Synthesis of New Amino—β-Cyclodextrin Polymer, Cross-Linked with Pyromellitic Dianhydride and Their Use for the Synthesis of Polymeric Cyclodextrin Based Nanoparticles

New water soluble amino β-cyclodextrin-based polymer was synthesized by reaction between amino cyclodextrin derivatives and pyromellitic anhydride. This experiment presents amino derivatives, which were synthesized by attaching amino groups to β-cyclodextrins (β-CDs) used mono-6-azido-6-deoxy-β-cyclodextrin (β-CD-N3) and triphenylphosphine (Ph3P) in anhydrous N,N-dimethylformamide (DMF). An amino blocking reaction was conducted. The obtained polymer was purified by ultrafiltration. In addition, an attempt was made to create nanospheres by encapsulating the polymer with chitosan (CT) in an acidic condition. For the first time, nanospheres were obtained in the reaction between an amino β-cyclodextrin polymer and chitosan. Scanning electron microscopy (SEM). 1H NMR and ESI-MS methods for confirmation of reaction product and for structural characterization were employed. The differential scanning calorimetry (DSC) studies of polymers were also carried out.

Preparation and Properties of Intrinsically Atomic-Oxygen Resistant Polyimide Films Containing Polyhedral Oligomeric Silsesquioxane (POSS) in the Side Chains

The relatively poor atomic-oxygen (AO) resistance of the standard polyimide (PI) films greatly limits the wide applications in low earth orbit (LEO) environments. The introduction of polyhedral oligomeric silsesquioxane (POSS) units into the molecular structures of the PI films has been proven to be an effective procedure for enhancing the AO resistance of the PI films. In the current work, a series of POSS-substituted poly (pyromellitic anhydride-4,4′-oxydianiline) (PMDA-ODA) films (POSS-PI) with different POSS contents were synthesized via a POSS-containing diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS). Subsequently, the effects of the molecular structures on the thermal, tensile, optical, and especially the AO-erosion behaviors of the POSS-PI films were investigated. The incorporation of the latent POSS substituents decreased the thermal stability and the high-temperature dimensional stability of the pristine PI-0 (PMDA-ODA) film. For instance, the PI-30 film with the DABA-POSS content of 30 wt% in the film exhibited a 5% weight loss temperature (T5%) of 512 °C and a coefficient of linear thermal expansion (CTE) of 54.6 × 10−6/K in the temperature range of 50–250 °C, respectively, which were all inferior to those of the PI-0 film (T5% = 574 °C; CTE = 28.9 × 10−6/K). In addition, the tensile properties of the POSS-containing PI films were also deteriorated, to some extent, due to the incorporation of the DABA-POSS components. The tensile strength (TS) of the POSS-PI films decreased with the order of PI-0 > PI-10 > PI-15 > PI-20 > PI-25 > PI-30, and so did the tensile modulus (TM) and the elongations at break (Eb). PI-30 showed the TS, TM, and Eb values of 75.0 MPa, 1.55 GPa, and 16.1%, respectively, which were all lower than those of the PI-0 film (TS = 131.0 MPa, TM = 1.88 GPa, Eb = 73.2%). Nevertheless, the incorporation of POSS components obviously increased the AO resistance of the PI films. All of the POSS-PI films survived from the AO exposure with the total fluence of 2.16 × 1021 atoms/cm2, while PI-0 was totally eroded under the same circumstance. The PI-30 film showed an AO erosion yield (Es) of 1.1 × 10−25 cm3/atom, which was approximately 3.67% of the PI-0 film (Es = 3.0 × 10−24 cm3/atom). Inert silica or silicate passivation layers were detected on the surface of the POSS-PI films after AO exposure, which efficiently prevented the further erosion of the under-layer materials.

Reduced Coefficients of Linear Thermal Expansion of Colorless and Transparent Semi-Alicyclic Polyimide Films via Incorporation of Rigid-Rod Amide Moiety: Preparation and Properties

Semi-alicyclic colorless and transparent polyimide (CPI) films usually suffer from the high linear coefficients of thermal expansion (CTEs) due to the intrinsic thermo-sensitive alicyclic segments in the polymers. A series of semi-alicyclic CPI films containing rigid-rod amide moieties were successfully prepared in the current work in order to reduce the CTEs of the CPI films while maintaining their original optical transparency and solution-processability. For this purpose, two alicyclic dianhydrides, hydrogenated pyromellitic anhydride (HPMDA, I), and hydrogenated 3,3’,4,4’-biphenyltetracarboxylic dianhydride (HBPDA, II) were polymerized with two amide-bridged aromatic diamines, 2-methyl-4,4’-diaminobenzanilide (MeDABA, a) and 2-chloro-4,4’-diaminobenzanilide (ClDABA, b) respectively to afford four CPI resins. The derived CPI resins were all soluble in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Flexible and tough CPI films were successfully prepared by casing the PI solutions onto glass substrates followed by thermally cured at elevated temperatures from 80 °C to 250 °C. The MeDABA derived PI-Ia (HPMDA-MeDABA) and PI-IIa (HBPDA-MeDABA) exhibited superior optical transparency compared to those derived from ClDABA (PI-Ib and PI-IIb). PI-Ia and PI-IIa showed the optical transmittances of 82.3% and 85.8% at the wavelength of 400 nm with a thickness around 25 μm, respectively. Introduction of rigid-rod amide moiety endowed the HPMDA-PI films good thermal stability at elevated temperatures with the CTE values of 33.4 × 10−6/K for PI-Ia and 27.7 × 10−6/K for PI-Ib in the temperature range of 50–250 °C. Comparatively, the HBPDA-PI films exhibited much higher CTE values. In addition, the HPMDA-PI films exhibited good thermal stability with the 5% weight loss temperatures (T5%) higher than 430 °C and glass transition temperatures (Tg) in the range of 349–351 °C.

Synthesis and characterization of new diacid monomers and poly (ester-imide) s: a study of thermal property relationship and solubility

Two dicarboxylic acids [2,2'-(((4-hydroxyphenyl) methylene) bis (3-Bromo-4,1- phenylene)) bis (1,3 dioxoisoindoline 5 carboxylic acid)) and 2,2 '(((2,4dichlorophenyl) methylene) bis (4,1-phenylene)) bis (1,3-dioxoisoindoline-5-carboxylic acid)] were made by the reaction of pyromellitic anhydride (PMDA) with diamine in a solvent of g pyridine/glacial acetic acid at refluxing temperature. The organization of the diacid monomers is defined by FTIR and 1H-NMR spectroscopy. The sequence of new poly (ester-imide) s are arranged of two di acids and aromatic diols: [Bis (4hydroxyphenyl) 2 furelmethaneand 4,4'((1,4phenylene (methanylyidene)) bis (azanylylidene)) diphenol] by employing the polycondensation in the company of the dibutyltine dilaurate as a catalyst. The PEIs were defined by FTIR, 1HNMR, and TGA. Poly (ester-imide) s showed excellent solubility in polar aprotic solutions because of the existence of flexible groups in the polymer backbone. Furthermore, they displayed better thermal constancy, and the heat at that 10% loss of weight happened about700 to 800°C.

Self-Healing Anti-Atomic-Oxygen Phosphorus-Containing Polyimide Film via Molecular Level Incorporation of Nanocage Trisilanolphenyl POSS: Preparation and Characterization

Protection of polymeric materials from the atomic oxygen erosion in low-earth orbit spacecrafts has become one of the most important research topics in aerospace science. In the current research, a series of novel organic/inorganic nanocomposite films with excellent atomic oxygen (AO) resistance are prepared from the phosphorous-containing polyimide (FPI) matrix and trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP–POSS) additive. The PI matrix derived from 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,5-bis[(4-amino- phenoxy)phenyl]diphenylphosphine oxide (BADPO) itself possesses the self-healing feature in AO environment. Incorporation of TSP–POSS further enhances the AO resistance of the FPI/TSP composite films via a Si–P synergic effect. Meanwhile, the thermal stability of the pristine film is maintained. The FPI-25 composite film with a 25 wt % loading of TSP–POSS in the FPI matrix exhibits an AO erosion yield of 3.1 × 10−26 cm3/atom after an AO attack of 4.0 × 1020 atoms/cm2, which is only 5.8% and 1.0% that of pristine FPI-0 film (6FDA-BADPO) and PI-ref (PMDA-ODA) film derived from 1,2,4,5-pyromellitic anhydride (PMDA) and 4,4’-oxydianline (ODA), respectively. Inert phosphorous and silicon-containing passivation layers are observed at the surface of films during AO exposure.

Using Microwave Irradiation for synthesis of Imides consist of Pyromellitimide

Bispyromellitimides are an important class of substrates in polymer chemistry as monomers in polyimides or their copolymers synthesis.A fast and efficient microwave-assisted synthetic procedure for the preparation of series of these compounds 3(a-h) from the reaction of pyromellitic anhydride and aniline or its derivatives (a-h) is described. Elemental analysis, FT-IR and1H-FT-NMR Spectra revealed the confirmation of these compounds in good agreement.

Rheological behavior of castor oil mixed with different pyromellitic esters

The paper presents the rheological behavior study of castor oil mixed with different pyromellitic esters. The pyromellitic tetraesters used were obtained through the esterification of pyromellitic anhydride with a special alcohol of a complex alkyl-aryl structure (2-phenoxy-ethanol) in conjunction with a linear aliphatic alcohol with variable length (n-butanol, n-decanol). The influence of pyromellitic esters? structure and concentration was determined, as well as that of temperature, on the rheological behavior, by setting the dependence between the shear stress ? and the shear rate ?. The analysis of dependence between ? and ? demonstrates that the studied solutions have Newtonian behavior. The evolution of samples' viscosity with temperature was characterized by Arrhenius type equations, being established the values of viscous flow activation energy, Ea. This constant can be correlated with the effect of reducing friction in the presence of additives. It was also realized a characterization of annulus fluids flow under the effect of rotational motion, calculating the values of Taylor-Reynolds number (TaRe).

Heat Resistant Poly(amide-imide)s Derived from N,N′-(4,4′-Pyromellitoyl)-bis-L-phenyl Acetic Acid and Aromatic Diamines: Synthesis and Properties

Six new heat resistant and optically active poly(amide-imide)s 5a–f were prepared by the direct polycondensation reaction of N,N′-(4,4′-pyromellitoyl)-bis-L-phenyl acetic acid 3 with various different diamines 4a–f in a medium consisting of triphenyl phosphite, N-methyl-2-pyrrolidone, pyridine and calcium chloride. These polymers were obtained in high yields and had inherent viscosities between 0.35–0.50 dL/g. The resulting polymers were characterized by viscosity measurements, thermal gravimetric analysis (TGA and DTG), differential scanning calorimeter (DSC), solubility test, specific rotation, FT-IR and 1H NMR spectroscopy. N,N′-(4,4′-pyromellitoyl)-bis-L-phenyl acetic acid 3 was prepared by an one-stop reaction of pyromellitic anhydride 1 with L-phenyl acetic acid 3 in acetic acid solution in quantitative yield.