New processable poly(ether-keto-sulfone)s,poly(arylene sulfone)s,and polyesters curable by intramolecular cyclization. XVII

New processable polyaromatic ether-keto-sulfones were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I), bis(p-phenoxybenzene)sulfone (V), isophthaloyl chloride (VI), terephthaloyl chloride (VII), and diphenylether (IX) in Friedel-Crafts-type polymerizations. By varying (VI):(VII) ratio and (V):(IX) ratio and by reducing the polymerization time, soluble, processable polymers were obtained. In these polymers, phenylacetylenyl groups were introduced by replacing the iodine. This process led to soluble and curable polymers. Transparent, tough films and fairly flexible glass fiber laminates can readily be prepared. After curing, the polymers were insoluble and showed excellent chemical and thermal resistance. The curing process increased the polymers' softening temperature by ca. 20°C and produced intersting new useful materials for laminates. Processable poly(arylene sulfone)s were prepared from I, V, and diphenylether-4,4′-disulfonylchloride (X) in a Friedel-Crafts-type polymerization. Different monomer ratios and polymerization times were used. Only low-molecular-weight polymers were obtained. The same result was shown by curable polyester formation from I, VI, VII, and 4,4′-sulfonyldiphenol (XI) in an interfacial polycondensation.     

A flame‐retardant phosphate and cyclotriphosphazene‐containing epoxy resin: Synthesis and properties

A novel flame‐retardant epoxy resin, (4‐diethoxyphosphoryloxyphenoxy)(4‐glycidoxyphenoxy)cyclotriphosphazene (PPCTP), was prepared by the reaction of epichlorohydrin with (4‐diethoxyphosphoryloxyphenoxy)(4‐hydroxyphenoxy)cyclotriphosphazene and was characterized by Fourier transform infrared, ³¹P NMR, and ¹H NMR analyses. The epoxy resin was further cured with diamine curing agents, 4,4′‐diaminodiphenylmethane (DDM), 4,4′‐diaminodiphenylsulfone (DDS), dicyanodiamide (DICY), and 3,4′‐oxydianiline (ODA), to obtain the corresponding epoxy polymers. The curing reactions of the PPCTP resin with the diamines were studied by differential scanning calorimetry. The reactivities of the four curing agents toward PPCTP were in the following order: DDM > ODA > DICY > DDS. In addition, the thermal properties of the cured epoxy polymers were studied by thermogravimetric analysis, and the flame retardancies were estimated by measurement of the limiting oxygen index (LOI). Compared to a corresponding Epon 828‐based epoxy polymer, the PPCTP‐based epoxy polymers showed lower weight‐loss temperatures, higher char yields, and higher LOI values, indicating that the epoxy resin prepared could be useful as a flame retardant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 972–981, 2000     

双邻位甲基取代的聚芳醚酮合成与表征

两种单体 2 ,2′ ,6 ,6′ 四甲基 4 ,4′ 二苯氧基二苯酮 (o M2 DPOBP)和 2 ,2′ ,6 ,6′ 四甲基 4 ,4′ 二苯氧基三苯二酮 (o M2 DPOTPDK) ,分别与对苯二甲酰氯 (TPC)和间苯二甲酰氯 (IPC)低温亲电溶液缩聚 ,合成了 4种含双邻位甲基侧基聚醚酮醚酮酮 (DM PEKEKK和DM PEKEKMK)及含双邻位甲基侧基聚醚酮酮醚酮酮 (DM PEKKEKK和DM PEKKEKMK)聚合物 .用FT IR、1 H NMR、DSC、TGA、WAXD等方法对聚合物进行了表征 ,研究了聚合物的溶解性能 .结果表明 ,该 4种聚合物具有较高的玻璃化转变温度 ,良好的热稳定性和优良的溶解性能 .     

Polyesters,polyurethanes, and epoxy resin derived from 2,2′-(1,4-phenylenedivinylene)bis-5-hydroxypyridine

2,2′-(1,4-Phenylenedivinylene)bis-5-hydroxypyridine (PBHP) was used as a starting material for preparing new polyesters and polyurethanes as well as a diepoxide-bearing styrylpyridine segments. The diesters were prepared by reacting PBHP with terephthaloyl or adipoyl dichloride utilizing the interfacial polycondensation method. The diesters were prepared from the reaction of PBHP with tolylene diisocyanate or methylenebis(4-phenylisocyanate). In addition, a model diester and diurethane were synthesized by reacting PBHP with benzoyl chloride and phenyl isocyanate, respectively. Both model compounds and polymers were characterized by IR and ¹H-NMR spectroscopy, as well as by DTA and TGA. A diepoxide was also prepared from the reaction of PBHP with epichlorohydrin which was polymerized in the presence of 4,4′-diaminodiphenylsulfone. The polyester derived from PBHP and terephthaloyl dichloride was the most thermostable polymer obtained. It was stable in N₂ up to 355°C and afforded an anaerobic char yield of 59% at 800°C. The thermal stabilities of polymers were improved by curing.     

Methylene-bridged aromatic polyesters. Synthesis,characterization, and radiation-induced crosslinking

Aromatic polyesters connected by methylene groups were synthesized. Two pairs of aromatic diacid chlorides, 3,3′-methylenedibenzoyl chloride and 4,4′-methylenedibenzoyl chloride were each polymerized via interfacial polycondensation with 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 3,3′-methylenediphenol, and 4,4′-methylenediphenol. For comparison, 3,3′-carbonyldibenzoyl chloride and 4,4′-carbonyldibenzoyl chloride were similarly polymerized with bisphenol A. Substitution of meta,meta' oriented phenylene groups for para,para' oriented phenylene groups had a significant and cumulative effect in reducing the glass transition temperatures of the polymers, thereby enhancing their processability. In air the methylene groups of the polyesters undergo oxidation and crosslinking at elevated temperatures. Electron beam irradiation of thin films of the methylene-linked polyesters at room temperature resulted in some chain extension and crosslinking, as evidenced by increased solution viscosity and gel formation. Irradiation at a temperature near or above the glass transition temperatures of the polymers greatly enhanced the tendency for the polymers to crosslink.     

New processable polyaromatic amides curable by intramolecular cyclization. XVI

New Processable Polyaromatic amides were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I) and several aromatic diamines. Phenylethynyl groups were introduced in these polymides by replacing the iodine groups with copper phenyl acetylide. On thermal curing, 2,2′-di(phenylethynyl)biphenyl group undergoes intramolecular cyclization to form 9-phenyl dibenzanthracene derivative. The cured polymers showed increased heat and chemical stabilities. No melting points were observed for all the polymers below 500°C. The viscosity of the polymers was decreased on substitution of the iodine by phenylethynyl groups.     

Synthesis and properties of conjugated enyne polysulfones

High-molecular-weight polysulfones that contained 1,3-enyne linkages in the polymer backbone were prepared by the reaction of potassium salts of (E)-1,3-bis(3-hydroxyphenyl)-1-buten-3-yne and 4,4′-dihydroxybiphenyl with 4,4′-dihalodiphenylsulfones in DMSO-sulfolane solvent mixtures. The polymers were soluble in methylene chloride and exhibited intrinsic viscosities as high as 0.74 (in DMAC at 30°C) with glass transition temperatures ranging from 179 to 214°C. It was postulated that on heating the polymers would cure via a intramolecular cycloaddition reaction to from a 2-phenylnaphthalene fused ring system along the polymer backbone. Thermal analytical data studies on cured polymer films and investigations of the products obtained from the thermal reactions of model compounds indicated that the primary curing reaction was intermolecular rather than intramolecular in nature. Additional data from testing fabricated composites indicated that the enyne polysulfones have suitable properties for use as high-temperature thermoplastic composite materials.     

Polymers from 4,4′-sulfonyldiphenol

Several polymers have been prepared from 4,4′-sulfonyldiphenol (SDP) or its bis-phenate salt as the nucleophile in condensation polymerizations. Ester-sulfone-amic acid polymers were of fairly high molecular weight, and could be imidized. Soluble film-forming poly ether-ester-sulfones were prepared from diphenyl ether diacid chloride.     

Preparation and properties of polyamides and polymides containing bibenzyl,stilbene, and tolan structures

Polyisophthalamides and polyterephthalamides were prepared by the solution polycondensation of the corresponding diacyl chlorides with 4,4′-diaminobibenzyl, trans-4,4′-diaminostilbene, and 4,4′-diaminotolan in N,N-dimethylacetamide (DMAc). Polypyromellitimides were synthesized in two steps by the ring-opening polyaddition of pyromellitic dianhydride with the aromatic diamines in DMAc, followed by thermal cyclodehydration. The amorphous polyisophthalamides were soluble in some amide solvents containing lithium chloride, while the polyterephthalamides having fair degree of crystallinity were insoluble in these solvents. The thermal stability of these aromatic polymers decreased in the order of the tolan-containing polymers > the stilbene-containing polymers > the bibenzyl-containing polymers, both in air and under nitrogen.     

Polyesters,polyurethanes and epoxy resins derived from 2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinaldine and 6-(4-hydroxystyryl)-3-hydroxypyridine

New polyesters and polyurethanes as well as diepoxides bearing styrylpyridine segments were prepared utilizing 2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinaldine (PBHQ) and 6-(4-hydroxystyryl)-3-hydroxypyridine (HSHP) as starting materials. The polyesters were prepared by reacting PBHQ or HSHP with terephthaloyl dichloride in the presence of an acid acceptor utilizing the solution polycondensation method. The polyurethanes were prepared from the reactions of PBHQ and HSHP with tolylene diisocyanate and methylenebis(4-phenylisocyanate). In addition, model diesters and diurethanes were synthesized by reacting PBHQ and HSHP with benzoyl chloride and phenyl isocyanate, respectively. Model compounds and polymers were characterized by FT-IR and ¹H-NMR spectroscopy as well as by DTA and TGA. Diepoxides were also prepared from the reactions of PBHQ and HSHP with epichlorohydrin which were polymerized in the presence of 4,4′-diaminodiphenylsulfone. The polyesters were the most thermostable polymers obtained. After curing at 240°C for 20 h, they were stable in N₂ up to 345–370°C and afforded anaerobic char yields of 65–75% at 800°C. © 1993 John Wiley & Sons, Inc.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. III

4,4′-Diphenoxydiphenylsulfone was polymerized with isophthaloyl chloride and terephthaloyl chloride in Friedel-Crafts polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone obtained either by using 1,3-bis(p-phenoxybenzoyl)-5-cyanobenzene or 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A terpolymer having 22 wt-% 5-cyanoisophthaloyl unit was also prepared from the Friedel-Crafts polymerization of 1,3-bis(p-phenoxybenzenesulfonyl)benzene and 5-cyanoisophthaloyl chloride. These terpolymers were crosslinked through heating to give insoluble products which proved to be thermally less stable than the uncrosslinked polymers.     

Aromatic polyether, -ketone, -sulfones as laminating resins. XII. Derivatives of 2,2′-diphenylethynyldiphenyl which cure by an intramolecular cyclization

Polymers made from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride, diphenyl ether, and isophthaloyl chloride have been made and converted to the 2,2′-diphenylethynyl derivatives. Introduction of units of isophthaloyl chloride reduced the melting point of these polymers to about 200°C, and they could then be cured by heating. A good glass laminate was prepared and cured from one of the polymers.     

Preparation and characterization of optically active and organosoluble poly(amide‐imide)s from polycondensation reaction of N,N′‐(4,4′‐sulphonediphthaloyl)‐bis‐L‐isoleucine diacid with aromatic diamines

3,3′,4,4′‐Diphenylsulfonetetracarboxylic dianhydride (1) was reacted with L ‐isoleucine (2) in acetic acid and the resulting imide‐acid (3) was obtained in high yield. The diacid chloride (4) was prepared from the diacid derivative (3) by reaction with thionyl chloride. The polycondensation reaction of diacid chloride (4) with several aromatic diamines such as 4,4′‐sulfonyldianiline (5a), 4,4′‐diaminodiphenyl methane (5b), 4,4′‐diaminodiphenylether (5c), p‐phenylenediamine (5d),m‐phenylenediamine (5e), 2,4‐diaminotoluene (5f) and 4,4′‐diaminobiphenyl (5g) 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% of radiation power. Several new optically active poly(amide‐imide)s with inherent viscosity ranging from 0.23 to 0.41 dl/g were obtained with high yield. All of the earlier polymers were fully characterized by 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.     

New processable polyaromatic ether–keto-sulfones curable by Diels-Alder cycloaddition

New Processable polyaromatic ether-keto-sulfones were prepared from the acid chloride of bis-m-carboxyphenyl acetylene (XII), isophthaloyl chloride (XX), diphenyl ether (XVIII), and 4,4′-diphenoxydiphenyl sulfone (XIX) in a Friedel-Crafts-type polymerization. These polymers were cured by Diels-Alder cycloaddition with 1,4-diphenyl-1,3-butadiene. The cured polymers showed an increase in T_g and in thermal and heat stabilities. The polymers form colorless, transparent, brittle films and can be cast into a glass fiber laminate. Both meta-and para-substituted acid chlorides of biscarboxyphenyl-1,3-butadiene yielded insoluble polymers under the same conditions but form processable polymers where combined with acetylene units in the polymer chain. Polymers that contained both acetylene and butadiene units were prepared but could not be cured by an intramolecular Diels-Alder cycloaddition reaction.     

Rigid-rod polymers with polysiloxane side chains. 2. Synthesis and characterization of aromatic polybenzobisoxazoles with polysiloxane side chains and composite formation with polysiloxane matrices

Aromatic polybenzobisoxazoles, having polydimethylsiloxane side chains (SCPBOs), were prepared using terephthaloyl chloride-terminated polydimethylsiloxane macromonomers and 3,3′-bis(trimethylsiloxy)-4,4′-bis(trimethylsilylamino)biphenyl for the purpose of dispersing rigid-rod molecules in silicone matrices for molecular reinforcement. The degree of polymerization of the side chain was varied from 7.8 to 45.4, and a small amount of (3-butenyloxy)terephthaloyl chloride was copolymerized to give the polymers a functionality that can be linked to the matrices. For all the SCPBOs, the WAXD pattern showed only diffuse reflections, suggesting limited structural regularity, although the polymers were optically anisotropic. No melting transition was observed below the side chain decomposition temperature, 350°C. A polydimethylsiloxane/polybenzobisoxazole composite elastomer was obtained first curing the polysiloxane matrix containing the prepolymer of the SCPBO, followed by in situ thermal ring closure of the prepolymer. Some reinforcement was observed, but the presence of plasticizing effect by the unbound SCPBO was suggested at the same time. © 1995 John Wiley & Sons, Inc.     

Synthesis and mesogenic properties of four series of polyesters derived from dicarboxylic and dihydroxylic aromatic monomers

Some members of four series of polyesters were synthesized by the direct polycondensation of two types of dicarboxylic acids (4,4′-dicarboxy-α,ω-diphenoxyalkanes and 4,4′-dicarboxy-α,ω-dibenzoyloxyalkanes) with two types of bisphenols (4,4′-dihydroxy-α,ω-diphenoxyalkanes and 4,4′-dihydroxy-α,ω-dibenzoyloxyalkanes) using tosyl chloride in pyridine in the presence of N, N-dimethylformamide. The ¹H-NMR spectra of the polymers synthesized showed that these polymers have an ordenated structure. The mesogenic properties of these polymers were studied by optical microscopy and differential scanning calorimetry. Many of the polymers show nematic mesomorphism.     

Polyquinoxalines. III

Six thermally stable polyquinoxalines have been prepared by the reactions of combinations of three tetraamines, 3,3′,4,4′-tetraaminodiphenyl sulfone (II), and 3,3′,4,4′-tetraaminodiphenyl ether (V), with two bisglyoxals, 4,4′-diglyoxalyldiphenyl sulfide dihydrate (III) and 4,4′-diglyoxalyldiphenyl sulfone dihydrate (IV). The polymers were prepared from polymerization in two stages. The first stage, a solution polymerization, produces an initially low or moderate molecular weight material, which is advanced to a high molecular weight (η_inh > 1.0) by heating at 375°C. under reduced pressure. All the polyquinoxalines have excellent thermal stability both in nitrogen and in air and improved solubility.     

New processable polyaromatic ether-keto-sulfones curable by intramolecular cyclization. XV

New processable polyaromatic ether-keto-sulfones were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I), bis(p-phenoxybenzene)sulfone (II), isophthaloyl chloride (III), and diphenyl ether (IV) in Friedel–Crafts-type polymerizations. In the most promising of the iodine-containing polymers phenylacetylenyl groups were introduced in place of iodine. This polymer, with an initial monomer ratio of I:II:III:IV = 1:5:7:3, was further investigated. It is soluble in DMF, DMA, pyridine, and sulfuric acid. After curing it was insoluble in all solvents used and lost only 1.1% of its weight at 300°C when heated in air for three days. Hence in this cured state it has excellent chemical and thermal resistance. It can be cast into a film from solution in DMAc and a glass fiber laminate is readily prepared. The film is tough, transparent, and brown in color. The cured film is tougher than the uncured. The glass fiber laminate is also tough and fairly flexible. A distinct advantage of this type of polymer is its ready availability in relatively cheap raw materials. The phenylacetylenyl-group-containing polymer showed a transition temperature at 175°C and two exotherm peaks at 243 and 361°C which disappeared after curing in a DSC thermogram. Before and after curing this polymer displayed softening temperatures at 149 and 171°C, respectively, measured by a Vicat apparatus at a heating rate of 1°C/min. No melting temperatures up to 500°C were observed for any of the polymers in this study.     

Synthesis of inherently dissymmetric polyamides,

The preparation of polyamides from derivatives of optically active biphenic acid is described. The diacid chlorides chosen were 2,2′-dinitro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride and 2,2′-dichloro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride, the diamines were phenyldiamines (o-, m-, p-) piperazine, trans-2,5-dimethylpiperazine, and 1,2-piperaazolidine. Polymerization was carried out by the method of interfacial polycondensation. The polymers of aromatic diamines were insoluble in common organic solvents but soluble in dimethylformamide containing 5% lithium chloride, triesters of phosphoric acid, and methanesulfonic acid. The polymers of aliphatic diamines were also insoluble in common organic solvents but soluble in trifluoroethanol. All polymers had melting points higher than 280°C.     

Aromatic polyamides and polyimides derived from 3,3′-diaminobiphenyl: Synthesis,characterization, and molecular simulation study

In this article a new synthesis of 3,3′-diaminobiphenyl (3,3′-DABP) is described, along with the preparation and characterization of polyamides and polyimides based on it. Reactivity of this monomer was calculated by a molecular simulation study, using ab initio quantum-mechanical methods. Terephthaloyl and isophthaloyl chloride were used for the synthesis of polyamides, while 3,3′,4,4′-biphenylenetetracarboxylic acid dianhydride and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride were used for the synthesis of polyimides. Medium to high molecular weight polymers were attained, with inherent viscosities near or higher than 1.0 dL/g, the solubility of the 3,3′-DABP polymers was much better than that of the homologous polymers from benzidine (4,4′-DABP), the glass-transition temperatures were lower, by about 40°C, and the thermal resistance, as measured by thermogravimetry, was virtually the same. Amorphous films, made from cast polymer solutions, showed excellent mechanical properties, comparable to conventional aromatic polyamides and polyimides. Theoretical calculations demonstrated that the radius of giration, end-to-end distance and density of poly(3,3′-DABP-isophthalamide) were lower than those of poly(4,4′-DABP-isophthalamide), as a consequence of the chain folding induced in the backbone by the m-substitution in 3,3′-DABP. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4646–4655, 1999