PHASE SEPARATION OF POLY(AMIC ACID-CO-IMIDE) SOLUTION

Poly(amic acid-co-imide) (PA-I) is an intermediate for preparation of polyimide from polyamic acid (PAA). Phase separation does not appear for the solution until a certain imidization degree. The experimental results of a rotation viscometer and FT-IR analysis showed that the critical point of phase separation (CPPS) was related to the imidization methods (thermal or chemical imidization) and the backbone structures (flexible ODPA-ODA or semi-rigid PMDA-ODA). Phase separation time is shorted with the increase of the initial PAA concentration, acetic anhydride amount, or temperature. When phase separation occurs, the solution viscosity increases, while the imidization degree is almost constant as the initial PAA concentration rises. The greater the chain mobility, the higher the imidization degree at phase separation point. At CPPS, higher imidization degree and lower solution viscosity are obtained in the thermal imidization than in the chemical imidization; ODPA-ODA system exhibits higher imidization degree and better solubility than that of PMDA-ODA system.     

Cyclodehydration of Poly (amic acid) to Polyimide

Abstract

It was observed that the cyclodehydration of PMDA-ODA or BTDA-ODA poly (amic acid) to polyimide in presence of ε-caprolactam takes place at a faster rate at lower temperature compared to the control film. It appears that the said lactam performed some catalytic function in the curing process and its influence was less in case of the PMDA based film than the BTDA based films. Also the rate of cyclodehydration of BTDA-ODA based poly (amic acid) to the corresponding polyimide is higher than the PMDA-ODA based poly (amic acid).     

Cohesive and continuum mixed-mode damage models applied to the simulation of the mechanical behaviour of bonded joints

The objective of this work is to discuss the adequacy of cohesive and continuum damage models for the prediction of the mechanical behaviour of bonded joints. A cohesive mixed-mode damage model appropriate for ductile adhesives is presented. The double cantilever beam and the end-notched flexure tests are proposed in order to evaluate the cohesive properties of the adhesive as a thin layer under mode I and mode II, respectively. A new data reduction scheme based on the crack equivalent concept is also proposed to overcome crack-monitoring difficulties during propagation in these fracture characterization tests. An inverse method to determine the cohesive parameters of the trapezoidal softening law is discussed. A continuum mixed-mode damage model is developed in order to better simulate the cases where adhesive thickness plays an important role. The model is applied to evaluate the effect of adhesive thickness on fracture characterization of adhesive joints. Some important conclusions about the advantages and drawbacks of cohesive and continuum damage models are reported.     

The chemistry involved in the loading of silver(I) into poly(amic acid) via ion exchange: A metal-ion-induced crosslinking behavior

Metal-ion-induced crosslinking of poly(amic acid) (PAA) was observed in the incorporation of silver ions into PAA through ion exchange. Studies on the interaction of silver ions with 3,3′,4,4′-benzophenonetetracarboxylic acid/4,4′-oxidianiline (BTDA/ODA)-based PAA suggest that the ion exchange reactions between poly(amic acid) and silver ions are not so simple as what we generally believed. It involves not only the formation of silver carboxylate but also the generation of diversified silver chemical entities arising from the strong chemical bonding of metal ions with the functional groups, such as carbonyl groups and amide groups, in the polymer chain, which are suggested to be responsible for the crosslinking behavior. Moreover, silver ions loaded into the film are readily self-reduced and provides us a convenient route to disperse very small metal nanoparticles into the polymeric matrix. Meanwhile, strong accelerating effect of silver ions was observed on the hydrolysis of PAA molecules and the characterization results indicate that about 14-16 wt% precursors were dissolved during the ion exchange in the aqueous silver ion solutions. Fortunately, it is found that the metal-ion-induced crosslinking structure formed in the silver-doped film has helped to prevent the damaging effect of silver ions and the essential structural features of PAA were retained in the remaining polymer matrix.     

The evolution of poly(hydroxyamide amic acid) to poly(benzoxazole) via stepwise thermal cyclization: Structural changes and gas transport properties

The thermally induced structure transformation and polymer chain rearrangement of a thermally rearranged (TR) material for gas separation has been explored in this work. A tremendous enhancement as high as 215 folds in CO₂ permeability has been achieved by converting the pristine poly(hydroxyamide amic acid) (PHAA) to the final polybenzoxazole (PBO) via thermal cyclization at 400 °C for 2 h. The evolution of the pristine polymer PHAA derived from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluropropane (BisAPAF) and trimellitic anhydride chloride (TAC) by thermal treatment from 130 °C to 400 °C has been examined by various characterization techniques including elemental analysis, TGA, TGA-IR, DSC, ATR-FTIR, XPS, XRD and Positron Annihilation Lifetime Spectroscopy (PALS). The stepwise cyclization process commences with cyclodehydration followed by cyclodecarboxylation. At the first step, PHAA transforms to poly(imide benzoxazole) (PIBO) up to 300 °C, while at the second step, the final structure of PBO is formed at 400 °C. Following the changes in the cyclization process, gas transport properties also show the stepwise changes. The significant enlargements of polymer inter-chain distance and free volume cavity radius provide the fundamental understanding for the changes of gas transport properties at the molecular level.     

Sorption and Permeation of Aqueous Alkyl Piperazines through Hydrophilic and Organophilic Membranes: A Transport Analysis

ABSTRACT

A detailed analysis of separation of N-methyl piperazine (NMP), N-ethyl pipera-zine (NEP), and water was undertaken by the pervaporation technique. A systematic study of sorption and permeation of the aqueous alkyl piperazines through poly(dimethylsiloxane) (PDMS), styrene-butadiene rubber (SBR), PDMS filled with zeolites NaX and silicalite (SA-5), polyimide (PI), and poly(acrylonitrile-co-acrylic acid) (PAN-co-AA) was carried out at different concentrations and temperatures. Organophilic membranes showed higher selectivity toward alkyl piperazines during sorption, but permeation was in favor of water. Hydrophilic membranes, however, showed higher affinity toward water during both sorption and permeation. PI membrane showed higher selectivity for water than PAN-co-AA. A model was used to estimate the diffusion coefficients of the various permeants. It was found that the transport selectivity for water in organophilic membranes was due to high diffusion selectivity (for water) although sorption selectivity favored the piperazines.     

Thermal Degradation of p-Hydroxybenzoic Acid in Macadamia Nut Oil,Olive Oil,and Corn Oil

p-Hydroxybenzoic acid (PHBA) plays a significant role in sustaining the oxidative stability of macadamia nut oil (MNO). However, PHBA undergoes thermal decarboxylation and loses its bioactive antioxidant properties. In this study, we determine PHBA degradation kinetics in oils at various heating temperatures, which provides fundamental understanding of PHBA thermal degradation in oils and oil quality changes during high-temperature processing. PHBA degradation kinetics in MNO, olive oil, and corn oil were evaluated at temperatures typical for cooking and frying. PBHA headspace concentration was measured using selected ion flow tube mass spectrometry. PHBA decarboxylation followed a zero-order reaction, where degradation could be affected by factors such as the type of oil matrix having different FA compositions, antioxidants, and component interactions. PHBA degradation activation energies (E _a) showed that PHBA was more stable against thermal decarboxylation in MNO (85 kJ mol^–1) than in olive oil (40 kJ mol⁻¹) or corn oil (22 kJ mol⁻¹). The higher enthalpy () of decarboxylation in MNO (82 kJ mol⁻¹) indicates that PHBA is more inhibited from decomposition than olive oil (37 kJ mol⁻¹) or corn oil (19 kJ mol⁻¹). Moreover, the negative entropy values () of PHBA degradation from MNO (−192 J mol⁻¹ K⁻¹), olive oil (−277 J mol⁻¹ K⁻¹), and corn oil (−325 J mol⁻¹ K⁻¹) indicates that these oils impart some inhibitory properties against PHBA thermal decarboxylation.     

Comparative Kinetic Study and Microwaves Non-Thermal Effects on the Formation of Poly(amic acid) 4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride (6FDA) and 4,4'-(Hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline (BAPHF). Reaction Activated by Microwave, Ultrasound and Conventional Heating

Green chemistry is the design of chemical processes that reduce or eliminate negative environmental impacts. The use and production of chemicals involve the reduction of waste products, non-toxic components, and improved efficiency. Green chemistry applies innovative scientific solutions in the use of new reagents, catalysts and non-classical modes of activation such as ultrasounds or microwaves. Kinetic behavior and non-thermal effect of poly(amic acid) synthesized from (6FDA) dianhydride and (BAPHF) diamine in a low microwave absorbing p-dioxane solvent at low temperature of 30, 50, 70 °C were studied, under conventional heating (CH), microwave (MW) and ultrasound irradiation (US). Results show that the polycondensation rate decreases (MW > US > CH) and that the increased rates observed with US and MW are due to decreased activation energies of the Arrhenius equation. Rate constant for a chemical process activated by conventional heating declines proportionally as the induction time increases, however, this behavior is not observed under microwave and ultrasound activation. We can say that in addition to the thermal microwave effect, a non-thermal microwave effect is present in the system.     

Effect of nucleation and plasticization on the crystallization of poly(lactic acid)

In this paper, different strategies to promote PLA crystallization were investigated with the objective of increasing the crystalline content under typical polymer processing conditions. The effect of heterogeneous nucleation was assessed by adding talc, sodium stearate and calcium lactate as potential nucleating agents. The PLA chain mobility was increased by adding up to 10 wt% acetyl triethyl citrate and polyethylene glycol as plasticizers. The crystallization kinetics were studied using DSC analysis under both isothermal and non-isothermal conditions. The isothermal data showed that talc is highly effective in nucleating the PLA in the 80-120 °C temperature range. In the non-isothermal DSC experiments, the crystallinity developed upon cooling was systematically studied at cooling rates of 10, 20, 40, and 80 °C/min. The non-isothermal data showed that the combination of nucleant and plasticizer is necessary to develop significant crystallinity at high cooling rates. The nucleated and/or plasticized PLA samples were injection molded and the effect of mold temperature on crystallinity was determined. It was possible to mold the PLA formulations using mold temperatures either below 40 °C or greater than 60 °C. At low temperature, the molded parts were nearly amorphous while at high mold temperatures, the PLA formulation with proper nucleation and plasticization was shown to achieve crystallinity levels up to 40%, close to the maximum crystalline content of the material. Tensile mechanical properties and temperature resistance of these amorphous and semi-crystalline materials were examined.     

Investigation of chemical transformations of thiophenylglycoside of muramyl dipeptide on the fumed silica surface using TPD-MS,FTIR spectroscopy and ES IT MS

In this study, chemical transformations of benzyl ester of О-(phenyl-2-acetamido-2,3-dideoxy-1-thio-β-d-glucopyranoside-3-yl)-d-lactoyl-l-alanyl-d-isoglutamine (SPhMDPOBn) on the fumed silica surface were examined, and the surface complex structure was characterized by temperature-programmed desorption mass spectrometry (TPD-MS), infrared spectroscopy (FTIR) and electrospray ion trap mass spectrometry (ES IT MS). Stages of pyrolysis of SPhMDPOBn in pristine state and on the silica surface have been determined. Probably, hydrogen-bonded complex forms between silanol surface groups and the C = O group of the acetamide moiety NH-(CH₃)-C = O…H-O-Si≡. The thermal transformations of such hydrogen-bonded complex result in pyrolysis of SPhMDPOBn immobilized on the silica surface under TPD-MS conditions. The shifts ∆ν of amide I band (measured from 1,626 to 1,639 cm^−l for SPhMDPOBn in pristine state) of 33 and 35 cm^−l which occurred when SPhMDPOBn was immobilized on the silica surface may be caused by a weakening of the intramolecular hydrogen bonding of the SPhMDPOBn because the interaction with the silica surface as hydrogen bond with silanol groups is weaker than that in associates.     

乳酸制备及其应用新进展

乳酸是公认的三大有机酸之一,目前已经在食品、医药、化工和聚合物材料等领域广泛应用。本文综述了乳酸的制备进展,尤其是近年来一些新的制备方法,同时对乳酸的应用进行了介绍,展望了乳酸行业未来研究和应用的主要方向。     

Study on the Crystallization Kinetic and Characterization of Poly(lactic acid) and Poly(vinyl alcohol) Blends

In this study, poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA) blends, with PLA/PVA mass ratios of 100/0, 90/10, 80/20, 70/30, 60/40, 50/50, and 40/60, were prepared by means of the melt blending method. The result of torque measurements and thermal gravimtric analysis tests showed that the addition of PLA can decrease the melt viscosity of PVA and that the second degradation step of PVA nearly disappeared for the PLA₈₀/PVA₂₀ blend. The absorbance peaks of the carbonyl group and the hydroxyl group in the Fourier transform infrared spectra of PLA/PVA blends had significant shifts to lower wave numbers, indicating that there were interactions between these two groups. Combined with the result of the differential scanning calorimetry curves, this interaction would be favorable for improving miscibility. The X-ray diffraction patterns and the polarized light microscope (PLM) micrographs showed that PVA can serve as a nucleating agent to promote the crystallization of PLA in PLA/PVA blends. Moreover, the PLA₈₀/PVA₂₀ blend gave the highest growth rate of PLA spherulite.     

生物降解材料制备及降解方法的研究进展

介绍了近年来淀粉基塑料、聚乳酸(PLA)基塑料的制备和降解方法。合适的改性剂、成型和降解方法,可以使淀粉和PLA成为力学性能和降解性能互补的共混体系。PLA/淀粉共混复合材料可作为以石油为原料的塑料的替代品。     

聚乳酸/纤维素及其衍生物共混复合材料的研究进展

介绍了聚乳酸(PLA)/纤维素、PLA/天然植物纤维、PLA/纤维素酯和PLA/纤维素醚共混复合材料最新的研究进展,综述了复合材料在相容性、分散性、力学性能和降解特性等方面存在的优点和缺点,为此类共混复合材料的进一步研究指明方向。     

An innovative approach for the chemical structural characterization of poly(styrene 4-vinylpyridine) copolymers by matrix-assisted laser desorption/ionization time of flight mass spectrometry

Poly(styrene-co-4-vinylpyridine) random copolymers with different molar composition were synthesized by nitroxide-mediated controlled-radical polymerization using 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) as a mediator. We record the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) spectra under various conditions, and we find (at last) that they show mostly intact ions [using 2(-4-hydroxyphenylazo-)benzoic acid as MALDI matrix]. Spectra are highly resolved, and thus they allow for the determination of all end-groups, even some less-abundant ones. Spectra are dominated by intact “dormant” copolymer chains terminated with TIPNO at one end and with (4-Bromo-phenyl)ethyl group (starting fragment) at the other one. Applying the mass analysis of copolymers (MACO) statistical model to the spectra, we show that the MACO/MALDI-TOF mass spectrometry (MS) analysis can be successfully applied to copolymers having a difference between the mass of the comonomers as small as 1 g mol⁻¹ (the styrene and 4-vinylpyridine units are 104.15 and 105.15 g/mol, respectively), which results in overlapping isotopic patterns. The results are accurate: chemical composition evaluated by means of MS agrees with that calculated by ¹H-nuclear magnetic resonance, for all copolymers investigated. This analytical method allows to extract detailed information on the composition of the copolymer samples and their structure. Glass transition temperatures of copolymers were also determined by differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46976.     

Quaternization of Cotton Stalks and Palm Tree Particles for Removal of Acid Dye from Aqueous Solutions

Cotton stalks and palm tree were independently grounded, washed thoroughly, and dried at ambient conditions. The cellulose of the obtained products was reacted with diepoxypropyl dimethyl ammonium chloride (III) along with 2-hydroxy-1,3-bis [(epoxypropyl dimethyl ammonium chloride) propane (IV)], thereby giving rise to quaternized products. Compounds III and IV were the resultants of activation with NaOH of a quaternizing agent known commercially as Refaktam K. Quaternization was carried out under different conditions, including material-to-liquor ratio, concentration of the activated Refaktam K, and time and temperature of the reaction. Nitrogen contents of the reaction products were taken as a measure of the extent of the reaction. Also reported was a thorough investigation into the ability of the quaternized products for acid dye adsorption by virture of their cationic nature. The adsorption data obey the Langmuir and Freundlish isotherms. It was further disclosed that the cationic products examined serve as excellent adsorbents for acid dye.     

Poly(lactic acid)–layered silicate nanocomposites: The effects of modifier and compatibilizer on the morphology and mechanical properties

Poly(lactic acid) (PLA) based nanocomposites were prepared to investigate the effects of types of nanoclays. Five different organically modified nanoclays (Cloisites^®15A, 25A, and 30B, and Nanofils^®5 and 8) were used. Two rubbery compatibilizers, ethylene‐glycidyl methacrylate (E‐GMA) and ethylene‐butyl acrylate‐maleic anhydride, were used in the nanocomposites as compatibilizer‐impact modifier. The degree of clay dispersion, the chemical compatibility between the polymer matrix and the compatibilizers, and changes in the morphology and mechanical properties of the nanocomposites were investigated. The mechanical properties and the morphological studies showed that the interactions between the different compatibilizers and PLA resulted in different structures and properties; such that the dispersion of clay, droplet size of the compatibilizer, and tensile properties were distinctly dependent on the type of the compatibilizer. Compatibility between C25A, C30B, and E‐GMA resulted in the best level of dispersion, leading to the highest tensile modulus and toughness among the compositions studied. In the mentioned nanocomposites, a network structure was formed owing to the high reactivity of the epoxide group of GMA towards the PLA end groups resulting in high impact toughness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42553.     

Structure and swelling of poly(acrylic acid) hydrogels: effect of pH, ionic strength, and dilution on the crosslinked polymer structure

The network formation of crosslinked polymer hydrogels made via a free radical polymerization mechanism is significantly influenced by the polymerization conditions. In particular, the crosslinked structure of ionic networks like poly(acrylic acid) copolymers is affected by the monomer concentration, the pH, and ionic strength during the polymerization. In this work experimental data as well as theoretical analysis are used to investigate how these factors control the degree of crosslinking and primary cyclization during the network formation of multifunctional monomers. It was found that the amount of water present during the polymerization increases primary cyclization rates, and this change affects the subsequent swelling behavior of the acrylic acid hydrogel. The effects of ionic strength and pH on the network structure are interrelated. An increase in the pH decreases the degree of primary cyclization while an increase in the ionic strength increases cyclization. To investigate further the effect of pH, a cationic polymer was formed that contained a monovinyl amine monomer and a novel diamine crosslinking agent synthesized in our laboratory. The combined effect of the ionizing backbone chain and crosslinking agent cause the degree of primary cyclization in this material to be extremely sensitive to the pH during polymerization. This result confirms the significant role of pH on the network formation in ionic materials.     

Solid-state C NMR analyses of the structures of crystallized and quenched poly(lactide)s: Effects of crystallinity, water absorption, hydrolytic degradation, and tacticity

The effects of crystallinity, water absorption, hydrolytic degradation, and tacticity on the solid structure and chain mobility of poly(lactide)s were investigated by solid-state ¹³C NMR spectroscopy. The following results were obtained from the line shapes of the carbonyl and methine carbons in ¹³C NMR spectra and their spin-lattice relaxation behavior. The crystallized poly(l-lactide) (PLLA) specimens in the dried, hydrated, and hydrolyzed states had two components, rigid and mobile components which can be, respectively, assigned to the crystalline and non-crystalline components. Upon water absorption, the chain mobility in the non-crystalline component of PLLA-C remained unvaried, reflecting a very small effect of the incorporated water molecules at room temperature. In contrast, the elevated chain mobility in the crystalline component and unclear splitting of carbonyl carbon strongly suggest that the water molecules are incorporated in the crystalline lattice. Upon removal of the non-crystalline components by hydrolytic degradation of crystallized PLLA, the chain mobility was slightly elevated in both crystalline and non-crystalline components by the lowered crystalline thickness and shortened non-crystalline chains. The non-crystalline specimens, PLLA (PLLA-Q) and poly(dl-lactide) (PDLLA), could be analyzed to contain two components, rigid and soft components, with the similar conformation but different restricted states of chains which cause high and low chain mobility. The insignificant difference in the spectral shapes and T_1C values between PLLA-Q and PDLLA strongly suggests that the effects of difference in the chain regularity and interaction on the spectral shapes and T_1C values are very low.     

Influence of molar mass and catalysts on the kinetics of crystallization and on the orientation of poly(ethylene terephthalate)

Poly(ethylene terephthalate) with different molar masses and different catalysts and additives (calcium acetate, manganese acetate, triphenylphosphate) was synthesized. The influence of the molar mass distribution, and of the additives used, on the rate of crystallization was studied. Also the dependence of the orientation obtained during drawing at elevated temperatures on the drawing conditions, on the average molar mass, and on the additives was investigated. It is shown that, under the same drawing conditions, an increase in molar mass leads to greater orientation. Also, at very small draw rates the orientation in the samples containing calcium acetate is greater than in those containing manganese acetate.