Polyimides Derived from 1,4-Bis [3-oxy-(N-aminophthalimide)] Benzene

A novel diamine, 1,4-bis [3-oxy-(N-aminophthalimide)] benzene (BOAPIB), was synthesized from 1,4-bis [3-oxy-(N-phenylphthalimide)] benzene and hydrazine. Its structure was determined via IR, H-1 NMR, and elemental analysis. A series of five-member ring, hydrazine-based polyimides were prepared from this diamine and various aromatic dianhydrides via one-step polycondensation in p-chlorophenol. The inherent viscosities of these polyimides were in the range of 0.17-0.61 dL/g. These polymers were soluble in polar aprotic solvents and phenols at room temperature. Thermogravimetric analysis (TGA) showed that the 5% weight-loss temperatures of the polyimides were near 450 degrees C in air and 500 degrees C in nitrogen. Dynamic mechanical thermal analysis (DMTA) indicated that the glass-transition temperatures (T(g)s) of these polymers were in the range of 265-360 degrees C. The wide-angle X-ray diffraction showed that all the polyimides were amorphous.

Gas permeation properties of copolyimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride

A series of aromatic copolyimides was prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride (6FDA) with 3,3'-dimethyl-4,4'-methylene dianiline (DMMDA) by a chemical imidization. The gas permeability coefficients of the copolyimides to H-2, CO2, O-2, N-2 and CH4 were measured under 7 atm. pressure. The fractional free volume of 6FDA-DMMDA is larger than that of HQDPA-DMMDA, while the chain segmental mobility of 6FDA-DMMDA is lower than that of HQDPA-DMMDA. The gas permeability of 6FDA-DMMDA is much higher than that of HQDPA-DMMDA but the permselectivity of 6FDA-DMMDA for H-2, CO2, O-2, N-2 over CH4 is lower than that of HQDPA-DMMDA. The experimental values of the gas permeability coefficients of the copolyimides are in satisfactory agreement with the values estimated from the gas permeability coefficients of the constituent homopolyimides and their weight fractions.

Gas separation properties of aromatic polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 3,5-diaminobenzic acid or its esters

The gas transport properties of a series polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) with 1,3-phenylenediamine or 3,5-diaminobenzic acid (DBA) or its esters are reported. The effects of carboxylic group (-COOH) and carboxylic ether groups (-COOR), at five positions of 1,3-phenylenediamine moiety, on H-2, CO2, O-2, and N-2 permeability, diffusivity, and solubility of the polyetherimides were investigated. The gas permeability, diffusion, and solubility coefficients of the polyetherimides containing COOR are bigger than those of HQDPA-PDA, but the ideal separation factors and ideal diffusivity selectivity factors are much smaller than that of HQDPA-PDA because COOR decreases chain segmental packing efficiency and increases chain segmental mobility. The permeability coefficients of HQDPA-DBA to H-2, CO2, and O-2 are bigger than those of HQDPA-PDA; the ideal separation factors for gas pairs H-2/N-2, CO2/N-2, and O-2/N-2 are also much bigger than those of HQDPA-PDA. Both the diffusion coefficients of CO2 and O-2 and the ideal diffusivity selectivity factors for CO2/N-2 and O-2/N-2 are bigger than those of HQDPA-PDA because COOH decreases both chain segmental packing efficiency and chain segmental mobility. The copolyimides, which were prepared from 3,5-diaminobenzic acid and 3,5-diaminobenzic esters, have both high permeability and high permselectivity. (C) 1997 John Wiley & Sons, Inc.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .2.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) with various aromatic diamines, to H-2, O-2 and N-2 have been measured under 7 atm and at the temperature range 30-100 degrees C. A significant change in the permeability and permselectivity resulting from the systematic variation in chemical structure of the polyetherimides was found. Among the polyetherimides, that were prepared from phenylenediamine and methyl substituted phenylenediamines, the increase of permeability is accompanied by a decrease of permselectivity. The polyetherimides that were prepared from 3,5-diaminobenzoic esters have lower permselectivity than the others. However, the polyetherimide from 3,5-diaminobenzoic acid possesses much higher permselectivity than the others due to cross-linking. Copyright (C) 1996 Elsevier Science Ltd

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .1.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and various aromatic diamines, to H-2, CO2, O-2, N-2 and CH4 have been measured under 7 atm pressure and over the temperature range 30-150 degrees C. A significant change in permeability and permselectivity, which resulted from a systematic variation in chemical structure of the polyetherimides, was found. Generally, increases in permeability of the polyetherimides are accompanied by decreases in permselectivity. The order of decrease of the permeability coefficients is as follows: HQDPA-IPDA > HQDPA-DDS > HQDPA-MDA > HQDPA-ODA > HQDPA-DABP > HQDPA-BZD. However, HQDPA-DMoBZD and HQDPA-DMoMDA, with bulky methoxy side-groups on the aromatic rings of the diamine residue, display both high permeability coefficients and high permselectivity. The favourable gas separation property, excellent thermal and chemical stability, and high mechanical strength make HQDPA-DMoBZD and HQDPA-DMoMDA promising candidates for membrane-based gas separation applications.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .3.

Gas permeability coefficients of a series of aromatic polyetherimides prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and four (methylene dianiline)s with a methyl side group to H-2, CO2, O-2, N-2, and CH4 were measured under 7 atm and within a temperature range from 30 to 150 degrees C. The gas permeabilities and permselectivities of these polymers were compared with those of the HQDPA-based polyetherimides from methylene dianiline (MDA) and isopropylidene dianiline (IPDA). The number and position of the methyl side groups on the benzene rings of the diamine residues strongly affect the gas permeabilities and permselectivities of the HQDPA-based polyetherimides. The gas permeability of the polyetherimide progressively increases with an increase in the number of the methyl side groups. Both the gas permeability and permselectivity of the polyetherimides with methyl side groups are higher than those of HQDPA-MDA. The polyetherimide prepared from 3,3'-dimethyl 4,4'-methylene dianiline (DMMDA1) possesses both higher permeability and permselectivity than the polyetherimides prepared from 2,2'-dimethyl 4,4'-methylene dianiline (DMMDA2). However, two of the polyetherimides prepared 2,2',3,3'-tetramethyl 4,4'-methylene dianiline (TMMDA1) or 2,2', 5,5'-tetramethyl 4,4'-methylene dianiline (TMMDA2) possess almost the same gas permeability and permselectivity.

Gas permeability in polyimides from oxydianiline and isomeric thiaphthalic dianhydride or 1,4-bis(dicarboxyphenoxy) benzene dianhydride

The gas permeability and permselectivity properties were investigated of polyimides, prepared from 3,3',4,4'- and 2,2',3,3'-thiaphthalic dianhydride (p-TDPA and m-TDPA, respectively), or 1,4-bis(3,4-dicarboxyphenoxy)- and 1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride (p-HQDPA and m-HQDPA, respectively), and 4,4-oxydianiline. The polyimides prepared from meta-dianhydrides, which have lower chain-segment packing density, possess higher permeability and lower permselectivity than those prepared from para-dianhydrides. Copyright (C) 1996 Elsevier Science Ltd.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Synthesis and crystal structure of triphenyltin-2-(1,2-ethylenedithio) methylene-3-oxo-5-aryl-4-pentenicate

Nine triphenyltin - 2 - (1,2 - ethylenedithio) methylene - 3 - oxo - 5 - aryl - 4 - pentenicates were synthesized. The crystal structure of the title compound 3b (C33H28O3S2Sn) was determined by X - ray diffraction analysis. The crystal belongs to triclinic system, space group P(1)overbar with a = 0.9074 (2) nm, b = 1.6809(3)nm, c = 2.1834(4)nm, alpha =77.57(3)degrees, beta = 88.04(3)degrees, gamma = 89.47(3)degrees, V = 3.2503nm(3), Z = 2, R = 0.0592. In crystal of 3b, there exist intramolecular 0-Sn coordination bonds, with carboxylate group acting as a bidentate ligand: Sn(1)-0(1) = 0.2086(5) and Sn(1)-0(2) = 0.2594nm, having a deformed trigonal bipyramidal geometry.

Studies on the structure of tricyclohexyltin-2-(1,2-dithioethylene)methylene-3-oxo-5-aryl-4-pentenicate

Three title compounds were prepared and the structure of title compound 2 was characterized by IR, H-1 NMR, C-13 NMR, Sn-119 NMR spectroscopy and the crystal structure of compound 2a was determined by X-ray analysis with the final R indices[I >2 sigma (I)] R-1 = 0.0350 and R-2,R-omega = 0.0888. The crystal of compound 2a belongs to triclinic system, space group P1 with a = 1.0598(6) nm, b = 1.307 4(10) nm, c = 1.378 6(10) nm, alpha = 62.666(7)degrees, beta = 72.530(2)degrees, gamma = 80. 680(2)degrees, V = 1.618 0 nm(3), D-x = 1. 444 g (.) cm(-3), Z = 1, F (000) = 728. The bond length of Sn1-O1 is 0. 2076 nm and Sn1 . . . O2 distance is 0.301 3 nm. The coordination about the tin atom can be considered as a distorted tetrahedral. The detail values of H-1 NMR, C-13 NMR, Sn-119 NMR, (2)J(119Sn-1H) and J(119Sn-13C) were obtained. delta (119Sn) = 23.836, (2)J(119Sn-1H) = 88.0 Hz, (1)J(119Sn-13C) = 347.1 Hz, (2)J(119Sn-13C) = 45.6 Hz.

Effect of the nucleating agent 1,3 : 2,4-di(3,4-dimethylbenzylidene) sorbitol on the gamma phase content of propylene/ethylene copolymer

The influence of the concentration of a nucleating agent (NA), namely 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS), on the gamma phase content in a propylene/ethylene copolymer was investigated by means of Differential Scanning Calorimetry (DSC), Wide-Angle X-ray Diffraction (WAXD), Small- Angle X-ray Scatter (SAXS) and Polarized Optical Microscopy (POM).

Synthesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benzene

A new fluorinated diamine monomer, [1,4-bis(4-amino-3-trifluoromethylphenoxy)benzene (2)], and a known isomeric analog 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (3) were synthesized. A series of organosoluble polyimides Ia-d and IIa were prepared from the diamines (2, 3) and dianhydrides (a-d) by a high-temperature one-step method. The effects of the trifluoromethyl substituents on the properties of polyimides were evaluated through the study of their soluble, thermal, optical, and gas permeability properties. Polyimides (Ia-d) had glass transition temperatures between 229 and 279 degrees C, and the temperatures at 5% weight loss ranged from 510 to 533 degrees C under nitrogen. These polyimides could be cast into flexible and tough membranes from DMAc solutions. The membranes had tensile strengths in the range of 137-169 MPa, tensile modulus in the range of 1.6-2.2 GPa and elongations at break from 11% to 14%. The polyimide la with trifluoromethyl groups ortho to the imide nitrogen exhibited enhanced gas permeability, solubility, transparency, and thermal stability compared with the isomeric polyimide IIa with the CF3 group meta to the imide nitrogen.

1,4-二丙氧基-2,3-二氰基萘的合成

以1，4－萘醌为原料，经溴化、氰化、烷基化合成了1，4－二丙氧基－2，3－二氰基萘，用SiemensP4四圆衍射仪测得了晶体结构。合成方法简便，反应时间短，产率高。