New poly(amide-imide) siloxane copolymers by polycondensation

Some new poly(amide-imide) siloxane copolymers have been synthesized by solution polycondensation of some aromatic diamines with siloxanic diacids having preformed imide rings. Two polycondensation techniques were used: polycondensation of aromatic diamines with diacid chlorides and direct polycondensation of aromatic diamines with diacids in the presence of organic phosphites, following the Yamazaki-Higashi phosphorylation technique. In all cases the reactions were carried out using equimolecular amounts of the two monomers, in polar aprotic solvents and inert atmosphere.The obtained compounds were characterized by elemental C, H and Si analysis, solubility tests, IR and ¹H-NMR spectrometry. Thermogravimetric curves were also recorded. All data agree with the proposed structures.     

Preparation of amphiphilic polyisobutylenes-b-polyethylenamines by mannich reaction. II. Study of mannich reaction on model systems

The study of the reactions which take place when α-methyl-ω-phenolpolyisobutylene is polycondensed with triethylenetetramine (TETA) and para-formaldehyde (Mannich condensation) is carried out on model systems including monofunctional [2,4-di-tert-butylphenol ( A ), dibutylamine ( B ), and dodecylamine ( B ′)] and difunctional reactants [4-tert-butylphenol ( A ′) and 1,6-hexamethylenediamine ( B ″)]. With the exception of the A + B system which gives only Mannich condensation, all the systems including at least one difunctional reactant are characterized by side reactions which accompany the Mannich condensation. However, when one of the compounds is monofunctional ( A + B ;′ A ′ + B ′) only nonpolymeric molecules are formed; their structures were determined by ¹H- and ¹³C-NMR spectroscopy. On the other hand, when both reactants are bifunctional ( A ′ + B ; A ′ + TETA) polymers are formed whose monomer units were identified by comparison of their spectra with those of the nonpolymeric molecules. © 1993 John Wiley & Sons, Inc.     

Structure–reactivity relationships and the rate–determining step in the reactions of methyl salicylate with primary amines

The aqueous cleavage of methyl salicylate has been studied in the buffer solutions of various primary mono- and di-amines as well as secondary amines at 30°C. Both ionized (MS^?) and nonionized (MSH) methyl salicylate are reactive toward primary mono- and di-amines. The second-order rate constants for the reactions of MS^? with primary mono- and di-amines of pK_a > 9.4 exhibit Bronsted plot of slope (β_nuc) of 0.82. This high value of β_nuc is attributed to an intramolecular proton transfer in a thermodynamically unfavorable direction in the rate-determining step in a stepwise process for the formation of monoanionic tetrahedral intermediate. However, a concerted process for the formation of a monoanionic tetrahedral intermediate in the reactions of MS^? with amine nucleophiles wherein expulsion of leaving group is a rate-determining step is not completely ruled out. The α-effect nitrogen nucleophiles hydroxylamine and hydrazine reveal, respectively, ca. 10⁴- and 10³-fold higher reactivity compared to other amine nucleophiles of comparable basicity. The value of β_nuc of 1.03 obtained for the reactions of primary monoamines with MSH is ascribed to the expulsion of leaving group as the rate-determining step. The significantly lower value of β_nuc of 0.60 obtained in the reactions of MSH with both monoprotonated and unprotonated diamines is explained in terms of possible occurrence of intramolecular general acid-base catalysis. Intramolecular general base catalysis is responsible for the enhanced nucleophilic reactivity of primary amines toward MS^?. Dimethylamine, piperidine, morpholine, and piperazine have no detectable nucleophilic reactivity toward MS^?.     

Polymeric Schiff Bases. III. Some Prototype Exchange Reactions of Schiff Bases

The amine moiety in Schiff bases can be exchanged quantitatively by another amine to yield new Schiff bases if the volatility of the replacing amine is lower than the derived amine, thereby allowing the latter to distilled from the reaction mass. This amine exchange was shown to be quantitative also for diamines and di-Schiff bases. Similarly, quantitative conversions were found for aldehydes and acetal exchanges with Schiff bases for both monofunctional and difunctional reactants. The bis exchange, involving two complementary Schiff bases, was quantitative also when the reactants were so selected that one of the new derived Schiff bases could be removed by distillation. The bis exchange was demonstrated with mono and di-Schiff bases.

Mechanisms are suggested for these Schiff base exchange reactions: attempts to isolate the proposed intermediates physically were unsuccessful; however spectroscopic evidence indicates the formation of intermediate compounds.

The Schiff base exchanges involving polyfunctional reactants are of interest in the synthesis of polymers.     

Synthesis and characterization of new optically active poly(amide‐imide)s containing epiclon and L‐methionine moieties in the main chain

Epiclon [3a,4,5,7a‐tetrahydro‐7‐methyl‐5‐(tetrahydro‐2,5‐dioxo‐3‐furanyl)‐1,3‐isobenzofurandione] (1) was reacted with L ‐methionine (2) in acetic acid and the resulting imide‐acid 3 was obtained in high yield. The diacid chloride 4 was prepared from diacid derivative 3 by reaction with thionyl chloride. Thermostable poly(amide‐imide)s containing epiclon structure were synthesized by reacting of diacid chloride 4 with various aromatic diamines. Polymerization reaction was performed by two conventional methods: low temperature solution polycondensation and short period reflux conditions. In order to compare conventional solution polycondensation reaction methods with microwave‐assisted polycondensation, the reactions were also carried out under microwave conditions with a small amount of o‐cresol that acts as a primary microwave absorber. The reaction mixture was irradiated for 6 min with 100% radiation power. Several new optically active poly(amide‐imide)s with inherent viscosity ranging from 0.15 to 0.36 dl/g were obtained with high yield. All of the above polymers were fully characterized by ¹H‐NMR, FT‐IR, elemental analyses and specific rotation techniques. Some structural characterizations and physical properties of these new optically active poly(amide‐imide)s are reported. Copyright © 2005 John Wiley & Sons, Ltd.     

Reaction de redistribution entre le tripropylbore et ses produits d'oxydation: Etude par résonance du Noyau 11B

A study by B¹¹ NMR of the system tripropylborane–boron trioxide shows that scrambling reactions occur between the alkylborane and its oxidation products; this involves a redistribution of the mono-(? C₃H₇) and difunctional (? O? ) substituents attached to boron, leading to molecules of varying size and structure.     

Synthesis and characterization of novel,optically active poly(amide‐imide)s from N,N′‐(4,4′‐sulfonediphthaloyl)‐bis‐L‐phenylalanine diacid chloride and aromatic diamines under microwave irradiation

3,3′,4,4′‐Diphenylsulfonetetracarboxylic dianhydride was reacted with L ‐phenylalanine in acetic acid, and the resulting imide acid ( 3 ) was obtained in high yield. The diacid chloride ( 4 ) was obtained from its diacid derivative ( 3 ) by reaction with thionyl chloride. The polycondensation reaction of 4 with several aromatic diamines such as 4,4′‐sulfonyldianiline, 4,4′‐diaminodiphenyl methane, 4,4′‐diaminodiphenylether, p‐phenylenediamine, m‐phenylenediamine, 2,4‐diaminotoluene, and 1,5‐diaminonaphthalene was developed with a domestic microwave oven in the presence of trimethylsilyl chloride and a small amount of a polar organic medium such as o‐cresol. The polymerization reactions were also performed with two other methods: low‐temperature solution polycondensation in the presence of trimethylsilyl chloride and reflux conditions. A series of optically active poly(amide‐imide)s with moderate inherent viscosities of 0.21–0.42 dL/g were obtained in high yield. All of the aforementioned polymers were fully characterized by IR, ¹H NMR elemental analyses, and specific rotation techniques. Some structural characterizations and physical properties of these optically active poly(amide‐imide) s are reported. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3974–3988, 2003     

Synthesis of AB(BA), ABA and BAB block copolymers of tert-butyl methacrylate (A) and ethylene oxide (B)

Well-defined AB(BA), ABA, and BAB block copolymers of tert-butyl methacrylate (tBMA) (A) and ethylene oxide (EO) (B) have been prepared by sequential living anionic polymerization of the two comonomers, irrespective of their addition order. Diphenyl methyl potassium and naphthalene potassium have been successfully used as mono- and difunctional initiators, respectively. In all cases, molecular weight and composition of the block copolymers can be predicted on the basis of the monomer over initiator molar ratio, and the molecular weight distribution is relatively narrow. Size exclusion chromatography, selective extractions of homopolymers, and ¹H- and ¹³C-NMR spectroscopy support that block copolymerization proceeds without homopolymer formation nor side reactions, e.g., transesterification reactions. The PtBMA blocks have been quantitatively hydrolyzed into polyacid ones with formation of polyacid-b-polyether block copolymers as supported by titration, ¹H-NMR, and IR analysis. © 1992 John Wiley & Sons, Inc.     

Aromatic polyimide-co-amides. I

A series of aromatic polyimide-co-amides of high thermal stability were synthesized. Low-temperature solution condensation involving aromatic diamines of varying basicity and bifunctional carboxylic acid chlorides containing performed imide rings was empolyed. This approach offers several advantages over the conventional polyamic acid route. The final polymers obtained are linear, soluble, and of high molecular weight. Solution of the final polymers are stable in contrast to polyamic acid solutions, which depolymerize hydrolytically due to the neighboring-group effect. Tough, flexible films were cast from solution and required no heat cure. The properties of one polymer made by the preformed ring approach were compared to its structurally related amide and imide homologs.     

Synthesis and characterization of new polyamideimides with a highly flexible soft block

Five new polyamideimides (PAI) were synthesized from five diacid chlorides with preformed imide rings and a telechelic α,ω-diamino-polyoxyethylene (Jeffamine JFA ED600). The diacid chloride monomers could be obtained in high yields (77–92%) from chlorinating the corresponding diacids which were obtained from the reaction of trimellitic anhydride with aromatic diamines (1,4-phenylene diamine; 2,2-bis(4-aminophenyl)methane; 2,2-bis(4-aminophenyl)propane; 4,4′-oxydianiline and 1,1-bis(4-aminophenyl)cyclohexane). The telechelic monomers were characterized by FTIR and ¹H-NMR. After a few preliminary experiments aimed at optimizing the polymerization conditions for particularly poorly soluble diacid chlorides, five new PAI were synthesized with inherent viscosities in the range of 0.35–0.65 dL/g. Their characterization by transmission FTIR and by advanced NMR techniques, including heteronuclear 2D NMR, fully confirmed their chemical structure as shown by the complete assignments of their ¹H and ¹³C-NMR spectra. Compared with other PAI described in the literature, these polymers proved to be much more sensitive towards polar organic solvents even showing significant solubilities in chloroform and tetrahydrofuran. These materials enabled the casting of transparent films which were very tough in the dry state. However, and as further evidenced by a DSC investigation, their phase separation is usually not sufficient to provide a very strong physical crosslinking by the aggregation of the polymer hard blocks. Consequently, their physical crosslinking would have to be significantly improved for preventing the material failure in highly solvating media and open the way for new performances in membrane separation systems. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2873–2889, 1999     

Heterocyclic Polyimides

This paper presents the synthesis of certain polyimides which contain one of the following heterocycles: oxadiazole, benzox-azinone, benzthiazole. Their properties, particularly thermal stability and hydrolytic stability, are compared to fully aromatic polyimides. Poly-1,3,4-oxadiazole-imides have been synthesized either by the reaction of ditetraeole monomers which contain preformed imide cycles with diacid chlorides, or by the reaction of an aromatic diamine containing a preformed oxadiazole ring with diacid chlorides containing preformed imide rings. Polybenz-oxazinone-imides have been synthesized by polycondensation of a bis(amino acid), 4,4′-diaminodiphenylmethane-3,3′-dicarboxylic acid, with diacid chlorides containing preformed imide rings. Polybenzthiazole-imides have been obtained by polycondensation of aromatic diamines containing a preformed benzthiazole ring with diacid chlorides containing preformed imide rings. Thermal stabilities of these heterocyclic polyimides are similar and in certain cases are higher than those of fully aromatic polyimides. It was also found that the hydrolytic stability of heterocyclic polyimides is definitely superior to that of aromatic polyimides.     

Ferrocene compounds. XXV. Synthesis and characterization of ferrocene‐containing oligoamides,their precursors,and analogues

A general method for preparation of ferrocene‐containing monoamines (5–7) and diamines (10, 11) starting from the corresponding quaternary ammonium iodide 3 and ferrocene mono‐ (4) and dithiaaliphatic acids (8, 9) was developed. Amines obtained have been characterized as acet‐ and benzamides (12–15). The oligoamide precursors (16, 17, 22, 23) were synthesized by reactions of succinic or glutaric anhydride with amines (6, 7, 10, 11). Their conversion into oligoamide analogs (20, 21, 25) failed. The desired diamides (20, 21) were prepared by condensation of amines (6, 7) with alkanedioyl chlorides, (CH₂)_n(COCl)₂ (n = 0, 1, 2, 3). Reactions of diamine 10 with succinic or glutaric anhydride gave amino acids 28—formal monomers for the planned oligomerization. Oligomers 29 were synthesized by condensation of equimolar amounts of diamines 10 and the above mentioned alkanedioyl chlorides in dichloromethane at 0°C. The structure of oligomers 29 was indicated from their IR and ¹H‐NMR spectra in comparison with the model substances 12–28. The degree of polymerization of compounds 29 was determined by ¹H‐NMR end‐group analysis (DP_n = 4–6). © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 25–36, 1999     

Synthesis of 2(5H)-Furanone Derivatives with Symmetrical and Unsymmetrical Bis-1,2,3-triazole Structure

The interesting bioactivities of 2(5H)-furanone, 1,2,3-triazole, and amino acid derivatives have promoted their combination into one multifunctional molecule. The symmetrical bis-1,2,3-triazoles and mono-1,2,3-triazoles with one free azide group are synthesized respectively by controlling the molar ratio of reactants, N-[5-alkoxy-2(5H)-furanonyl] amino acid propargyl ester and 1,4-diazidobutane. The unsymmetrical bis-1,2,3-triazoles are afforded by the subsequent reaction of mono-1,2,3-triazoles with other terminal alkynes with good to excellent yields in a short time under the same mild “click” reaction conditions. The 32 new compounds obtained in the reactions are characterized by Fourier transform infrared, ¹H NMR, ¹³C NMR, mass spectrometry, and elemental analysis. Because of the diversity of four or five basic units in molecule, this methodology provides easy access to different chiral 2(5H)-furanone compounds with polyheterocyclic structure, especially with unsymmetrical bis-1,2,3-triazole moiety. Importantly, a simple approach is provided for the synthesis of unsymmetrical bis-1,2,3-triazoles using common diazides.     

Polydisuccinimides: Polyaddition reactions of aliphatic and aromatic diamines to N,N′-bismaleimide

Polyaddition reactions of aliphatic and aromatic diamines to N,N′-bismaleimide and model compounds have been investigated in order to establish some properties of this imide. Glacial acetic acid has a catalytic effect when used as solvent in the preparation of aspartimide compounds. Aromatic diamines show a much smaller reactivity than aliphatic, the former giving polydisuccinimides and the latter polyamides under the same reaction conditions. Addition reactions of N,N′-bismaleimide proceed either by an ionic mechanism in polar solvents or by a homolytic process in solvents precluding ion formation. The thermal stability and the infrared spectra of the new polymers are discussed.     

Cyclic Aromatic Polyamides via the Triphenylphosphite Method

Abstract

5‐tert‐Butyl‐isophthalic acid (TIPA) was polycondensed with three different aromatic diamines by means of triphenylphosphite (TPP) and pyridine. The resulting polyamides were characterized by solution viscosities and MALDI‐TOF mass spectra (m.s.). These m.s. revealed significant fractions of cyclic oligo‐ and polyamides in all samples. In polyamides of high molecular weight, only cycles were detectable (observed up to masses of 13,000 Da). Three poly(amide‐imide)s were prepared by TPP‐mediated polycondensation of trimellitic anhydride (TMA) and three aromatic diamines. Although relatively high molar masses were obtained, the MALDI‐TOF m.s. displayed the peaks of linear chains in addition to those of cyclic polymers. The results together suggest that the side reactions mainly occur at the amino endgroups.     

High-pressure alkylation of bis(benzylidene)phenylenediamines

The reactions of alkyl chlorides with bisanils (obtained from o-, m-, and p-phenylenediamines) under high pressure (10 kbar) were studied. Depending on the structure of the starting diamines and the solvent nature, hydrolysis of the reaction mixtures gave pure N-monoalkyl- or N,N"-dialkylphenylenediamines in high yields. The effect of the phase transition of the solvent on the direction of alkylation is discussed.     

Comparison of the reactivity of N‐(p‐toluenesulfonyl)‐sulfinimidoyl fluorides and chlorides toward triphenylphosphine

The path of the reaction of aryl‐N‐(p‐toluenesulfonyl)‐sulfinimidoyl fluorides and triphenylphosphine is highly dependent on the order of the reactants addition. Addition of triphenylphos‐phine to aryl‐N‐(p‐toluenesulfonyl)‐sulfinimidoyl fluorides results in the formation of triphenyl(aryl‐thio)phosphonium salts of N,N′‐bis(p‐toluenesul‐fonyl)aryl‐sulfinamidines and triphenyldifluorophosphorane. By changing the reagent addition order, we obtained triphenyldifluorophosphorane, P,P,P‐triphenyl‐N‐(p‐toluenesulfonyl)‐phosphine imide, and diaryl disulfides. The outcome of the reaction aryl‐N‐(arenesulfonyl)‐sulfinimidoyl chlorides and triphenylphosphine does not depend on the order of addition of the reactants. P,P,P‐Triphenyl‐N‐(arenesulfonyl)‐phosphine imides, triphenyldichloro‐phosphorane, and diaryl disulfides were formed as a result. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:66–71, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20408     

Effect of multiple H‐bonding on the properties of polyimides containing the rigid rod groups

To investigate the influence of hydrogen bonding on the properties of polyimides (PIs) containing rigid rod‐like groups, five symmetrical diamines containing benzimidazole, benzoxazole, and hydroxy group were synthesized, and then a series of PIs were prepared. Results showed that hydroxyl‐containing poly(benzoxazole imide)s possess higher glass transition temperature (T_g) and dimensional stabilities than their corresponding poly(benzoxazole imide)s. Moreover, the corresponding poly(benzimidazole imide)s presented the best performances, such as the highest T_g, the highest char yield and the highest dimensional stabilities. The influence of hydrogen bonding of benzimidazole on the properties of PIs was stronger than that of hydroxyl groups. Hydroxyl‐containing poly(benzoxazole imide)s were formed in crosslinking structures after heat treatment at 400 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 570–581     

Preparation and Thermal Decomposition of Cyclic Azoamidinium Salts as Water-Soluble Radical Initiators for Polymerization over A Wide Temperature Range

Abstract

A series of cyclic azoamidinium chlorides as water-soluble initiators were prepared by reactions of the iminoether derived from 2,2′-azobisisobutyronitrile with substituted alkylene diamines. The first-order rate constants for the decomposition of the azoamidinium salts varied from 0.59 × 10^?5 to 14.1 × 10^?5 s^?1 with the ring size and the alkyl substitution of the ring. Decomposition of 2,2′-azobis[2-(imidazoline-2-yl)propane] dihydrochloride was found to be accelerated by alkyl substitution on the imidazolinium ring. However, the azoamidinium compounds having larger rings, 2,2′-azobis[2-(3,4,5-trihydropyrimi-dine-2-yl)propane] dihydrochloride and 2,2′-azobis[2-(4,5,6,7-tetra-hydro-1H-1,3-diazepine-2-yl)propane] dihydrochloride, decomposed at a slower rate than the unsubstituted azobis[2-(imidazoline-2-yl)-propane] dihydrochloride. These new initiators were found to be capable of initiating radical polymerizations of acrylamide and vinyl acetate.     

Benzheterocycle–imide and amide–imide fibers derived from diacid chlorides containing preformed imide groups

Fibers of benzoxazole–imide ordered copolymers were prepared by cyclodehydrating the amide–phenol units of precursor polyamide–o-hydroxyimide fibers at 375°C in nitrogen. The precursor polyamide–o-hydroxyimides were obtained by the reaction of 3,3′-dihydroxybenzidine with diacid chlorides containing preformed imide rings. The benzoxazole–imide fibers are very thermally stable, especially with respect to retention of tensile properties after heat aging in air. For example, the benzoxazole–imide fibers after heating aging in air for 35 days retained 75% or more of their original tenacities and 50% or more of their original elongations to break. The original fibers did not have high tenacities, probably because of the rather extreme thermal treatment required to cyclodehydrate the amide–phenol units of the precursor fiber. The ultraviolet light stability of one benzoxazole–imide fiber was outstanding for a fiber of the polyheterocycle type: there was no loss in strength or elongation after 140 hr of exposure in a Fade-Ometer. Fibers of ordered amide–imide polymers based on the same imide-containing diacid chlorides used for the benzoxazole–imide polymers were also prepared. They were substantially less thermally stable than their benzoxazole–imide fiber counterparts, as expected.