Effects of solvent basicity on free radical polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane initiated by barbituric acid

The polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) initiated by barbituric acid (BTA) carried out in a variety of solvents at 130°C were studied. The nitrogen‐containing cyclic solvents such as N‐methyl‐2‐pyrrolidinone acted as a catalyst to promote the formation of the three‐dimensional crosslinked network structure. By contrast, the polymerization in a cyclic solvent that did not contain nitrogen such as γ‐butyrolactone resulted in nil gel content. The higher the solvent basicity, the larger the amount of insoluble polymer species formed. The molar ratio of BTA to BMI also played an important role in the polymerizations. The resultant polymers, presumably having a hyper‐branched structure, exhibited much narrower molecular weight distributions than those prepared by conventional free radical polymerizations. The BMI polymerizations using BTA as the initiator could not be adequately described by conventional free radical polymerization mechanisms. A polymerization mechanism that took into account the generation of a ketone radical pair between BTA and BMI and the subsequent initiation, propagation and termination reactions was proposed. It was concluded that the nitrogen‐containing cyclic solvents were capable of participating in the ketone radical pair formation process, thereby increasing the extent of polymer crosslinking reactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of novel polyaspartimides derived from 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl and various diamines

A novel bismaleimide, 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl, containing noncoplanar 2,2′‐dimethylbiphenylene and flexible ether units in the polymer backbone was synthesized from 2,2′‐dimethyl‐4,4′‐bis(4‐aminophenoxy)biphenyl with maleic anhydride. The bismaleimide was reacted with 11 diamines using m‐cresol as a solvent and glacial acetic acid as a catalyst to produce novel polyaspartimides. Polymers were identified by elemental analysis and infrared spectroscopy, and characterized by solubility test, X‐ray diffraction, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis). The inherent viscosities of the polymers varied from 0.22 to 0.48 dL g⁻¹ in concentration of 1.0 g dL⁻¹ of N,N‐dimethylformamide. All polymers are soluble in N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethylsulfoxide, pyridine, m‐cresol, and tetrahydrofuran. The polymers, except PASI‐4, had moderate glass transition temperature in the range of 188°–226°C and good thermo‐oxidative stability, losing 10% mass in the range of 375°–426°C in air and 357°–415°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 279–286, 1999     

Investigation on the properties of a three‐component copolymer consisting of tris(allylphenoxy) triazine monomer and a diamine‐chain‐extension bismaleimide

A new type of modified bismaleimide resin was obtained by copolymerization between tris(allylphenoxy)triazine monomer (TAPT) and an aromatic diamine‐chain‐extension bismaleimide [e.g., 4,4′‐diaminodiphenylmethane (DADPM)‐chain‐extension 4,4′‐bismaleimidodiphenylmethane (BMDPM)]. The new three‐component‐polymer system had good processibility and mechanical properties. Better results were obtained when the weight ratio of TAPT to the DADPM‐chain‐extension BMDPM resin was 30%. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 475–480, 2004     

Addition polyimides. I. Kinetics of cure reaction and thermal decomposition of bismaleimides

The thermal polymerization of four structurally different bismaleimide resins, prepared by reacting maleic anhydride with four aromatic diamines, viz., 4,4′-diaminodiphenyl methane, 4,4′-diamino diphenyl ether, 4,4′-diamino diphenyl sulfone, and 3,3′-diamino diphenyl sulfone, was followed by differential scanning calorimetry (DSC). The enthalpy change and the kinetic constants for the polymerization reactions were evaluated from the DSC curves. Thermal stability of the cured polymers was studied by thermogravimetry (TG). The kinetic parameters, viz., activation energy E and preexponential factor A, for the thermal decomposition of the cured bismaleimides were calculated from the TG curves using three nonmechanistic integral equations. The kinetic constants (E and A) follow a trend similar to the thermal stability of the polymers.     

Synthesis and thermal behavior of some anthracene‐based copolymers obtained by Diels–Alder cycloaddition reactions

New polymer structures have been synthesized via Diels–Alder cycloaddition of bisdiene compounds bearing two anthracene groups and different bisdienophiles, all containing bismaleimide or biscitraconimide functions. The monomers and polymers were characterized by FTIR, UV, and ¹H NMR techniques and compared with two models having a cycloadduct structure. The polymers were studied by thermogravimetric analyses. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Heat-resistant polyimides and polyamides prepared from 2, 7-diamino-9-dicyanomethylene-fluorene

9-Fluorenone was nitrated with fuming nitric acid to yield 2,7-dinitro-fluorenone (1). It was condensed with malononitrile in the presence of glacial acetic acid and a catalytic amount of piperidine to afford 2,7-dinitro-9-dicyanomethylene-fluorene (2). It was catalytically hydrogenated to the corresponding diamine (3). The latter was used as starting material for the preparation of new polyimides and polyamides bearing dicyanomethylene units. In addition, a bismaleimide was synthesized from the reaction of 3 with maleic anhydride and subsequent cyclodehydration of the intermediate bismaleamic acid. The FTIR spectra of polymers were in agreement with those of the synthesized model compounds. The polymers and bismaleimide yielded crosslinked resins upon curing at 300°C for 40 h in the presence of a catalytic amount of 4,4′-diaminodiphenylmethane. They were stable up to 355–430°C in N₂ or air and afforded anaerobic char yield of 52–57% at 800°C. © 1994 John Wiley & Sons, Inc.     

Ketone derivatives of diels‐alder adducts of levopimaric acid with acrylic acid and maleic anhydride: Synthesis,characterization, and polymerization

Two new ketone‐type derivatives were synthesized by the dehydrodecarboxylation of levopimaric acid acrylic acid adduct and of levopimaric acid maleic anhydride adduct in the presence of sulfonic catalysts. The two compounds were also synthesized by coupling of acrylic acid or maleic anhydride with dipimaryl ketone. These ketones, or rather ketone‐diacids, were condensed with polyalkylenepolyamines to give poly(amide)s or poly(imide)s with good thermal properties. New crosslinked polymers were obtained when these poly(amide)s or poly(imide)s were substituted with epichlorohydrin. The structures of the resulted ketone‐diacids and polymers were investigated by the usual physical and chemical methods. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2240–2252, 2004     

Kinetics of Michael addition polymerizations of n,n′‐bismaleimide‐4,4′‐diphenylmethane with barbituric acid

With the addition of sufficient hydroquinone to completely suppress the free radical polymerization, the kinetics of Michael addition polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) and barbituric acid (BTA) with BMI/BTA = 2/1 (mol/mol) in 1‐methyl‐2‐pyrrolidone was investigated independently. A mechanistic model was developed to adequately predict the polymerization kinetics before a critical conversion (ca. 60%), at which point the diffusion‐controlled polymer reactions started to predominate in the latter stage of polymerization. The Michael addition polymerization rate constants and activation energy in the temperature range 383–423 K were determined accordingly. Beyond the critical conversion, a relatively stationary limiting conversion (ca. 69%) independent of the reaction temperature was achieved. A diffusion‐controlled polymerization model taken from the literature satisfactorily predicted the limiting conversion data. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Modification of three‐component bismaleimide resin by poly(phthaloyl diphenyl ether) and related copolymers

A three‐component bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane (BDM), o,o′‐diallyl bisphenol A (DBA), and o,o′‐dimethallyl bisphenol A (1.0/0.3/0.7 eq ratio) was used as a parent bismaleimide resin. Modification of the three‐component bismaleimide resin was examined by blending it with poly(ether ketone ketone)s. Poly(ether ketone ketone)s include poly(phthaloyl diphenyl ether) (PPDE), poly(phthaloyl diphenyl ether‐co‐isophthaloyl diphenyl ether) (PPIDE), and poly(phthaloyl diphenyl ether‐co‐terephthaloyl diphenyl ether) (PPTDE). The PPIDE (51 mol % isophthaloyl) and PPTDE (44 mol % terephthaloyl) were more effective as modifiers for the bismaleimide resin than was PPDE. For example, the fracture toughness (K_IC) for the modified resin increased 30% with no deterioration in the flexural strength and modulus with a 15 wt % inclusion of PPTDE (MW 23,400) compared to the parent three‐component bismaleimide resin: the K_IC increased 95% compared to the value for the Matrimid 5292 resin composed of BDM and DBA. The morphologies of the modified resins changed from particulate to cocontinuous phase structures, depending on the modifier structure and concentration. Toughening of the cured bismaleimide resin could be achieved because of the cocontinuous phase structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2991–3000, 2001     

An ESR study of the film formation steps of vapor deposition polymerization of polyamic acid

A film of polyamic acid is formed by vapor deposition polymerization of pyromellitic dianhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA). We have taken ESR spectrum during the polymerization process and compared it with the ESR spectrum of films obtained from solution polymerization. In the intermediate polymers during vapor deposition polymerization, the amide bond (? CONH? ) is coplanar with the benzene ring and two protons in the PMDA molecule. This intermediate polymer has one unpaired electron that interacts with the two nitrogen nuclei equally. On the other hand, in the polymer obtained by solution polymerization, the amide bond and the benzene ring of PMDA are not coplanar. In this polymer, too, some of the molecules have an unpaired electron that seems to have almost no coupling with NH groups. These results imply that the polymer formation via vapor deposition proceeds through different intermediates and different molecular configurations from that via the solution process.     

Synthesis of novel organoboron polymers by hydroboration polymerization of bisallene compounds

This paper describes synthesis of novel organoboron polymers by hydroboration polymerization of bisallene compounds. The polymers were prepared by polyaddition between thexylborane and bisallenes. The polymers obtained have allylborane units in their main chains and can be expected as a novel type of reactive polymers. The polymer was subjected to a chain transformation reaction and the corresponding polyalcohol was obtained. Hydroboration polymerization of bisallene with mesitylborane was also carried out. It was found that the polymer prepared from mesitylborane showed higher stability than that prepared from thexylborane. Received: 20 December 1996/Accepted: 7 February 1997     

Surface grafting of polymers onto glass plate: Polymerization of vinyl monomers initiated by initiating groups introduced onto the surface

The surface grafting of polymers onto a glass plate surface was achieved by the polymerization of vinyl monomers initiated by initiating groups introduced onto the surface. Azo groups were introduced onto the glass plate surface by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with isocyanate groups, which were introduced by the treatment with tolylene-2,4-diisocyanate. The radical polymerization of various vinyl monomers was initiated by azo groups introduced onto the glass plate surface and the corresponding polymers were grafted from the surface: The surface grafting of polymers was confirmed by IR spectra, and the contact angle of surface, with water. The contact angle of the glass plate increased by the grafting of hydrophobic polymers, but decreased by the grafting of hydrophilic polymers. The radical postpolymerization was successfully initiated by the pendant peroxycarbonate groups of grafted polymer on the surface to give branched polymer-grafted glass plate. The cationic polymerization of vinyl monomers was also successfully initiated by benzylium perchlorate groups introduced onto the glass plate surface and the corresponding polymers were grafted onto the surface. The contact angle of the glass plate surface obtained from the cationic polymerization of styrene was larger than that obtained from the radical polymerization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2165–2172, 1997     

Synthesis and characterization of cross‐linkable poly(phthalazinone ether ketone)s

A novel class of crosslinkable poly(phthalazinone ether ketone)s with relative high molecular‐weight and good solubility were successfully synthesized by the copolymerization of bisphthalazinone containing monomer, 3,3′‐diallyl‐4,4′‐dihydroxybiphenyl and 4,4′‐di‐ fluorobenzophenone. The synthesized polymers with inherent viscosities in the range of 0.42 to 0.75 dL/g can form flexible and transparent membranes by casting from their solution. The crosslinking reaction of these polymers can be carried out by thermally curing of the virgin polymers in or without the presence of crosslinking agent. The experimental results demonstrated that the crosslinking reaction also occurred to some extent during the polymerization. The crosslinked polymers exhibited equivalent glass transition temperature (T_g) at lower crosslinking density, and showed higher T_g than virgin polymers at higher crosslinking density. The crosslinked high‐temperature polymer can be used as the base material for high temperature adhesive, coating, enamel material, and composite matrices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Novel poly(ether ketone)arylates: Synthesis,characterization and properties

In order to reduce the melt temperature (T_m) of the thermotropic crystalline polyarylate and improve its compatibility with poly(ether ether ketone) (PEEK), a series of poly(ether ketone)arylates (PEKARs) containing aryl ether ketone units (AEK) are synthesized through melt transesterification reaction from p‐acetoxybenzoic acid, 1,3‐bis(4′‐carboxylphenoxy)benzene and 4,4′‐bis(p‐acetoxyphenoxy)benzophenone. The inherent viscosities of these polymers are in the range 0.35–0.81 dL/g. The morphologies and properties of PEKARs are characterized by polarized optical microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, thermal gravimetric analysis, etc. The results show that all PEKARs are semi‐crystalline polymers, and the introduction of AEK units can reduce the symmetry of the main chains, leading to decreasing the crystallizability and changing the crystalline form. The PEKARs with AEK less than 30% can exhibit thermotropic liquid crystalline state. The initial and the maximum decomposition temperatures increase with the increase in AEK content. These PEKARs are expected to act as processing agents for PEEK to reduce its processing viscosity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Phosphorus-Containing polymers. I. Low temperature polycondensation of phenylphosphonic dichloride with bisphenols

This paper describes the synthesis of aryl polyphosphonates from the reactions of phenylphosphonic dichloride [benzene phosphorus oxydichloride (BPOD)] with 4,4′-thiodiphenol (TDP) and with 4,4′-sulfonyldiphenol (SDP) employing a dry chlorinated hydrocarbon polymerization solvent, an amine acid acceptor and under low temperature conditions. The glass transition temperatures of the polymers from BPOD/TDP are 146°C and 83°C, respectively, and the polymers begin to lose weight at about 395°C in a nitrogen atmosphere. These polymers have good flame retardancy (FR), as indicated by high limiting oxygen indices (LOI) of 50–60. Thermoplastic polybutylene terephthalate containing 7% BPOD/SDP or BPOD/TDP polymer as an FR additive has LOI values of 29 and 30, respectively.     

Synthesis and characterization of poly(ether ketone ether ketone ketone)/poly(ether ether ketone ketone) copolymers containing naphthalene and pendant cyano groups

2,6‐Bis(β‐naphthoxy)benzonitrile (BNOBN) was synthesized by reaction of β‐naphthol with 2,6‐difluorobenzonitrile in N‐methyl‐2‐pyrrolidone (NMP) in the presence of KOH and K₂CO₃. Poly(ether ketone ether ketone ketone)(PEKEKK) /poly(ether ether ketone ketone) (PEEKK) copolymers containing naphthalene and pendant cyano groups were obtained by electrophilic Friedel‐Crafts polycondensation of terephthaloyl chloride (TPC) with varying mole proportions of 4,4′‐diphenoxybenzophenone (DPOBP) and 2,6‐bis(β‐naphthoxy)benzonitrile (BNOBN) using 1,2‐dichloroethane (DCE) as solvent and NMP as Lewis base in the presence of anhydrous AlCl₃. The resulting polymers were characterized by various analytical techniques, such as FTIR, DSC, TG, and WAXD. The results indicated that the crystallinity and melting temperature of the polymers decreased with increase in concentration of the BNOBN units in the polymer, the glass transition temperature of the polymers increased with increase in concentration of the BNOBN units in the polymer. Thermogravimetric studies showed that all the polymers were stable up to 536°C in N₂ atmosphere. The copolymers have good resistance to acidity, alkali, and organic solvents. Because of the melting temperature (T_m) depression with increase in the BNOBN content in the reaction system, the processability of the resultant coplymers could be effectively improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

How the monomer concentration of polymerization influences various properties of polybenzimidazole: A case study with poly(4,4′‐diphenylether‐5,5′‐bibenzimidazole)

In this work, a series of poly(4,4′‐diphenylether‐5,5′‐bibenzimidazole)s (OPBIs) were synthesized from 4,4′‐oxybis(benzoic acid) and 3,3′,4,4′‐tetraaminobiphenyl through the variation of the initial monomer concentration with a solution polycondensation technique in a poly(phosphoric acid) medium. The resulting polymers were characterized by various techniques such as infrared (IR), nuclear magnetic resonance, dynamic mechanical analysis (DMA), and thermogravimetric analysis. The initial monomer concentration in the polymerization mixture played an important role in controlling the molecular weight of the resulting polymers. A temperature‐dependent IR study showed that the free movement of the ? NH group of the imidazole ring was blocked by the absorbed moisture. The DMA study showed that the glass‐transition temperature (T_g) varied with the molecular weight, and the presence of the ether linkage in the OPBI polymer backbone had a significant influence on T_g. A high‐molecular‐weight OPBI polymer tended to form a supramolecular organization, which influenced the thermal characteristic of the polymer. Photophysical studies demonstrated the fluorescent characteristics of the OPBI polymers in both solid and solution states. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization of a bisanthracene compound with bismaleimides by Diels–Alder cycloaddition

Four new polymers have been synthesized via succesive Diels–Alder cycloadditions of a bisdiene compound bearing two anthracene groups and four bisdienophiles, all containing bismaleimide functions. The polycondensation reaction was performed in N,N‐dimethylacetamide at 120 °C leading to polymers soluble in polar solvents having molecular weights lower than 6000 g mol^?1. © 2001 Society of Chemical Industry     

Synthesis and characterization of poly(ether sulfone) and poly(ether sulfone ketone) copolymers

Poly(ether sulfone) and poly(ether sulfone ketone) copolymers (I–V) were synthesized by the nucleophilic substitution reaction of 4,4′-dihydroxy diphenyl sulfone (DHDPS, A) with various mole proportions 4,4′-difluoro benzophenone (DFBP, B) and 4,4′-difluoro diphenyl sulfone (DFDPS, C) using sulfolane as solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by physicochemical and spectroscopic techniques. All polymers were found to be amorphous, and the glass transition temperature (T_g) was found to increase with the sulfonyl content of the polymers. ¹³C-nuclear magnetic resonance (NMR) spectral data was interpreted in terms of the compositional triads, BAB, BAC, CAC, ABA, and ABB, and indicate that transetherification occurs at high concentration of DFBP units in the polymer (IV). The good agreement between the observed and calculated feed ratios validates the triad analysis. Thermal decomposition studies reveal that the thermal stability of the polymers increases with increase in the carbonyl content in the polymer. Activation energies for thermal decomposition were found to be in the range of 160–203 kJ mol⁻¹ with the cleavage of ϕ SO₂ bond being the preponderant mode of decomposition and depended on the block length of the sulfonyl unit. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2113–2121, 1999     

BTDA型聚酰胺酸和聚酰亚胺的微波辐射合成

在微波辐射条件下,将3,3′,4,4′-二苯酮四羧酸二酐(BTDA)、4,4′-二氨基二苯醚(ODA)和3,5-二氨苯甲酸(DABA)在少量非极性溶剂N,N′-二甲基甲酰胺(DMF)的存在下进行共缩聚反应,快速而高效地合成了聚酰胺酸(PAA)和聚酰亚胺(PI)。采用特性粘数、红外光谱(FT-IR)和核磁共振(1HNMR)对聚合物的结构进行了表征,利用热失重分析(TGA)对其热性能进行了测试,并测定了聚合物在多种溶剂中的溶解性。实验结果表明,微波辐射溶液聚合能够提高PAA的特性粘数及产率,微波的引入大大缩短了反应时间;FT-IR表明,在1779cm-1、1723cm-1、1239cm-1和1378cm-1处观察到聚酰亚胺特征峰;TG表明,PI在氮气中10%热失重温度(Td10%)为576℃。