Polyimides with alicyclic diamines. I. Syntheses and thermal properties

The polyaddition reactions of alicyclic diamines such as 1,4-diaminocyclohexane (1,4-CHDA) or 4,4′-diaminodicyclohexylmethane (DCHM) and configurational isomers of 1,4-CHDA or DCHM with tetracarboxylic aromatic anhydrides in aprotic solvents were carried out to prepare high molecular weight poly(amic acid)s. Through the thermal imidization of poly(amic acid)s, several flexible polyimide films were prepared. Because of the stiffness of the alicyclic moieties in diamines, the resulting polyimides exhibit high glass transition temperatures (220–340°C) almost similar to those for corresponding aromatic polyimides which have phenylene groups in place of cyclohexyl groups, and show good thermal stability. The partial crystallization was observed for polyimides with trans-cyclohexyl moiety during the heating in differential scanning calorimetry and ascertained by wide-angle x-ray diffraction. Thus, the inhibition of the occurrence of charge transfer in polyimides is accomplished by introducing alicyclic diamines in place of aromatic diamines without reducing their thermal stability. © 1993 John Wiley & Sons, Inc.     

Phospha-s-triazines. I. Syntheses and properties of mono(diarylphospha)-s-triazines

A series of monophospha-s-triazines, namely l-diphenylphospha-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis[C₃F₇-[OCF(CF₃)CF₂]_xOCF(CF₃)]-2,4,6-triazine (x = 1 and 2), and the penta-fluorophenyl-substituted analogues were prepared, in yields of 50-75%, from the respective imidoylamidines and trichlorophosphoranes. The physical properties of the corresponding phenyl and pentafluorophenyl monophospha-s-triazines did not differ significantly; the perfluoroalkyl-substituted materials were low melting solids whereas the perfluoroalkyl-ether-containing compositions were liquids. Preliminary degradative studies showed these compounds to be thermally and oxidatively stable. The l-diphenylphospha-3,5-bis[C₃F₇OCF(CF₃)CF₂OCF(CF₃)]-2,4,6-triazine was found to be an effective anti-corrosion additive for perfluoroalkylether type fluids.     

Polyschiff bases—I.: Syntheses and properties of polyschiff bases from 5,5′-thiobisfurfural

PolySchiff bases have been synthesized from 5,5′-thiobisfurfural and various diamines such as o-, m- and p-phenylenediamines, benzidine, 3,3′-dimethoxybenzidine, 3,3′-dimethylbenzidine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulphone and aliphatic diamines such as ethylenediamine and hexamethylenediamine under various experimental conditions. The polymers have been characterized by i.r. spectral and thermal studies and by measurement of electrical conductivity at various temperatures.     

Syntheses,crystal structures and properties of dinuclear copper(I) complexes

Two dinuclear molecule-bridged Cu(I) complexes, (μ-bpym)[Cu(PPh₃)Cl]₂ (1), [(μ-bpym)(CuL)₂](ClO₄)₂·(CH₃CN)₂(H₂O) (2) (bpym = 2,2′-bipyrimidine, L = (R)-(+)-2,2′-bis(diphenylphospho)-1,1′-dinaphthalene) have been synthesized and characterized. The molecular structures of the two new dinuclear compounds exhibit bridging of two copper(I) centers by the symmetrically bis-chelating bpym ligand. Intriguingly, compound 1 features a remarkable “intramolecular organic sandwich” configuration where the central 2,2′-bipyrimidine bridging ligand interacts in π/π/π fashion with two phenyl rings from the coligands above and below the central plane, while chiral compound 2 exhibits second-order nonlinear optical effect and temperature-dependent luminescence. Upon decreasing the temperature from 298 to 10 K, compound 2 shows a red light emission.     

Syntheses and properties of benzodipyrrinones

2,3‐Benzannelated dipyrrinone analogs ( 1 and 2 ) of xanthobilirubic acid ( 3 ) are prepared by base‐catalyzed condensation of isoindolinone ( 5 ) and indolin‐2‐one ( 6 ) respectively, with methyl 3‐(2‐formyl‐3,5‐dimethyl‐1H‐pyrrol‐4‐yl)propanoate ( 4 ). Nuclear Overhauser effect H‐nmr studies indicate that both 1 and 2 adopt preferentially a syn‐Z configuration. The former forms a hydrogen‐bonded homodimer in nonpolar solvents; the latter is intramolecularly hydrogen bonded.     

Syntheses and properties of cured epoxy resins containing the perfluorobutenyloxy group. I. Epoxy resin cured with perfluorobutenyloxyphthalic anhydride

Perfluorobutenyloxyphthalic anhydride (PFPA) has been synthesized as a new curing agent for epoxy resins, and the properties of epoxy resin cured with PFPA have been investigated. Good PFPA synthesis yields were realized by a dehydrating ring closure of perfluorobutenyloxyphthalic acid, which was obtained through the reaction of hexafluoropropene trimers with 4-hydroxyphthalic acid. Epoxy resin cured with PFPA was found to have several excellent properties. Its boilding water absorption was 0.45%, which is about a one-fourth that for conventionally cured epoxy resin. Its heat resistance was excellent, and its critical surface tension was almost the same as for PTFE.     

Syntheses and antifungal activities of dl-griseofulvin and its congeners. I

dl-Griseofulvin (1a) was prepared by two synthetic pathways. New 6'-congeners (3 and 4) of griseofulvin were also prepared. Their antifungal activities were evaluated and compounds 3 and 4 were found to be less active than 1a. Molecular calculations on 1a, dl-epigriseofulvin (1b), 3 and 4 were undertaken.     

Studies of poly(ortho-acylstyrenes). I. Syntheses and characterization

The syntheses of a number of o-acylstyrenes (o-acetyl through o-hexanoyl) have been described. Polymerizations were carried out radically at 80°C under high vacuum. While all polymerizations conform to the usual free radical kinetic scheme, rates are sensitive to the nature of the acyl substituent, and this has been ascribed to steric effects, the bulky substituents adjacent to the propagating radicals inhibiting the approach of monomer. Molecular weight and polydispersity data indicate that both combination and disproportionation occur during terminations. UV spectra consist of two absorptions associated with n → π^* and π → π^* transitions. ¹³C-NMR spectra have been analyzed and assignments made on the basis of spectral editing. The considerable variation of glass transition temperatures has been accounted for in terms of a combination of steric and dipolar interactions.     

Syntheses and characterizations of thermally reworkable epoxy resins. Part I

To meet the need for reworkable epoxy resins, a series of cycloaliphatic diepoxides containing thermally cleavable carbamate linkages were synthesized and characterized. These materials were shown to undergo curing reactions with cyclic anhydride in a similar fashion as a commercial cycloaliphatic epoxide, except that the carbamate group within the diepoxides can act as the internal catalyst. Furthermore, cured samples of the formulations from these diepoxides started to decompose at lower temperatures, i.e., between 200–300°C as compared with 350°C for the cured sample of the commercial cycloaliphatic epoxide, which showed their potential to be used as reworkable underfill encapsulants in the electronic packaging area. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2991–3001, 1999     

苯并咪唑金属铼(I)配合物的合成及发光性质的研究

以过渡金属铼为中心金属离子,合成了2-(2-吡啶)苯并咪唑(HL1)和2,6-二(苯并咪唑)吡啶(HL2)配合物.该配合物荧光量子产率高、化学性质稳定,在固体状态下,最大发射峰分别是543 nm、577 nm,处在绿光和黄光区.其发光基理是基态金属离子电荷向激发态配体跃迁(MLCT),属于金属离子与配体间的dπ→π~*(L)的跃迁发光.     

Syntheses and properties of selenium-bridged bischromones

The preparation of the new selenium-bridged chromones 5a-e is described. Compound 5c reacts with m-CPBA under various conditions to give the corresponding selenoxide 7 and the Pummerer products 8 and 9 . The selenides 5a-c react with excess m-CPBA to form the diselenides 13a-c . Oxidation of 13c with hydrogen peroxide afforded the chromone-3-seleninic acid 22 .     

Syntheses and properties of phosphorus-containing copolyamides

Caprolactam was copolymerized with 1,5-dioxo-1-methyl-4-azaphosphepane or methylphosphacaprolactam. The molecular weight of the resulting copolymers decreased with increasing concentration of the thermally labile phosphorus moieties. Copolymers based on ≥40% caprolactam were shown to be crystalline by differential scanning calorimetry and x-ray techniques. As the concentration of the phosphorus structures in the copolymers increased, the glass transition and crystallization temperatures increased while the melting temperatures, crystallinities, and thermal stabilities decreased. Melt blends of nylon 6 and polymethylphosphacaprolactam were shown by differential scanning calorimetry, a selective extraction technique, and elemental analysis to contain appreciable amounts of block copolyamides, and no crystalline random structures were detected. The thermal stabilities of the melt blends were similar to those of random copolymers having comparable concentrations of the phosphorus-containing sequences.     

Syntheses and Investigation of Some New Polyarylates and Copolyarylates. Part I

By the interfacial condensation of acid chlorides I, II, and III, respectively, with bifunctional phenols (IV-X), soluble or mold-able thermostable polyarylates were obtained. Similarly, copolyarylates were prepared from a mixture of the acid chlorides I + II or I + III. With bisphenol-A (VIII), soluble polymers are usually obtained. Methylene dichloride and/or carbon tetra-chloride-water systems were the best media for interfacial condensations, and the polymers formed showed the highest reduced viscosity values.

Polyester films are useful in many industrial applications because of their broad range of mechanical, optical, and electrical properties. The aromatic polyesters‐polyarylates-dominate the field of industrial polyester films [1].

Polyarylates prepared from dihydric phenols and purely aromatic dicarboxylic acid chlorides are highly heat resistant materials [2], but they are insoluble and nonmoldable [3]. However, by the introduction of ether linkages in the aromatic dicarboxylic acid moiety, soluble and/or moldable polyamides were obtained [4].     

Syntheses and properties of syndiotactic polystyrene

Syndiotactic polystyrene (SPS) is a new crystalline engineering thermoplastic. With a melting point of 270 °C and its crystalline nature, SPS has high heat resistance, excellent chemical resistance and water/steam resistance. Since SPS has excellent dielectric properties, it is useful as a capacitor insulation material. The rate of crystallization is very fast in comparison with isotactic polystyrene (IPS), thus, SPS can be used in a number of forming operations, including injection molding, extrusion and thermoforming. A system composed of a homogeneous titanium compound and methylaluminoxane (MAO) is an effective catalyst for syndiospecific polymerization of styrene. On the other hand heterogeneous titanium compounds containing halogen make a mixture of isotactic and syndiotactic components. The amount of syndiotactic polystyrene obtained is dependent on the mole ratio of Al to Ti. The result of ESR measurement suggests the Ti³⁺ species are important as a highly active site for producing syndiotactic polystyrene. A comparison of the stereoregularities of polypropylene and polystyrene formed by various metallocene catalysts is studied. The (C₆H₆)₂C(η₅-C₅H₄)(η₅-C₉H₆)TiCl₂/MAO system gives a homogeneous catalyst for the polymerization of propylene giving isotactic rich polypropylene and of styrene to give syndiotactic polystyrene.     

Syntheses and properties of H-1,2,3-triazoles

About twenty new H-1,2,3-triazoles (T) were readily synthesized by nucleophilic attack of sodium azide on activated acetylenes in dimethylformamide. Typical activating groups were COR, COOR, O₂NC₆H₄ PO(OC₂H₅, COT, and (C₆H₅)₃P⁺. Propynyl 4-triazolyl ketone or phenylethynyl 4-triazolyl ketone may be converted to acylic adducts (triazolylketoenamines), biheteroaromatic systems (isoxazolytriazoles, pyrazolytriazoles), as well as to ditriazolyl ketones. Certain T properties were examined in detail. The apparent pK′s for our group of ca 30 triazoles were in the range 4·95?9·45 in ethanol-water (v/v 1/1) at 25°. The Hammett correlation for five 4-aryl-T was log K_a = 0·89σ^? ?9·21 and for seven 4-aryl-5-carbethoxy-T was log K_a = 1·45σ?6·95. The UV spectra of T are similar to those of other heteroaromatic and phenyl compounds: interesting analogies between triazolyl and phenyl, e.g., ”ortho“ crowding effects, appear to be indicated in the spectra of compounds related to biphenyl, stilhene and benzophenone. With regard to structure assignment on the basis of spectra, characteristic features of UV and IR spectra of the H-1,2,3-triazoles are discussed.     

Syntheses and some properties of N-unsubstituted sulfilimines

A variety of S-aminosulfonium mesitylenesulfonates, R¹R²S⁺NH₂·X⁻, were prepared in high yields by the reaction of sulfides with O-mesitylenesulfonylhydroxylamine (MSH). The thermal stability of the derived sulfilimines was examined. Reaction of allyl sulfides with MSH afforded directly the salts of allylamines in good yields, presumably via [2,3]-sigmatropic rearrangement of unisolable allylsulfilimines followed by S---N bond cleavage. The reactions of disulfides and thioketone with MSH are also described.     

Cobaltacarborane-phthalocyanine conjugates: Syntheses and photophysical properties

Syntheses of two new cobaltacarborane-phthalocyanine conjugates, one anionic (Pc 6) and one zwitterionic (Pc 7), were accomplished via cyclotetramerization of the corresponding cobaltacarborane-substituted phthalonitriles (4 or 5) with excess phthalonitrile in quinoline. X-ray structures of two phthalonitrile precursors (2 and 3) were obtained and are discussed, and the absorption and emission properties of the two cobaltacarborane-phthalocyanine conjugates in several solvents were investigated. The anionic conjugate 6 exists mainly as a monomer in polar organic solvents and has fluorescence quantum yields in the region 0.2-0.3. The zwitterionic conjugate 7 aggregates in solution and displays lower quantum yields ∼0.1 in organic solvents.     

Syntheses, structures, and photophysical properties of mono- and dinuclear sulfur-rich gold(I) complexes

The dinuclear gold complexes [{Au(PPh 3)} 2(mu- dmid)] ( 1) ( dmid = 1,3-dithiole-2-one-4,5-dithiolate) and [{Au(PPh 3)} 2(mu- dddt)] ( 2) ( dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) were synthesized and characterized by X-ray crystallography. Both complexes exhibit intramolecular aurophilic interactions with Au...Au distances of 3.1984(10) A for 1 and 3.1295(11) A for 2. A self-assembly reaction between 4,5-bis(2-hydroxyethylthio)-1,3-dithiole-2-thione ( (HOCH 2 CH 2 ) 2 dmit) and [AuCl(tht)] affords the complex [AuCl{ (HOCH 2 CH 2 ) 2 dmit}] 2 ( 4), which possesses an antiparallel dimeric arrangement resulting from a short aurophilic contact of 3.078(6) A. This motif is extended into two dimensions due to intra- and intermolecular hydrogen bonds via the hydroxyethyl groups, giving rise to a supramolecular network. Three compounds were investigated for their rich photophysical properties at 298 and 77 K in 2-MeTHF and in the solid state; [Au 2(mu- dmid)(PPh 3) 2] ( 1), [Au 2(mu- dddt)(PPh 3) 2] ( 2), and [AuCl{( HOCH 2 CH 2 ) 2 dmit}] ( 4). 1 exhibits relatively long-lived LMCT (ligand-to-metal charge transfer) emissions at 298 K in solution (370 nm; tau e approximately 17 ns, where M is a single gold not interacting with the other gold atom; i.e., the fluxional C-SAuPPh 3 units are away from each other) and in the solid state (410 nm; tau e approximately 70 mus). At 77 K, a new emission band is observed at 685 nm (tau e = 132 mus) and assigned to a LMCT emission where M is representative for two gold atoms interacting together consistent with the presence of Au...Au contacts as found in the crystal structure. In solution at 77 K, the LMCT emission is also red-shifted to 550 nm (tau e approximately 139 mus). It is believed to be associated to a given rotamer. 2 also exhibits LMCT emissions at 380 nm at 298 K in solution and at 470 nm in the solid state. 4 exhibits X/MLCT emission (halide/metal to ligand charge transfer) where M is a dimer in the solid state with obvious Au...Au interactions, resulting in red-shifted emission band, and is a monomer in solution in the 10 (-5) M concentration (i.e., no Au...Au interactions) resulting in blue-shifted luminescence. Both fluorescence and phosphorescence are observed for 4.     

冠醚螺吡喃化合物的合成和光致变色性质

合成了四个新的6位带不同取代基的含冠醚结构单元吲哚啉螺苯并吡喃化合物(5a-5d),研究了其光致变色性质和离子诱导光致变色作用及取代基的影响。结果表明冠醚能稳定螺吡喃开环形式,碱金属离子对冠醚螺吡喃的生色有诱导作用;6位为吸电子基团时,螺吡喃开环形式的稳定性增加,而6位为推电子基团时,螺吡喃开环形式的稳定性降低。另外,就稳定螺吡喃开环体的作用来说,吲哚啉环上的取代基效应和苯并吡喃环上的正好相反。