Sulfur-containing polymers. II. Preparation and properties of polycarbamoylsulfenamides

Polycarbamoylsulfenamides have been prepared by interfacial and solution polycondensation of chlorocarbonylsulfenyl chloride with diamines. In preparing the polycarbamoylsulfenamides, the following types of diamines were used: primary aliphatic diamines, a mixed primary-secondary aliphatic diamine, primary aromatic diamines, and secondary aromatic diamines. The properties of the resulting polymers depended primarily on the kind of diamines used. Transparent, tough films were obtained from the polymer based on N,N′-dimethyl-4,4′-diaminodiphenylmethane. The photochemical decomposition of the polymers has been studied.     

Heat-resistant polymers with thianthrene analog units. II . Aromatic polyamides

A series of polyamides which contained thianthrene, phenoxatiin, and dibenzo-p-dioxin units was synthesized from tricyclic fused-ring diamines and aromatic diacid chlorides by solution polycondensations at a low temperature. The amorphous polyisophthalamides were highly soluble in polar organic solvents, whereas some of the polyterephthalamides with a fair degree of crystallinity were insoluble. The solubility of the series of polyamides increased in the order of the dibenzo-p-dioxin-containing polymers < phenoxatiin-containing polymers < thianthrene-containing polymers. The thermal stability increased in the reverse order and the dibenzo-p-dioxinpolyamides were more thermostable than the corresponding open-chain polymers with diphenyl ether linkages. The polyamides derived from 2,8-oriented tricyclic diamines showed somewhat lower glass transition temperatures than those from 2,7-oriented diamines.     

Synthesis of polyamideamines from 5-oxazolones

Polyamideamines with a sequence of two amide and one amine linkage in a main chain were synthesized from the polyaddition of 2-isopropylidene-4-alkyl-3-oxazolin-5-ones and primary diamines. The polyaddition reaction proceeded through 1,4-conjugate addition of an amine group to 3-oxazolin-5-one and subsequent ring opening of the intermediate addition product with another amine. Although aliphatic diamines gave oily polymers, xylylenediamines afforded amorphous solid polymers. The reduced viscosities and polymer melt temperature of the polymers were 0.05–0.12 and 90–130°C., respectively.     

Preparation and properties of polyamides and polyimides containing phenoxathiin units

Novel polyimides and polyimides having phenoxathiin units have been prepared. Polyamides with inherent viscosities in the range of 0.5–2.9 were readily prepared by the polycondensations of phenoxathiin diamines with aromatic diacyl chlorides and of aromatic diamines with new phenoxathiin diacyl chlorides. The polyimides were synthesized from phenoxathiin diamines and pyromellitic dianhydride by using a two-step procedure. The polyamic acids which formed in the first step had inherent viscosities ranging from 1.0 to 1.6, and they were converted to the polyimides by thermal cyclodehydration. Some of the phenoxanthiin-containing polyamides were highly soluble in polar amide solvents and dimethyl sulfoxide. A series of novel polymers containing phenoxathiin units were much more thermostable than the corresponding polymers having open-chain diphenyl ether linkages.     

Differential reactivity of aromatic diamines during polyimide formation in water

A series of mono and di-imide compounds were synthesized by the reaction of common aromatic diamines with 4,5-dichlorophthalic acid in aqueous solution (at temperature between 160 °C and 200 °C) as a precursor to determining the chemical reactivity changes in these diamines during copolyimide synthesis under the same conditions. The reactivities of the second amino group were shown to reduce dramatically, in number of examples, after substitution had occurred on the first amino group. The effect of these reactivity changes on polymer and copolymer properties was examined by the synthesis of a series of polymers containing two of the diamines with very different reactivity behaviours.The model compounds and polymers were characterized by FTIR, ¹H NMR and where possible by mass spectroscopy. The polymers were also characterized by GPC, Tg and some mechanical properties.     

Synthesis and investigation of polymers based on the nitriles of polycarboxylic acids and diamines

The influence of the reaction medium on the polycondensation of the tetranitriles of tetracarboxylic acids and diamines has been investigated. The reaction in phenol and cresols yields polymers with macroheterocycles in the chain—polyhexasocyclanes. If phenols with electron-accepting substituents are used as reaction medium, nonmacrocyclic polymers with side aroxyl groups in the chain, polyisoindoxazenes—are formed. The properties of these polymers were studied. Macroheterocyclic compounds formed by condensation of phthalodinitrile with diamines can be used as one of the initial substances in polyhexasocyclane synthesis. Polyamidohexasocyclanes were prepared by polycondensation of macroheterocycles with dicarboxylic acid dichlorides. Some regularities of their formation and their properties were investigated.     

Sulfur-containing polymers. VIII. Preparation and properties of poly(carbamoyl disulfides)

Poly(carbamoyl disulfides) have been prepared for the first time by the stepwise condensation of chlorocarbonylsulfenyl chloride with dithiols and diamines. The polymers obtained in high yields had inherent viscosities up to 1.86. The properties of the polymers depended primarily on the kind of diamines used. Some of the polymers gave transparent, tough films from chloroform solution. The polymer films decomposed by ultraviolet irradiation with liberation of carbonyl sulfide. All the polymers gradually became brittle during storage for 6–8 months under diffused light.     

New high-temperature polymers. II. Ordered aromatic copolyamides containing fused and multiple ring systems

Symmetrical diamines, containing preformed carbonamide linkages, were prepared by reacting nitrobenzoyl chlorides with aromatic diamines and reducing the dinitro intermediates. The diamines were polymerized with aromatic diacid chlorides to give wholly aromatic ordered copolyamides of exceptionally high thermal stability. Ordered diamines were prepared containing only phenylene units as the aromatic portion, and others containing phenylene and naphthylene or biphenylene groups. Low-temperature solution polymerization of these diamines with isophthaloyl chloride, 4,4′-bibenzoyl chloride, or 2,6-naphthalenedicarbonyl chloride, gave thirteen ordered copolyamides, each containing a naphthylene and/or biphenylene group in its repeating unit. Differential thermal analyses and thermogravimetric analyses showed these polymers to have melting points or decomposition temperatures of from 420 to over 500°C. Films of one of the polymers had a breakdown voltage of 3000 v./mil at 180°C. Fibers of the same composition had tenacities of up to 8 g/den.; a 5.5 g/den. sample retained 85% of its tenacity after 17 hr. at 300°C. and 21% after 9 days.     

Synthesis and characterization of polymers derived from 2,5-dimethoxy-terephthaldehyde and 2,5-dimethoxy-terephthalic acid

Polyamides were synthesized from 2,5-dimethoxyterephthaloyl dichloride and diamines. Also, polyimines and polyaldoles were prepared from 2,5-dimethoxy-terephthaldehyde with diamines and ketones. The polymers were characterized by elemental analysis and infrared and NMR spectroscopy. Their intrinsic viscosity, glass transition temperature, and thermaldecomposition temperatures were determined.     

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.     

Soluble polyimides containing alicyclic structures

A series of novel aromatic diamines containing kinked cycloalkane structures between two phenyl rings were synthesized by HCl-catalyzed condensation reaction of excess aniline and corresponding cycloalkanone derivatives. The structures of the diamines were indentified by ¹H NMR, ¹³C NMR, FT-IR spectroscopy and elemental analysis. The polyimides were synthesized from the obtained diamines with various aromatic dianhydrides by one-step polymerization in m-cresol. The polymerization was conducted for 6∼8 h with refluxing, which was enough to obtain the polymers with high molecular weight. The inherent viscosities of the resulting polyimides were in the range of 0.37∼1.66 dl/g. All polymers were readily soluble in common organic solvents such as chloroform, tetrachloroethane, dimethylacetamide, etc. and the glass transition temperatures were observed at 290 to 372°C. UV-visible spectra were obtained to measure the transparency of polymer films. Most of the polymers showed high transmission above 90 % in the wavelength of 450 ∼ 600 nm.     

Sulfur-containing polymers. V. Preparation of polyoxycarbonylsulfenamides by polycondensation of bis(oxycarbonylsulfenyl chlorides) with diamines

Polyoxycarbonylsulfenamides (POSA) have been prepared by interfacial polycondensation of bis(oxycarbonylsulfenyl chlorides) with diamines. The polymers obtained ranged in physical form from crystalline solids to resinous materials depending on the kind of both bis(oxycarbonylsulfenyl chlorides) and diamines used. Some of the polymers gave transparent pliable films from chloroform solution. The polymer films decomposed with liberation of carbonyl sulfide on being subjected to ultraviolet radiation.     

新型含金属元素二胺的合成与表征

本文分别用液相法和固相法合成了一系列含不同金属元素的二胺,并通过红外光谱,~1HNMR、~(13)CNMR,紫外光谱,电化学分析及元素分析对其进行表征,还通过DSC和TG对其热性能进行了研究,结果发现这些二胺具有良好的耐热性,是合成一些耐热高聚物的优良原料.     

Phenoxasilin-containing polyamides and polyesters

Silicon-containing polyamides and polyesters of a new type have been synthesized. They contain phenoxasilin rings with double-stranded structure. The polymers were synthesized by the interfacial polycondensation of 2,8-dichloroformyl-10,10-diphenylphenoxasilin with diamines and bisphenols, and were obtained in nearly quantitative yields. Their reduced viscosities were in the range of 0.53–1.47 dl g^?1 m dimethylformamide (DMF), m-cresol or chloroform. Some of the polyamides were soluble in polar aprotic solvents such as DMF and N-methyl-2-pyrrolidone (NMP) and the polyesters had good solubility in chloroform, phenol-sym tetrachloroethane (60:40 by wt %) and acidic solvents (m-cresol and nitrobenzene). The polymers hardly dissolved in cone. H₂SO₄ and some of them coloured in it. Only the polyester having sulphide bonds was soluble in benzene in addition to the above organic solvents. These polymers hardly degraded below 400° except for the polyamides derived from aliphatic diamines. The polymers from aliphatic diamines melted at 290–325°; the other polyamides and the polyesters decomposed without melting.     

Synthesis of polyenamines by vinylogous nucleophilic substitution polymerization of 2,2′-disubstituted bis(4-ethoxymethylene-5-oxazolone) with diamines

A new class of polyenamines was synthesized by the vinylogous nucleophilic substitution polymerization of 2,2′-p-phenylenebis(4-ethoxymethylene-5-oxazolone) with diamines in polar aprotic solvents under very mild conditions. The polymers derived from aliphatic diamines were soluble in these solvents and had inherent viscosities in the range of 0.3–0.9. The dilute solutions showed marked decrease in viscosity with time, presumably due to hydrolytic chain scission of the enamine structures in the polymer backbone. The polymers exhibited no melting temperature, and onset of breakdown under thermogravimetric analysis in a nitrogen atmosphere occurred at 250–300°C.     

Polyurethanes and polyureas having long methylene chain units

Polyurethanes and polyureas containing long methylene chain units have been prepared from the following six series of monomer combinations; aliphatic diisocyanates with aliphatic glycols or diamines, methylene bis(4-phenyl isocyanate) with aliphatic glycols or diamines, and p-xylylene diisocyanate with aliphatic glycols or diamines. A good linear relationship was noted between the polymer melting points of each series against the concentration of functional groups. Both polyurethanes and polyureas from p-xylylene diisocyanate showed higher melting points than those from methylene bis(4-phenyl isocyanate) with corresponding aliphatic monomers. The relations between the melting points of these polymers with long methylene chains, including polyamides which were previously reported, and the chain components were discussed. The higher melting points of polymers containing p-xylylene group are attributed to the high rigidity of this group.     

New high temperature polymers. I. Wholly aromatic ordered copolyamides

Wholly aromatic ordered copolyamides of unusually high thermal stability were prepared by the condensation of aromatic diacid chlorides with symmetrical diamines containing preformed aromatic amide units in an ordered arrangement. The preservation of order in the condensation step was assured by using interfacial or solution polymerization techniques at temperatures below 50°C. Each polymer contains units derived from aminobenzoic acids, arylene diamines, and arylene diacids. By use of para- and meta- phenylene units, eight different polymers are possible; all were prepared. Differential thermal analyses and thermogravimetric analyses showed these polymers to have melting points or decomposition temperatures in a range from 410°C. for the all-meta polymer to 555°C. for the all-para one. Substitution of the internal N-hydrogens of the diamines with methyl groups or phenyl groups leads to additional ordered copolymers. Several were prepared, but their melting points were much lower than those of the parent polymers limiting their usefulness in high temperature applications. Tough pliable films were prepared from all eight unsubstituted polymers, and crystalline fibers with tenacities of ca. 6 g./den. were prepared from three of the polymers. The properties of the fibers were retained to a high degree even when determined at temperatures up to 400°C. Fibers aged at 300°C. for extended periods of time showed remarkable retention of fiber properties.     

Chemical reactions and reactivity of primary,secondary, and tertiary diamines with acid functionalized polymers

Reactive melt processing of different types of diamines with polyethylene containing carboxylic acid groups and polystyrene containing anhydride groups was carried out. The reactivity of primary, secondary, and tertiary diamines with these acid polymers was determined using various techniques. Molecular weight increases due to crosslinking were observed through (1) changes in the torque during the reactive processing, (2) decrease in melt flow indices, and (3) decrease in solubility of the reaction products. The chemical compositions of the reaction products were examined by Fourier transform infrared (FTIR) spectroscopy. Thermal analysis using differential scanning calorimetry (DSC) was carried out to determine the crystallization behavior, glass transition temperatures, and thermal stabilities of the reaction products. Results show that the primary amine is the most reactive towards carboxylic acid or anhydride groups followed by the secondary and then the tertiary amine. Anhydride groups on polymers are of higher activity towards secondary or primary amino groups than carboxylic acid groups in the nucleophilic acyl substitution reactions. Reaction products crosslinked with the primary diamine are less stable than their parent acidic polymers. On the other hand, crosslinking with the secondary or tertiary diamine gives products with higher thermal stability than the parent acidic polymers. The formation of reversible and irreversible crosslinks with different types of diamines is also reported. © 1992 John Wiley & Sons, Inc.     

Processable heat-resistant polymers—XVI: Polyamideimidesulphonamides

Polyamideimides having sulphonamide linkages were prepared by low temperature polycondensation of 2-sulphoxy-1,3-dioxoisoindoline-5-carboxylic acid with various diamines in the presence of thionyl chloride. The polymers were soluble in highly polar solvents. The solubility parameters of the polymers were calculated from Small's group contributions. Isothermogravimetric data indicated that the polymers were fairly thermostable.     

Synthesis and characterization of novel soluble and thermally stable polyamides based on pyridine monomer

Nucleophilic aromatic substitution reaction of 4-aminophenol and also 5-amino-1-naphthol with 2,6-dichloropyridine in N-methyl-2-pyrrolidone (NMP) as solvent, in the presence of potassium carbonate, afforded two aromatic ether diamines. Eight soluble, thermally stable polyamides were prepared by polycondensation reaction of the obtained diamines with aromatic and aliphatic diacid chlorides including terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), adipoyl chloride (AC), and sebacoyl chloride (SC). The prepared monomers and polymers were characterized by conventional spectroscopic methods. Physical and thermal properties of the polymers, such as thermal behavior, thermal stability, solution viscosity, and solubility behavior were also studied.