetry over two temperature regions. The Avrami equation describes the primary stage of isothermal crystallization kinetics with the exponent n approximate to 2 for both melt and cold crystallization. With the Hoffman-Weeks method, the equilibrium melting point is estimated to be 406 degrees C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter (K-g) of the isothermal melt and cold crystallization is estimated. In addition, the K-g value of the isothermal melt crystallization is compared to those of the other poly(aryl ether ketone)s. (C) 2000 John Wiley & Sons, Inc.

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) (PEKEKK) were investigated by differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could only describe the primary stage of nonisothermal crystallization kinetics of PEKEKK. Also, the Ozawa equation could not describe its nonisothermal crystallization behavior. A convenient and reasonable kinetic approach was used to describe the nonisothermal crystallization behavior. The crystallization activation energy were estimated to be -264 and 370 KJ/mol for nonisothermal melt and cold crystallization by the Kissinger method. (C) 2000 John Wiley & Sons, Inc.

Novel macrocyclic precursors of poly{aryl ether ketone (sulfone)} containing hexafluoroisopropylidene units: Synthesis, characterization, and polymerization

Cyclic oligomers containing hexafluoroiso-propylidene(HFIP) units were prepared in excellent yields by a nucleophilic aromatic substitution reaction of 4,4(7)- (hexafluoroisopropylidene) diphenol with difluoro-monomers in the presence of anhydrous potassium carbonate under pseudo high dilution conditions. A combination of GPC, MALDI-TOF MS and NMR analysis confirmed the structure of the cyclic oligomers. All macrocyclic oligomers are crystalline and undergo facile melt polymerization to give high molecular weight fluorinated polyethers.

Crystallization behavior of a novel ether ketone polymer containing meta-phenylene linkage: PEKEKK (T/I)

Nonisothermal and isothermal melt crystallization kinetics of a novel aryl ether ketone polymer containing meta-phenylene linkages, PEKEKK (T/I), were studied by differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny and a new approach by combining the Avrami equation with the Ozawa equation could describe the nonisothermal crystallization. Isothermal crystallization could also be described by the Avrami equation. The activation energies were 187 and 159 kJ/mol for nonisothermal and isothermal crystallization, respectively. Using the Hoffman-Weeks method, the equilibrium melting point T-m(o) was estimated as 353 degrees C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter K-g of the isothermal melt crystallization was estimated as 5.49 x 10(5) K-2. The crystallization characteristics of PEKEKK (T/I) were compared with those of all-para PEKEKK. The differences were explained by differences in the chain flexibility of the two polymers.

The single crystal-like banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group

The banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group have been studied by means of transmission electron microscopy(TEM), electron diffraction(ED) and atomic force microscopy (AFM). The crystallization-induced Landed texture without external shear can be formed when the thin films were annealed at the temperature range(320-330 degrees C) of the liquid crystalline state from the melt, The results show that the banded regions have high orientation of single crystal based on the orthorhombic packing and the growing direction of the Lands is along the b axis of the crystals, This kind of single crystal-like bands is due to the different orientation of the packing molecular chains, The molecular chains of the dark bands in the bright field electron micrograph are perpendicular to the film plane, while the ones of the bright Lands are tilt along the b axis with the tilt angle upto +/-20 degrees.

X-ray crystal structure and molecular mechanics calculations of (2,6-iso-dipropyl-phenylamide) dimethyl (tetra-methylcyclopenta-dienyl) silane titanium dichloride

Crystal and molecular structure of (2.6-dipropylphenylamide) dimethyl (tetra-methyl cyclopentadienyl) silane titanium dichloride (I) was fully characterized by X-ray diffraction. The crystal is obtained from a mixture of ether/hexane as orthorhombic. with a = 12.658 (3) Angstrom. b = 16.62 (3) Angstrom. c = 11.760 (2) Angstrom. V = 2474.2 (9) Angstrom(3). Z = 4, space group Pnma. R = 0.0399; Componud I compose of the pi-bounded ring with its dimethylsilyl-dipropyl phenyl amido group and the two terminal chloride atoms coordinated to central metal to form a so-called constrained geometry catalyst (CGC) structure. The result of molecular mechanics (MM) calculations on compound I shows that bond lengths and bond angles from the MM calculation are comparable to the data obtained from the X-ray diffraction study. The relation of the structure of CGCs and their catalytic activity by MM calculations is also discussed.