Fluorescence and IR characterization of epoxy cured with aliphatic amines

Cure reactions of the stoichiometric mixtures of diglycidyl ether of bisphenol A (DGEBA) and two very low molecular weight aliphatic polyether diamines (PED) were studied by using fluorescence and mid- and near-IR spectroscopic techniques. As the cure proceeded, the primary amine groups in PED are converted to the secondary and the tertiary amines. Near-IR spectral analysis was used to calculate the concentration of the three amine groups as a function of cure time. The decrease in the fluorescence intensity of DGEBA at about 307 nm was observed due to more effective quenching of the tertiary amine groups in PED, in comparison to the primary and the secondary amine groups. A large decrease in fluorescence intensity at 75 and 95 °C cure was observed. The amount of all the amine species was estimated from NIR spectra to shed light on the cure kinetics of PPO (polypropylene oxide) in comparison with PEO (polyethylene oxide) epoxy, as well as to explain their fluorescence behavior.The fluorescence intensity changes were correlated to the extent of epoxy reaction obtained by mid- and near-IR spectroscopy.     

Modification of poly(octadecene‐alt‐maleic anhydride) films by reaction with functional amines

Thin films of poly(octadecene‐alt‐maleic anhydride) on top of Si wafers and glass plates were modified by reactions with different functional amines to be used in future studies on the relevance of certain molecular surface properties for the covalent immobilization of proteins. For that aim, a strategy was developed and applied to convert the anhydride moieties of the copolymer by functional amines into side chains bearing hydrophilic groups of acidic (carboxylic acid, sulfonic acid), basic (amines), or neutral (poly(ethylene oxide) (PEO), glucose) character. The modification of the copolymer films was achieved through the two‐step formation of a cyclic imide, which was very stable in aqueous solution. Depending on the reactivity of the applied amine, the adjustment of the reaction time was suitable for the preparation of partially converted surfaces of the polymer film. Degrees of modification between 5 and 30% (according to X‐ray photoelectron spectroscopy data) were obtained. Annealing the modified polymer films induced efficient back‐formation of the anhydride groups. By reaction of the layered polyanhydrides with highly crosslinked diamines, amine‐functionalized polymer films were produced that were capable of binding secondary polyanhydride layers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1255–1266, 2003     

A GC–MS study of the addition reaction of aryl amines with acrylic monomers

Previous studies have shown that the interaction of carboxylic acid groups with the amine functionalities of aryl amines, especially secondary and tertiary aryl amines, can lead to the free-radical polymerization of acrylic monomers such as methyl methacrylate. In this study, the Michael addition reaction of primary and secondary aryl amines with acrylic monomers such as acrylic acid (AA) was investigated. Equivalent amounts of either p-toluidine (PT) or N-phenylglycine (NPG) and AA were combined in polar solvents such as ethanol. The reactions were conducted at ambient (23°C) or near-ambient (37–60°C) temperatures. Samples (about 3–5 mg) of these products were then trimethylsilylated with a solution consisting of 0.4 mL of bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 0.4 mL of acetonitrile by heating for 30 min at 140°C under N₂. These derivatives were characterized by gas chromatography–mass spectrometry (GC–MS). The GC–MS analyses suggest that 1 mol of the primary amine PT had reacted with 2 mol of AA to yield the expected N-p-tolyliminodipropionic acid. Similarly, the secondary amine NPG added to 1 mol of AA yielded the corresponding mixed iminodiacid, N-phenyliminoacetic–propionic acid. It would appear that the Michael reaction of primary and secondary amines with acrylic monomers may offer a general, facile synthetic route to a variety of tertiary amines. Aryl amino acids of the type synthesized in this study may find use in a number of dental applications, e.g., as surface-active adhesive agents and as polymerization initiators or activators. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 67:1545–1551, 1998     

Immobilization of amines at carbon fiber surfaces

The reaction between amines acting as nucleophiles and the C=C bonds on the carbon fiber surface acting as electrophilic vinyl groups has not yet been explored. In this contribution it is demonstrated that both thermal reactions and electrochemical oxidation of amines at carbon fibers allow the covalent bonding of these molecules directly to the carbon fiber surface, presumably via nucleophilic attack of the amine at electrophilic C=C sites at the surface and subsequent formation of C–N bonds between the surface and the amine. A novel strategy for a quantitative assay of the number of amines attached to the surface is developed in which Fe(CN)₆³⁻ is electrostatically bound to the protonated, cationic amine sites, followed by electrochemical determination of the amount of bound Fe(CN)₆³⁻ as a function of its concentration in solution. Analysis of the isotherm for this electrostatic binding process then provides a measure of the number of interfacially immobilized amines. The composition of the amine layer is also probed using X-ray photoelectron spectroscopy (XPS). Mechanisms are discussed by which attachment of amines at the electrophilic vinyl groups of the carbon fibers can occur. The likely influence that this type of reaction has on the interfacial shear strength in carbon fiber/epoxy composite materials is also discussed.     

Kinetics of isocyanate amine reactions

Development of polyurea-urethane and polyurea reaction injection molding (RIM) systems has created a need for kinetics of polyurea formation. Adiabatic batch reactions in solution were used to determine heats of reaction and relative reactivity of several aromatic amines and n-butanol with phenyl isocyanate (PI). In addition to comparing times required to reach 25, 50 and 75% conversion for both catalyzed and uncatalyzed reactions, n-th order models with Arrhenius rate constants were used to fit some of the exotherms. The reaction of 3,5-diethyl toluene (2,4 and 2,6)-diamine and PI could not be modeled due to unequal reactivity of the two amine groups. This unequal reactivity was studied using high performance liquid chromatography (HPLC) separation of the reaction products. The reactions of primary aliphatic amines and aromatic isocyanates were too rapid to be monitored in the batch apparatus. With a flow apparatus the reaction half time was estimated to be ～ 0.002 s.     

Network formation by aza‐Michael addition of primary amines to vinyl end groups of enzymatically synthesized poly(glycerol adipate)

A highly efficient approach for the synthesis of polyester‐based networks via aza‐Michael addition of primary amines to α,β‐unsaturated (vinyl) end groups of poly(glycerol adipate) (PGA) was achieved. By acylation of PGA with 6‐(Fmoc‐amino)hexanoic acid side chains via Steglich esterification, protected amine‐functionalized PGA was obtained. This was followed by the removal of fluorenylmethyloxycarbonyl (Fmoc) protecting groups and the synthesis of PGA‐based networks under catalyst‐free conditions. The successful conjugate addition of primary amines to vinyl end groups and network formation were confirmed using ¹³C magic angle spinning NMR and Fourier transform infrared spectroscopy. Network heterogeneity and defects were quantitatively investigated using ¹H double‐quantum NMR spectroscopy. Finally, a hydrogel was prepared with potential biomedical applications.     

Etherification versus amine addition during epoxy resin/amine cure: An in situ study using near-infrared spectroscopy

The reactions between a multifunctional epoxy resin, tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) and a monofunctional amine, methylaniline (mAnil) are studied. Due to the existence of a tertiary amine catalytic center within the TGDDM molecule, the etherification reaction during cure of TGDDM is usually more significant than in other epoxide systems. The importance of this reaction relative to the amine addition reactions is investigated. In situ near-infrared spectroscopy is used to obtain kinetic data during the cure reactions. The reaction rate constants are calculated from linear regression analysis for both amine addition and etherification reactions based on the reaction mechanisms proposed. Arrhenius relationships are observed for all the reaction rate constants involved. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:895–901, 1998     

The Acidity of Zeolites: Concepts,Measurements and Relation to Catalysis: A Review on Experimental and Theoretical Methods for the Study of Zeolite Acidity

In this article, we considered all aspects of acidity (nature of acid sites, strength, density, etc.) in solid catalysts and in zeolites in particular. After reminding the definition of acidity in liquid and solid acids, we emphasized acidity characterization by the most used physical techniques, such as Hammett's indicator titration, microcalorimetry of adsorbed probe molecules (ammonia, pyridine or other amines for acidity characterization and CO₂ or SO₂ for basicity characterization), ammonia or any amine thermodesorption, IR spectroscopy of hydroxyl groups and of several probe molecules adsorbed (ammonia, pyridine, piperidine, amines, CO, H₂, etc.), MAS-NMR of ²⁷Al, ²⁹Si, ¹H elements and of ¹H, ¹³C, ³¹P, etc. of adsorbed probe molecules, and model catalytic reactions.

Modeling the way the acid features of zeolites influence the catalytic activity of these catalysts toward acid-catalyzed reactions (relation between ammonia desorption activation energy values and catalytic activities, reaction mechanism, and kinetics) completes the general analysis of acidity and zeolite chemistry.     

Kinetic study of the urethane and urea reactions of isophorone diisocyanate

Kinetic studies of the catalyzed urethane reactions between isophorone diisocyanate (IPDI) and alcohols and of the urea reactions between an isocyanate‐terminated prepolymer [IPDI–PPG2000–IPDI, where PPG2000 is poly(propylene glycol) with a number‐average molecular weight of 2000 g/mol] and water in the bulk state were performed with Fourier transform infrared (FTIR) spectroscopy. Dibutyltin dilaurate was used as the catalyst for the urethane reaction, and various tertiary amines were used as catalysts for the urea reactions. The reactions were followed through the monitoring of the change in the intensity of the absorbance band for NCO stretching at 2270 cm^?1 in the FTIR spectra; the activation parameters were determined through the evaluation of the kinetic data obtained at various temperatures (within the range of 30–60°C). The kinetic data indicated that the catalyzed isocyanate/alcohol and isocyanate/water reactions both followed second‐order kinetics during their initial stages but later followed third‐order kinetics resulting from the autocatalytic effects of hydrogen bonding between the hydroxyl groups and the newly formed urethane and urea groups. Furthermore, activation energies of 64.88 and about 80 kJ/mol for the isocyanate/alcohol and isocyanate/water reactions, respectively, indicated that the urea‐forming reactions were more sensitive to the reaction temperature than the urethane‐forming reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Kinetics and simulation of the imidization of poly(styrene‐co‐maleic anhydride) with amines

The imidization of poly(styrene‐co‐maleic anhydride) with amines may improve some of its end‐use properties. The objective of this study was to examine the mechanism and kinetics with aniline (ANL) as an amine of the preparation of poly(styrene‐co‐N‐phenyl maleimide). The reaction was carried out in a tetrahydrofuran solution at 25–55°C and in an ethylbenzene solution at 85–120°C. The extent of the reaction was determined by conductance titration, a new and simple method. Two consecutive reactions were involved in the imidization: ring opening to produce an acido‐amide group and ring closing to form a corresponding imide group. The imidization rate was greatly influenced by the reaction temperature and the molar ratio of ANL to the anhydride. A model for the imidization kinetics over a wide range of reaction temperatures and concentration ranges was developed and validated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2744–2749, 2006     

An experimental and theoretical study on the effects of amine chain length on CO2 absorption performance

To explore the effect of amine chain length on CO₂ absorption performance, the reaction kinetics of CO₂ absorption in aqueous 1-dimethylamino-2-propanol (DMA2P), 1-diethylamino-2-propanol (DEA2P), 2-(methylamino)ethanol (MAE), and 2-(ethylamino)ethanol (EAE) solutions with different concentrations were explored using the stopped-flow apparatus. Additionally, Density Functional Theory (DFT) calculations were conducted to examine the reaction mechanism and the free energy barrier of the elementary reactions underlying CO₂ absorption in these four aqueous amine solutions. Kinetic models for CO₂ absorption in tertiary amines and secondary amines were established, based on the base-catalyzed hydration mechanism and the zwitterion mechanism, respectively, both of which perform well in predicting the relationship between k₀ and the amine concentration. The free energy barrier obtained by DFT is consistent with the activation energy barrier trend obtained by experiment. In addition, the effect of chain length on the free energy barrier was investigated through the chemical bond and weak interaction analysis.     

Diamine versus amines blend for CO2 chemical absorption

Present work analyses the behavior of aqueous solutions of N,N-dimethylethylenediamine as chemical solvent for carbon dioxide separation by gas–liquid absorption. The interest of this molecule is centered on the presence of different types of amino centers that confer it the capability to act as a solvent based on amines blend. For this reason, a comparison between diamine and amines blend solvent has been carried out in order to understand the differences between these solvents using absorption and nuclear magnetic resonance studies. This experimental work analyses the influence of amine type, concentration, and ratio between different amines. Also, the effect of gas flow rate used in the bubble column reactor upon the absorption kinetics has been analyzed.     

Influence of structure of amines on the properties of amines‐modified reduced graphene oxide/polyimide composites

Graphene oxide (GO), as an important precursor of graphene, was functionalized using alkyl‐amines with different structure and then reduced to prepare reduced amines grafted graphene oxide (RAGOs) by N₂H₄ · H₂O. The successful chemical amidation reaction between amine groups of alkyl‐amines and carboxyl groups of GO was confirmed by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA). Then RAGOs/polyimide nanocomposites were prepared via in situ polymerization and thermal curing process with different loadings of RAGOs. The modification of amine chains lead to homogenous dispersion of RAGOs in the composites and it formed strong interfacial adhesion between RAGOs and the polymer matrix. The mechanical and electrical properties of polyimide (PI) were significantly improved by incorporation of a small amount of RAGOs, the influence of structure of amines grafted on RAGOs on the enhancement effects of composites was discussed. The research results indicated that the proper structure of amine could effectively enhance the properties of composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43820.     

CO2 capture by pyrrolidine: Reaction mechanism and mass transfer

A new carbon dioxide capture process by means of gas–liquid absorption using pyrrolidine aqueous solutions in a bubble column reactor obtaining suitable results in comparison with other commonly used amines is analyzed. The influence of several operation variables such as amine concentration and gas flow rate has been studied. Carbon dioxide mass‐transfer rate data have shown a different behavior than other amine‐based systems because a constant value in absorption rate was observed in the middle of batch experiments. ¹³C and ¹H NMR spectroscopy studies were performed to analyze the species present during the experiments. These data and the carbon dioxide loading allowed to explain the reaction mechanism existed between these reagents. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1098–1106, 2014     

New evidence related to reactions of aminated silane coupling agents with carbon dioxide

The nature of the product of the reaction between an aminated silane and carbon dioxide was re-examined with the aid of simple model compounds, several amines, and several aminosilanes. Since the reaction products previously proposed include the amine bicarbonate and a carbamate derived from the amine, ammonium bicarbonate and ammonium carbamate were studied as models for the anions. Carbon dioxide adducts of neat model amines were prepared and studied. Results from a variety of techniques are summarized. Among the most useful was Fourier transform infrared (FTIR) spectroscopy of fluorolube mulls. FTIR spectra were distinctive and assignments characteristic of the two species were extracted from the spectral data. Comparisons of these assignments with the products of the reaction between carbon dioxide and various amines were made. The results indicate that alkylammonium carbamates are the principal product. Nuclear magnetic resonance (NMR) spectra in D₂O indicated much dissociation and were not helpful in defining the products.     

Mass spectrometric analysis of polymers derived from N-aryl-α-amino acid initiators

Previous studies have demonstrated that the interaction of carboxylic acids with aryl amines produces free radicals that can initiate the polymerization of acrylic monomers. N-Aryl-α-amino acids (NAAA) represent a special class of this type of initiator that combines in one molecule the carboxylic acid and aryl amine functionalities necessary for the generation of radical species. The mechanism(s) of radical formation in these molecules is thought to involve both electron transfer and hydrogen abstraction reactions that can occur by intra- and intermolecular pathways. Acrylic monomers, i.e., methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA), were activated with various amounts of several NAAAs. Specific NAAAs investigated include N-phenylglycine (NPG) and N-p-tolylglycine (NTG). Polymerization was conducted at ambient or near ambient temperatures, and the polymers then were analyzed by electron impact mass spectrometry. Results indicate that these polymers have end groups derived directly from the NAAA initiators. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:561–565, 1997     

Study on the acidic hydrolysis process of poly(N‐vinylformamide/acrylonitrile) fiber

A convenient method of preparing chelating fiber with amine groups on the fiber surface was developed. The precursor polymer of Poly(N‐vinylformamide/acrylonitrile) (P(NVF/AN)) was synthesized via solution polymerization, using N‐vinylforaimde as a functional monomer. The solution of P(NVF/AN) was spun through a wet spinning method and the precursor fiber was hydrolyzed in the hydrochloric acid solution to convert formamide moieties to the corresponding amine. The influence of hydrolytic conditions on hydrolysis degree, such as hydrolysis temperature, hydrolysis time, and hydrochloric acid concentrations were examined experimentally. The hydrolysis degree of the precursor fiber was evaluated by potentiometric and conductometric titrations. The changes of the structure and properties of the fibers were characterized through infrared spectroscopy, scanning electron microscopy, and tensile strength tester. The results showed that the hydrolysis degree was limited in acidic hydrolysis because of the electrostatic repulsion among the cationic amine groups and proton. The hydrolysis degree of precursor fiber reached nearly 60%, and the chelating fiber remained the adequate mechanical properties under the suitable hydrolysis condition. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synergistic effect between hindered amine light stabilizers and partially hindered oligomeric amines in polyethylene

The synergistic effect between novel synthesized oligomeric amines and a commercial hindered amine light stabilizer (Chimassorb 944) was studied in medium‐density polyethylene (MDPE). Mixtures of the synthesized oligomeric amines and commercial additives were prepared at different concentrations and then were evaluated by ultraviolet and thermal aging. The evaluation was carried out on films prepared by compression molding, and the oxidation rates were monitored with Fourier transform infrared, which was used to measure the formation of different functional groups: carbonyl, vinylic, and hydroperoxide. The data showed that, independently of the concentration of the commercial additives, when they were combined with oligomeric amines, they produced a synergistic effect with a magnitude depending on the MDPE aging conditions and the additive concentrations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 280–287, 2004     

New biobased epoxy hardeners: Thiol-ene addition on oligobutadiene

We report the synthesis and characterization of oligobutadienes functionalized with primary amine groups and theirs use as hardeners for epoxy resins. The functionalization of polybutadiene (with 59% of 1,2 double bonds) was carried out by the addition of 2-amino-3-mercaptopropanoic acid (cysteamine) in different ratios through thiol-ene coupling. The thiol-ene addition was performed in tetrahydrofurane solvent with 2,2′-azobis(2-methylpropionitrile) as radical initiator at 70 °C. The ratio polymer/cysteamine was varied in order to obtain several number of amine functions per polymer chain and to compare the reactivity of thiol onto 1,2 and 1,4 double bonds of polybutadiene. The different characterizations of synthesized polymeric amines allowed us to identify the quantities of amine groups grafted onto 1,2 and 1,4 double bonds, the cyclization side reactions of 1,2 double bonds and the unreacted 1,2 and 1,4 double bonds. These polymeric amines were mixed with epoxy resins (BADGE) and led to materials with glass transition temperatures between 20 °C and 60 °C depending on the polymeric amines functionalities. The thermal properties of synthesized resins are similar to the ones measured on epoxy resins obtained with commercial hardeners (cycloaliphatic amine and 1,10-diaminodecane).     

Cinnamylidene-amine-sensitized photodegradation of polyethylene

The activity of Schiff's bases of cinnamic aldehyde and aromatic amines in the controlled photodegradation of polyethylene (PE) was studied. N-cinnamylidene anilines containing different substituents in the amine ring (methyl group, halogen, or amine group) and N-cinnamylidene α-naphthyl amine were synthesized and introduced into the polyethylene films by compression molding or extrusion, and they were exposed to the filtered ultraviolet light produced by mercury lamp. The changes in molecular weight, tensile strength, and characteristic IR absorptions were followed during irradiation to control the processes undergoing in the polymer films. It was discovered that N-cinnamylidene anilines containing methyl or halogen substituents and N-cinnamylidene α-naphthyl amine accelerated the photodegradation of polyethylene. Their sensitizing activity increased when the mixtures of Schiff's bases and stannous laurate were introduced into the polymer. PE films containing these additives became brittle after 600 h exposure to the artificial UV light which was the equivalent of 1.5–2 years exposure to the natural sunlight in the medium geographic latitudes. The mechanism of the initial step of photodegradation is discussed.