High temperature phosphorylated or nonphosphorylated laminating resins based on maleimido-substituted aromatic s-triazines

Several new phosphorylated or nonphosphorylated maleimide or nadimide systems containing s-triazine rings were synthesized. Their synthesis was accomplished by simple methods utilizing readily available and relatively inexpensive starting materials. All polymer precursors were characterized by infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. They were thermally polymerized to heat-resistant laminating resins. Thermal characterization of monomers and their cured resins was achieved using differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The cured resins were stable up to 304–330°C both in nitrogen and air atmospheres and formed anaerobic char yield 49–59% at 800°C. The phosphorylated polymers showed a lower temperature of initial weight loss but afforded higher anaerobic char yield than did the corresponding nonphosphorylated polymers. The thermal properties of the polymers were correlated with their chemical structure.     

Bismaleimides and bisnadimides derived from 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene and their polymerization to heat-resistant matrix resins

Six new structurally different bismaleimides or bisnadimides based on 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene (BADT) were synthesized and characterized by infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. Chain-extension of several bismaleimides was accomplished by incorporating various imide, amide, and urea groups. The bismaleimide and bisnadimide prepared by reacting BADT with maleic or nadic anhydride, respectively, were soluble in various organic solvents. The monomers were thermally polymerized or by a Michael reaction with certain aromatic diamines. Curing behavior was investigated by differential thermal analysis (DTA). The thermal and thermo-oxidative stability of polymers was evaluated by dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The polymers derived from bismaleimide of BADT as well as from the bismaleimides chain-extended by imide groups were stable up to 355–392°C in N₂ or air and afforded anaerobic char yield 66–74% at 800°C. The polymers obtained by curing the bismaleimide-diamine adducts showed a relatively lower thermal stability.     

Thermally stable polymers based on bismaleimides containing amide,imide, and ester linkages

Seven new structurally different bismaleimides were synthesized and characterized by infrared and proton nuclear magnetic resonance spectroscopy. The chain of these polymer precursors was extended by incorporating amidized, imidized, and esterified 4-chloroformyl phthalic anhydride. The bismaleimides containing amide and imide linkages were prepared by a simple synthetic route based on the reaction of the monomaleamic acid derived from various aromatic diamines (1 mol) with 4-chloroformyl phthalic anhydride (0.5 mol) and subsequent cyclodehydration of the intermediate triamic acid. In addition, chain extended bismaleimides were prepared by reacting the monomaleamic acid derived from p-phenylenediamine with several dianhydrides such as p-phenylene bis(trimellitamide anhydride), p-phenylene bis(trimellitate anhydride), and bis-phenol A bis(trimellitate anhydride). The differential thermal analysis scans of bismaleimides showed exotherms at 221–304°C associated with their polymerization reactions. The thermogravimetric analysis traces of polymers did not show a weight loss up to 351–393 and 344–372°C in N₂ and air atmospheres, respectively. The anaerobic char yield of polymers at 800°C was 44–61%. These polymers can be used for fabrication of composites having improved properties.     

Studies on metathetical and thermal polymerization of 5-norbornene 2,3-dicarboximide end-capped resins Pt-II

The article deals with synthesis, characterization, and polymerization of 5-norbornene-2,3-dicarboximide end-capped resins (bisnadimides) based on 4,4′-diaminodiphenylether, 1,4/1,3-bis(4′-aminophenoxy) benzene, 2,2′-bis[4-(4′-aminophenoxy)phenyl]propane, and bis[4-(4′-aminophenoxy)phenyl]sulphone. Both exo and endo bisnadimides were prepared by reacting the aromatic diamines with exo or endo nadic anhydride in glacial acetic acid at 120°C. The exo or endo bisnadimides could be distinguished on the basis of differences observed in IR or ¹H-NMR spectra. Both thermal (in solid state) and metathetical polymerization (using WCl₆/tetramethyltin catalyst and chlorobenzene solvent) of bisnadimides was carried out. Only exo bisnadimides could be polymerized using metathesis reaction whereas thermal polymerization of both endo and exo bisnadimide could be successfully carried out at 300°C in static air atmosphere. The polymers were highly crosslinked and insoluble in common organic solvents. The polymers obtained by metathesis polymerization were light brown in color whereas those obtained by thermal polymerization were dark brown in color. Thermal stability of the thermally polymerized exo or endo bisnadimides was comparable. These polymers were stable up to 400°C and decomposed in a single step above this temperature. The char yield at 800°C depended on the structure of the polymer and was in the 39–56% range. The polymers formed by metathesis polymerization showed a 1–3% weight loss in the temperature range 226–371°C and decomposed in a single step above 440°C. The char yields were higher in these polymers (53–71%) compared to those obtained by thermal polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2323–2331, 1997     

Solid-state ultraviolet irradiation of some maleimides and bismaleimides

The solid-state photoreactivity of a series of maleimides and bismaleimides is studied Various crystalline maleimides are found to dimerize on irradiation by ultraviolet light Based on this discovery, the photopolymerizability of the related bismaleimides in the crystalline state is examined. As a result it is found that some N,N,-alkylenebismaleimides polymerize into highly crystalline polymers. The polymers do not melt below their decomposition temperature (>300°C) and are practically insoluble in all solvents. The obtained irradiation products are different from the reaction products of the solution-phase photochemistry. Closely related bismaleimides, such as members of a homologous series, show substantial differences in their solid-state photochemical behavior; on excitation they either lead to polymers or are not reactive. This indicates that the solid-state photoreactivity of maleimides and bismaleimides is controlled by the geometry of their crystal structure.     

Convergent Versus Divergent Three-Step Synthesis of the First (4-Aminophenoxy)alkanoic Acid–Based Tripodal Melamines

Starting from N-(4-hydroxyphenyl)acetamide (Paracetamol, convergent approach) or from cyanuric chloride in reaction with 4-aminophenol (divergent approach), two synthetic routes toward novel tripodal N-substituted melamines as s-triazine derivatives of (4-aminophenoxy)acetic acid or of 4-(4-aminophenoxy)butyric acid are comparatively defined. The key steps consist of Williamson etherification of N-masked forms of 4-aminophenol and acidic hydrolysis of the N- and/or O-protected (4-aminophenoxy)alkanoic segments.     

Synthesis and characterization of novel poly(amide urea)s,materials with outstanding mechanical properties

Four novel A‐B condensation monomers containing an amine and a carboxylic acid function are described, along with their polymerization to give main chain aromatic poly(amide urea)s. The monomers, and the polymer structural unit, are N,N′‐diphenylurea derivatives. When comparing wholly aromatic polyamides, or aramids, with the poly(amide urea)s described herein, we find that the chemical resistance to hydrolysis of the later polymers increases and their thermal resistance is diminished due to the main chain urea groups, whereas their water uptake is not greatly modified. The most striking result of the new poly(amide urea)s is their outstanding mechanical resistance: their Young's modulus rises as high as 5.5 GPa and their tensile strengths as high as 170 MPa for unoriented films prepared at laboratory scale by casting. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5398–5407, 2007     

Distannylated Bithiophene Imide: Enabling High‐Performance n‐Type Polymer Semiconductors with an Acceptor–Acceptor Backbone

A distannylated electron‐deficient bithiophene imide (BTI‐Tin) monomer was synthesized and polymerized with imide‐functionalized co‐units to afford homopolymer PBTI and copolymer P(BTI‐BTI2), both featuring an acceptor–acceptor backbone with high molecular weight. Both polymers exhibited excellent unipolar n‐type character in transistors with electron mobility up to 2.60 cm² V^?1 s^?1. When applied as acceptor materials in all‐polymer solar cells, PBTI and P(BTI‐BTI2) achieved high power‐conversion efficiency (PCE) of 6.67 % and 8.61 %, respectively. The PCE (6.67 %) of polymer PBTI, synthesized from the distannylated monomer, is much higher than that (0.14 %) of the same polymer PBTI*, synthesized from typical dibrominated monomer. The 8.61 % PCE of copolymer P(BTI‐BTI2) is also higher than those (<1 %) of homopolymers synthesized from dibrominated monomers. The results demonstrate the success of BTI‐Tin for accessing n‐type polymers with greatly improved device performance.     

New poly(amide–imide) syntheses. XXI. Synthesis and properties of aromatic poly(amide–imide)s based on 2,6-bis(4-trimellitimidophenoxy)naphthalene and aromatic diamines

A novel polymer-forming diimide–diacid, 2,6-bis(4-trimellitimidophenoxy)naphthalene, was prepared by the condensation reaction of 2,6-bis(4-aminophenoxy)naphthalene with trimellitic anhydride (TMA). A series of novel aromatic poly(amide–imide)s containing 2,6-bis(phenoxy)naphthalene units were prepared by the direct polycondensation of the diimide–diacid with various aromatic diamines using triphenyl phosphite (TPP) in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. Thirteen of the obtained polymers had inherent viscosities above 1.01 dL/g and up to 2.30 dL/g. Most of polymers were soluble in polar solvents such as DMAc and could be cast from their DMAc solutions into transparent, flexible, and tough films. These films had tensile strengths of 79–117 MPa, elongation-at-break of 7–61%, and initial moduli of 2.2–3.0 GPa. The wide-angle X-ray diffraction revealed that some polymers are partially crystalline. The glass transition temperatures of some polymers could be determined with the help of differential scanning calorimetry (DSC) traces, which were recorded in the range 232–300°C. All the poly(amide–imide)s exhibited no appreciable decomposition below 450°C, and their 10% weight loss temperatures were recorded in the range 511–577°C in nitrogen and 497–601°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 919–927, 1998     

Fire- and heat-resistant adhesive resins based on maleimido and citraconimido substituted 1-[(dialkoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzenes

A novel class of fire- and heat-resistant bisimide resins was prepared by thermal polymerization of maleimido or citraconimido derivatives of 1-[(dialkoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzenes (1). The neat bisimide resin prepared by curing 1-[di(2-chloroethoxyphosphinyl)methyl]-2,4- and -2,6-bismaleimidobenzene exhibited a limiting oxygen index 75% higher and smoke evolution about 30 times lower compared with the parent polymer obtained by curing m-phenylenebismaleimide. The char yield of cured bisimide resins at 700°C was 58–70% in a nitrogen atmosphere and 35–60% in air. An increase in formula weight between the imide groups slightly reduced the char yield. The polymer precursors were synthesized by reacting the phosphorus-containing diamines (1) (1 mol) with maleic anhydride/citraconic anhydride (2 mol) or by reacting the monomaleimido derivative of (1) with benzophenone tetracarboxylic dianhydride/methylenebis(4-phenylisocyanate) in a 2:1 mole ratio. The monomers were characterized by elemental analysis, Fourier-transform–infrared (FT-IR), proton nuclear magnetic resonance (¹H-NMR) spectroscopy, and gas chromatography–mass spectroscopy (GC-MS). Direct cleavage of the P? C bond and inversion of the synthesis reaction may occur during their pyrolysis. The thermal polymerization of the monomers was investigated by differential scanning calorimetry (DSC). Biscitraconimides are thermally polymerized at a relatively lower temperature than the corresponding bismaleimides.     

Synthesis,characterization, and thermal stability of bismaleimides derived from maleimido benzoic acid

Bismaleimides containing ester, amide, urethane, and imide groups in the backbone were synthesized from maleimido benzoic acid via its acid chloride or isocyanate with 4,4′-dihydroxy-diphenyl-2,2-propane, 3,3′-diamino diphenyl sulfone, and 3,3′,4,4′-benzophenone tetracarboxylic acid anhydride by simple condensation or addition reaction. The new bismaleimides are characterized by IR, ¹H-NMR, and elemental analysis. DSC studies of these bismaleimides indicated a curing exotherm in the temperature range 150–270°C with heat of polymerization 30–50 J/g. Thermogravimetric analysis of the uncured resins showed high thermal stability and char yield for imide containing bismaleimide. The observed char yields of the bismaleimide resins are in accordance with the calculated C/H ratios.     

Synthesis and characterization of novel heat resistant poly(amide imide)s

A series of new poly(amide imide)s was prepared from new diacid containing sulfone, ether, amide and imide groups with various aromatic diamines. The diacid was synthesized via four steps, starting from reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide afforded N-(4-hydroxy phenyl)-4-nitrobenzamide. In the second step, reduction of nitro group resulted in preparation of 4-amino-N-(4-hydroxy phenyl) benzamide. In the next step for the preparation of diamine, the reaction of 4-amino-N-(4-hydroxy phenyl) benzamide with bis-(4-chlorophenyl) sulfone in the presence of K₂CO₃ was achieved. The prepared sulfone ether amide diamine was reacted with two moles of trimellitic anhydride to synthesize related sulfone ether amide imide diacid. The precursors and final monomer were characterized by FT-IR, H-NMR and elemental analysis. Direct polycondensation reaction of the sulfone ether amide imide diacid with different diamines in the presence of triphenyl phosphite afforded five different poly (sulfone ether amide imide amide)s. The obtained polymers were fully characterized and their physical properties including thermal behavior, thermal stability, solubility, and inherent viscosity were studied.     

Synthesis and properties of polyurethanes containing s-triazine rings in the main chain

Eight new diisocyanate monomers containing s-triazine ring have been prepared from the parent diacids via the Curtius rearrangement of the corresponding diacyl azides. The parent diacids were synthesised by the reaction of p- and m-hydroxybenzoic acid with 6-methoxy-2,4-dichloro-s-triazine, 6-phenoxy-2,4-dichloro-s-triazine, 6-phenyl-2,4-dichloro-s-triazine, and 2-diphenylamino-4,6-dichloro-s-triazine respectively. Polyurethanes have been synthesised by solution polymerization of these diisocyanates with ethylene glycol in N,N-dimethylacetamide (DMAC). The resulting polymers were characterized by IR spectroscopy, viscosity measurement, solubility tests, and softening points.     

Thermostable laminating resins based on aromatic diketone bis- and tetramaleimides

Twelve structurally different bis- and tetramaleimides were synthesized by Friedel–Crafts reaction between 4-maleimido-benzoylchloride or 3,5-bismaleimido-benzoylchloride and various aromatic reagents. They were characterized by infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. Crosslinked resins were obtained by curing the monomers at 250°C/6 h. Thermal characterization of monomers and cured resins was accomplished by differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA), and isothermal gravimetric analysis (IGA). Tetramaleimides were polymerized at lower temperatures than did the respective bismaleimides. The cured resins were stable up to 317–385°C in N₂ atmosphere and formed an anaerobic char yield of 52–66% at 800°C.     

Thermally resistant polymers containing the s-triazine ring

Aromatic dinitriles cyclize to form aromatic polymers containing the s-triazine ring. In this paper, these polymers are compared thermally with each other and with aromatic melamine polymers prepared via the aromatic diamine and cyanuric chloride. One perfluoroaromatic melamine polymer was prepared and compared with the other two types of polymers. The polymers (triazines and melamine) in which biphenyl was the backbone were increasingly stable up to 1000°C. in nitrogen. The triazine polymers as a group were the most stable. The perfluoroaromatic polymer was the most stable melamine up to 500°C. in air but was very unstable above 700°C.     

Synthesis,physical, and thermal properties of linear poly(dialkoxyphosphinyl-s-triazine)s

A novel class of linear poly(dialkoxyphosphinyl-s-triazine)s were prepared by interfacial or solution polycondensation reactions of various diamines such as ethylenediamine, hexamethy-lenediamine or bis(4-aminocyclohexyl)methane with 2-dialkoxyphosphinyl-4,6-dichloro-s-triazines. The latter were synthesized by reacting cyanuric chloride with an equimolar amount of trialkyl phosphite. The phosphorous-containing polymers were characterized by inherent viscosity measurements as well as by infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The thermal properties of polymers were investigated by differential thermal analysis (DTA) and thermogravimetric analysis (TGA). Pyrolysis of all polymers was exothermic. Polymers were stable up to 150–200°C both in nitrogen and air atmosphere. They afforded 16–42% char yield at 700°C under anaerobic conditions.     

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.     

New poly(amide–imide)s syntheses. XXIII. Synthesis and properties of poly(amide–imide)s derived from 4,4′‐[1,4‐phenylenebis(isopropylidene‐1,4‐phenyleneoxy)]dianiline and various bis(trimellitimide)s

A series of poly(amide–imide)s III_a–m containing flexible isopropylidene and ether groups in the backbone were synthesized by the direct polycondensation of 4,4′‐[1,4‐phenylenebis(isopropylidene‐1,4‐phenyleneoxy)]dianiline (PIDA) with various bis(trimellitimide)s II_a–m in N‐methyl‐2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The resulting poly(amide–imide)s had inherent viscosities in the range of 0.80–1.36 dL/g. Except for those from the bis(trimellitimide)s of p‐phenylenediamine and benzidine, all the polymers could be cast from DMAc into transparent and tough films. They exhibited excellent solubility in polar solvents. The 10% weight loss temperatures of the polymers in air and in nitrogen were all above 495°C, and their T_g values were in the range of 201–252°C. Some properties of poly(amide–imide)s III were compared with those of the corresponding poly(amide–imide)s V prepared from the bis(trimellitimide) of diamine PIDA and various aromatic diamines. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 69–76, 1999     

Bismaleimides chain-extended by imidized benzophenone tetracarboxylic dianhydride and their polymerization to high temperature matrix resins

Heat-resistant polymers were obtained by thermal polymerization of several bismaleimides or their substituted derivatives. The chain of the polymer precursors was extended by incorporation of imidized benzophenone tetracarboxylic dianhydride between the maleimide rings in order to impart a degree of flexibility in the polymers. The bismaleimides and their corresponding tetraamic acids were characterized by infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The differential thermal analysis (DTA) thermograms of the monomers showed exotherms at 200–340°C attributed to the thermally induced polymerization reactions. The influence of different substituents in the maleic double bond on the curing temperature was investigated. The thermal stability of the cured resins was evaluated by thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). They were stable up to 367–433°C both in nitrogen and air atmosphere and afforded 57–68% char yield at 800°C under anaerobic conditions. The structure of the aromatic and aliphatic diamines utilized for imidization was correlated with the thermal stability of the cured resins. The bismaleimide derived from p-phenylenediamine gave the most heat-resistant resin because of its higher rigidity.     

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.