The effect of molecular structure on the gas transmission rates of aromatic polyimides

A series of high-molecular weight condensation polyimides was evaluated to determine the effect of polymer molecular structure on the transmission rate of oxygen, carbon dioxide, and water vapor. The polyimide films were prepared from either 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) or pyromellitic dianhydride (PMDA) with various diamines. The study shows that molecular structure had a strong influence on gas transmission rates with results for some films varying three orders of magnitude from that of other polyimide films. In general, the BTDA series of polyimides had overall lower gas transmission rates than the PMDA-derived series. Polymers prepared with meta-oriented diamines characteristically displayed lower gas transmission than those prepared with para-oriented diamines.     

Effects of molecular structure on the permeability and permselectivity of aromatic polyimides

Permeability coefficients of H₂, O₂, and N₂ were measured under 10 atm at the temperature from ambient temperature up to 150°C in a series of structurally different aromatic homo-and copolyimides, which were prepared from 4,4′-oxydianiline (ODA) or 4,4′-methylene dianiline (MDA) with various aromatic dianhydrides. The study shows that the molecular structure of the polyimides strongly influences gas permeability and permselectivity. As a result, the permeability coefficients of the polyimide membranes for each gas vary by over two orders of magnitude. In general, among the polyimide membranes studied, the increase in permeability of polymers is accompanied by the decrease in permselectivity, and the MDA-based polyimide membranes have higher permeability than ODA-based ones. Among the polyimides prepared from bridged dianhydrides, the permeability coefficients to H₂, O₂, and N₂ are progressively increased in the order BPDA <BTDA <ODPA ∼ TDPA <DSDA <SiDA <6FDA, while H₂/N₂ and O₂/N₂ permselectivity coefficients are progressively decreased in the same order. The copolyimide membranes, which were prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride (SiDA), and ODA, have favorable gas separation properties and are useful for H₂/N₂ separation applications. © 1996 John Wiley & Sons, Inc.     

The effects of chemical structure on the shear rheology of aliphatic polycarbonates

Aliphatic polycarbonates are a relatively new class of polymer, which are characterized by an instability at the functional group, which makes them easily degraded and capable of biodegradation; as such, they constitute a potentially powerful group of polymers for exploitation in green technology. Rheological properties in shear flow are presented for the seven following different aliphatic polycarbonate samples: polyethylene carbonate, polypropylene carbonate, linear pentene polycarbonate, linear hexene polycarbonate, linear octene polycarbonate, cyclohexene polycarbonate, copolymer of propylene oxide (20%), and cyclohexene oxide (80%), using parallel plate rheometry. No studies of the rheological properties of aliphatic polycarbonates have been reported in the literature to date. The steady‐state and the dynamic properties of these new polymers are investigated, and the resulting flow curves and the dynamic relaxation spectra of the aliphatic polycarbonate melts are presented. One of the major problems encountered in trying to characterize the melt rheology and relate behavior to the underlying molecular structure is the instability of the polymers. Because of this, a narrow processing window is present for each polymer, and it makes it impossible to compare all polymers at a constant temperature or range of temperatures in the melt. Nevertheless, some progress can be made. In all cases, the rheological response is discussed in terms of molecular characteristics, in particular, the length of the side chain and the molecular weight distribution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 534–544, 2004     

The effect of monomer structure on oxygen inhibition of (meth)acrylates photopolymerization

Oxygen inhibition during the free-radical photopolymerization of various monomers containing ether groups was investigated using photo-DSC and real-time FTIR (RTIR). Methacrylates and acrylates containing different number and types of ether groups were selected to determine the effects of ether group concentration and structure on oxygen inhibition. Also, the oxygen sensitivity of the free-radical polymerization of methacrylate and acrylate was compared. Compared to acrylates, methacrylates are much less sensitive to oxygen. Model poly(tetramethylene oxide) and poly(propylene glycol) system were evaluated to determine the effect of ether groups on polymerization kinetics in air. The polymerizations of the (meth)acrylates containing ether groups were found to be relatively insensitive to oxygen inhibition. The reduction of oxygen inhibition occurs by a series of chain transfer/oxygen scavenging reactions.     

Effect of pore structure on gas permeability constants of porous alumina

Porous alumina was fabricated using different particle size, sintering temperature, and particle size and content of poly (methyl-methacrylate) (PMMA) as pore former. The Forchheimer equation was used to investigate the relationship between porosity and average pore size, and obtain the permeability constants k₁ and k₂ (the viscous effect and the inertial effect, respectively). Compared to Darcy's law, the Forchheimer equation established a more realistic and reliable relationship between fluid pressure and fluid velocity. k₁ and k₂ were found to be more sensitive to the average pore size than to the porosity of alumina. Moreover, reliable relationships were confirmed between the average pore size and k₁, k₂, and their ratio (k₁/k₂).     

Relationship between structure and aromatic solvent permeability of crosslinked polyurethanes based on hyperbranched polyesters

This work investigates the relationship between structure and aromatic solvent permeability of polyurethanes based on trimethylolpropane (TMP) as a classical crosslinker and self‐made hyperbranched polyesters (HBPEs) as newly developed crosslinking agents. For this purpose three groups of samples were synthesized using toluene diisocyanate, poly(tetramethylene glycol) and different pseudo‐generation numbers of crosslinkers in the variable hard segment content. The results obtained from characterization tests indicate that replacing TMP by HBPE leads to an increase of crosslink density resulting in significant reduction of sorption capacity and conversely leads to an increase of the diffusion coefficient due to the lower glass transition temperature (T_g) of soft segments. In this way, the toluene permeability of hyperbranched polyurethane (HBPU) is considerably lower than that of classical polyurethane. The HBPUs with sufficient amount of hard segment have the lowest solvent uptake and diffusion coefficient leading to optimal barrier performance. By increasing the generation number of HBPE, the crosslink density of HBPU increases, but the crystallinity as well as T_g of soft segments decrease. These two contradictory changing trends of the structural characteristics cause a slight decrease in sorption coefficient of membranes and an increase of diffusivity. Therefore the barrier performance of HBPUs is weakened with increasing generation number of crosslinkers. © 2015 Society of Chemical Industry     

The influence of monomer ratios on the properties of copolymers of 3,3′-spirobiphthalide and bisphenol A diglycidyl ether

Summary A spirobislactone, 3,3-spirobiphthalide (SBP), has been copolymerized with the diglycidyl ether of bisphenol A (DGEBA), and the properties of the products have been evaluated and related to the proportion (1–15%) of SBP monomer used. Polymers were characterized by infrared spectral analysis,¹³C NMR, thermal analysis, and mechanical testing. Polymers containing SBP have lower glass transition temperatures and higher decomposition temperatures than DGEBA polymers cured with phthalic anhydride (PA). Materials with higher SBP content have higher T_alpha values. Mechanical properties of the SBP copolymers are similar to those of DGEBA-PA polymers.     

The gas permeability of extruded graphite

The gas permeability of extruded graphite is extremely sensitive to the direction in which gas flow is measured. The technique of permeability measurement has been used to study the variation of pore structure of an extruded graphite and the data showed that a distinct directional pore pattern is present in this material. The factors which affect the pore structure of extruded graphites are discussed.     

The effect of phase separation on the structure and permeability of gelatin–dextran films

The effect of polymer–polymer phase separation on the transport properties of gelatin–dextran films has been studied. In the gelatin–dextran–water system, the phase separation and gel formation do not occur due to the presence of a nonsolvent, but depend entirely on the temperature and the total polymer concentration. It has been found that the permeability of polymer blend films to aqueous solutes can be varied not only by changing the volume ratio of the phases, but also by varying the size of the individual domains of the two phases in the films. Under the conditions of restricted demixing (e.g., after gel formation), the course of the phase separation process can be changed by varying the length of time allowed for unrestricted separation. The two most important parameters affecting the result are the total polymer concentration in the casting solution, and the temperature regime. An exponential dependence of the permeation coefficient on the volume fraction of the solvent in the film is shown.     

The effect of hydrogen pressure and aromatic structure on methane yields from the hydropyrolysis of aromatics

The chemistry of the formation of methane from the hydrogasification of naphthalene, substituted naphthalenes and toluene has been investigated using a flow tube. Temperatures were varied between 650–1050 °C (depending on the aromatic) and pressures ranged over 0.5–2 MPa. The results show that methane yields increase with increasing hydrogen pressure. For naphthalene the methane yield increases linearly with temperature for a given pressure. Methyl substituents are lost from aromatic rings, in a reaction which is insensitive to hydrogen pressure, to form 1 mole of methane and the parent aromatic. At these hydrogen pressures the phenolic group in 1-naphthol is removed predominately as H₂O to form naphthalene and the methane yields from this species parallel those from naphthalene. Analyses of the condensed products demonstrate that increased hydrogen pressure results in a reduction in the amounts of high molecular weight condensation products resulting in increased yields of methane.     

Synthesis,characterization, and gas permeability of aromatic polyimides containing pendant phenoxy group

A diamine containing a pendant phenoxy group, 1-phenoxy-2,4-diaminobenzene, was synthesized and condensed with different aromatic dianhydrides [4,4′-oxydiphthalic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracorboxylic dianhydride, and pyromellitic dianhydride] by one-step synthesis at a high temperature in m-cresol to obtain polyimides in high yields. Most of the polyimides exhibited good solvent solubility and could be readily dissolved in chloroform, sym-tetrachloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, and nitrobenzene. Their inherent viscosities were in the range of 0.33–1.16 dL/g. Wide-angle X-ray spectra revealed that these polymers were amorphous in nature. All these polyimides were thermally stable, having initial decomposition temperatures above 500°C and glass-transition temperatures in the range of 248–281°C. The gas permeability of 4,4′-oxydiphthalic dianhydride and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride based polyimides was investigated with pure gases: He, H₂, O₂, Ar, N₂, CH₄, and CO₂. A polyimide containing a  C(CF₃)₂ linkage showed a good combination of permeability and selectivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

双酚A型二胺和二酐与含吡啶环二胺共聚改性

用2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)和4-苯基-2,6-双(4-氨基苯基)吡啶(PBA P)作为二胺,双酚A型二酐(BPADA)作为二酐,以N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法.分别经热亚胺化和化学亚胺化过程合成了3种聚酰亚胺(PI).用傅里叶变换红外光谱表征聚合物的结构.结果表...     

The fire-resistance properties of polycarbonates

Summary The present paper describes two types of polycarbonates possessing fire-resistance. The first type is obtained by reacting dialkyl bis(hydroxy-4-phenyl) alkyl phosphonates with phosgene and the second type is a copolymer of bisphenol A and dialkyl bisphenol phosphonates.We show that the incorporation of dialkyl bisphenol phosphonates into the bisphenol A polycarbonate chains can be satisfactorily carried out using interfacial polycondensation.The products with groups-P (OCH₃)₂ possess high oxygen indices (OI).     

Impact strength of polymers. 3: The effect of annealing on cold worked polycarbonates

Cold working (rolling) of polycarbonates introduces residual stresses and molecular orientation both of which can improve, the notched Izod impact value. Annealing relieves both residual stresses and orientation. Annealing for various time periods established the critical level of residual stress necessary for the ductile failure mode of polycarbonate in the Izod impact test. The relaxation of both residual stress and molecular orientation was measured as a function of annealing temperature, for annealing times of 2 hs, and the relative changes have thus been determined. It is shown that residual stresses cannot be entirely removed without significantly influencing orientation for 2 h annealing times.     

Photopolymerization of an expanding monomer with an aromatic dioxirane

The objective was to study the photocationic polymerization of an expanding monomer, 1,5,7,11‐tetraoxaspiro[5.5]undecane (TOSU), and an aromatic dioxirane, bisphenol A diglycidyl ether (BADGE). Both homopolymerizations and binary polymerizations were conducted. The homopolymer, poly(TOSU), was found to be a linear poly(carbonate), which was soluble in acetone. Poly(BADGE) products contained ether linkages in addition to primary and secondary alcohol functionalities. Binary polymerization products varied depending on the irradiation time and length of dark cure. ¹³C‐NMR analysis of binary polymerizate products revealed peaks not seen in homopolymer spectra consistent with the formation of copolymer linkages. Mass spectrometry data revealed peaks consistent with oligomers that contained both TOSU and BADGE mer units. The structures of key reaction products were proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 62–71, 2004     

Synthesis,crosslinking, and abrasion and weathering properties of (meth)acrylate-terminated bisphenol A polycarbonates

(Meth)acrylate terminated bisphenol A polycarbonates [(M)AC PCs] were prepared under interfacial conditions by reaction of (meth)acryloyl chloride with bisphenol A (BA) followed by phosgenation. Addition of (M)ACl to an interfacial mixture of BA containing a catalytic amount of triethylamine followed by phosgenation gave linear polymers with good control of molecular weight. Thermal crosslinking of MAC PCs was generally achieved only in the presence of dicumyl peroxide. Between 75 and 98% gel was obtained by using 2 wt % initiator and heating for 30 min each at 150 and 200°C. All of the AC PCs crosslinked without added initiator to form 92–100% gel by heating for 30 min at 250°C. Coatings of high crosslink density (M)AC PCs on linear BA PC plaques were prepared by a combination of solvent casting, compression molding, and (optionally) oven curing. Moderate to high crosslink density (M)AC PC coatings showed relatively high pencil hardness values and good abrasion resistance. In weathering studies, both MAC and AC PC-coated plaques showed low YI increases, but the MAC PC coating developed higher haze due to microcracking. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 663–675, 1999