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.     

Regular Copolyamides. IX. Some Aliphatic Aromatic Copolyoxamides

Abstract

Aromatic/aliphatic regular copolyoxamides were prepared from aromatic diamine-oxamides and aliphatic diacid chlorides of various lengths of methylene groups by solution polymerization. The aromatic diamine oxamides, N,N′-bis(4-aminophenyl)oxamide and N,N′-bis(3-aminophenyl)oxamide were prepared and both were reacted with adipoyl chloride, suberoyl chloride, and sebacoyl chloride to form six new regular copolyoxamides. The polymers formed were soluble in sulfuric acid and also in some polar amide solvents. All copolyoxamides were high melting, with the meta-phenylene copolyoxamides melting from 346 to 373°C with decreasing length of the aliphatic diacid chloride, and the para-phenylene copolyoxamides decomposing prior to melting at near 400°C. The new polymers were characterized by UV spectrophotometry, differential scanning calorimetry, and thermal gravitational analysis.     

Novel thermally stable poly(thiourea-amide-imide)s bearing CS moieties and pyridine units in the backbone: Synthesis and properties

Novel thermally stable and organosoluble poly(thiourea-amide-imide)s (PTAIs) were synthesized through the condensation of various diamines with a new kind of aromatic diacid chloride monomer containing pyridine units, 2-(3-(2-(3-(chlorocarbonyl)pyridin-2-yl)-1,3-dioxoisoindoline-5-carbonyl) thioureido) nicotinoyl chloride, CPDITNC. Spectroscopic and elemental analyses were carried out for the structure elucidation of synthesized monomers. Accordingly, the ensuing PTAIs were characterized by FTIR, ¹H and ¹³C NMR techniques along with crystallinity, organosolubility, inherent viscosity and GPC measurements. Consequently, polymers bearing phenyl thiourea and pyridine moieties in the backbone exhibited good organosolubility in a variety of highly polar solvents such as DMAc, DMF, DMSO and NMP. PTAIs encompassed η_inh of 1.24-1.46 dL/g and two of the polymers showed crystalline behavior. Moreover, GPC measurements of polymers revealed M_w around 33,000-50,000. Thermal stability of these polymers was ascertained via 10% weight loss temperatures in the range of 548-562 °C (inert atmosphere). Ultimately, these polymers own high glass-transition temperatures about 264-270 °C.     

含联苯二氮杂萘酮结构聚芳酰胺的合成与表征

用类双酚单体4[4(4羟基苯基)苯基]2H二氮杂萘1酮(DHPZpP)与对氯苯腈进行亲核取代反应后碱性水解合成一种扭曲、非共平面杂环芳香二酸,4{4[4(4羧基苯氧基)苯基]苯基}2(4羧基苯基)二氮杂萘1酮(2).由二酸2和各种芳香二胺进行膦酰化缩聚反应制得了一系列的含联苯二氮杂萘酮结构聚芳酰胺,其特性粘数在0.42～0.72dLg之间.该类聚芳酰胺均可溶解于NMP、DMAc和DMSO等极性有机溶剂中,并且可用DMAc为溶剂制成具有良好机械性能的透明聚合物薄膜,聚合物薄膜的拉伸强度为80～89MPa.该类聚芳酰胺具有优异的耐热性,玻璃化转变温度Tg在298～328℃之间,10%的热失重温度(Td)在470℃以上.     

Synthesis and characterization of optically active polyamides based on 2-(1,3-isoindolinedione-2-yl)glutaric acid by direct polycondensation

<正>Five new optically active polyamides(PAs) 6a-6e were prepared by direct polycondensation reaction of 2-(1,3- isoindolinedione-2-yl)-glutaric acid 4 as a new chiral diacid with various aromatic diamines 5a-5e in a medium consisting of triphenyl phosphite(TPP),calcium chloride,pyridine(Py) and N-methyl-2-pyrrolidone(NMP).The polycondensation reaction produced a series of polyamids 6a-6e in quantitative yields with inherent viscosities of 0.26-0.39 dL/g.The resulting polymers were fully characterized by means of ~1H-NMR,FT-IR spectroscopy,elemental analysis,inherent viscosity and specific rotation.Thermal properties of these polymers were investigated using thermal gravimetric analysis (TGA) and differential thermal gravimetry(DTG).Phthalimide rings as a bulky pendent group in the polymer chains disturb the interchain and intrachain interactions and make these PAs readily soluble in polar,aprotic solvents such as N,N-dimethyl acetamide(DMAc),N,N-dimethyl formamide(DMF),dimethyl sulfoxide(DMSO),N-methyl-2-pyrrolidone(NMP) and sulfuric acid.     

Polymers from a levopimaric acid–acrylonitrile Diels–Alder adduct: Synthesis and characterization

The Diels–Alder adduct of levopimaric acid with acrylonitrile was efficiently prepared from resin acids. Excellent addition reaction yields (ca. 95%) were obtained. The adduct was converted into polyamides by polycondensation with diamines. When the same adduct was subjected to a dehydrodecarboxylation reaction, a novel ketone dinitrile derivative was obtained. This trifunctional product was also converted into polyamides by polycondensation with diamines. When the ketone dinitrile was hydrolyzed in the presence of alkalies and the reaction product was chlorinated, a ketone diacid chloride was obtained. A polyester was synthesized by the polycondensation of the diacid chloride with a diol. The structures of the Diels–Alder adduct, ketone dinitrile derivative, ketone diacid chloride, and polymers were established by means of elemental analysis, IR and NMR spectroscopy, and molecular weight determinations. Both the polyamides and the polyester were low‐molecular‐weight polymers soluble in polar solvents. The thermal behavior of the monomers and polymers was evaluated by thermogravimetric analysis. The thermal studies showed that the polymers were fairly thermostable substances, except the polyester, which appeared to be a substance with good thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6308–6322, 2005     

Polymers from a levopimaric acid–acrylic acid Diels–Alder adduct: Synthesis and characterization

The Diels–Alder adduct of levopimaric acid with acrylic acid was efficiently prepared from resin acids. When the adduct was subjected to a dehydrodecarboxylation reaction, a ketone diacid derivative was obtained. New ketone type linear polymers were synthesized by the advanced dehyrodecarboxylation, a nonconventional polycondensation reaction, of both the above in presence of sulfonic catalysts. The polyketones turned out to be excellent tackifiers in adhesive formulae. The ketone polymers were condensed with diamines to give crosslinked polyazomethines. The structures of the monomers and polymers were established by means of elemental analysis, IR and NMR spectroscopy, and molecular weight determinations. Both the polyketones and polyazomethines were low‐molecular‐weight polymers, soluble in some polar and nonpolar solvents. The thermal behavior of the monomers and polymers was evaluated by thermogravimetric analysis. The thermal studies showed that the polymers were substances with good thermal stability, except the polyazomethine synthesized by the condensation of polyketone with an aromatic diamine, which appeared to be a substance with high thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5979–5990, 2007     

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.     

Synthesis and thermal properties of crosslinkable phosphazene copolymers

Polyphosphazenes of formula [NP(OC₆H₄CN)_x(OCH₂CF₃)_2?x] (x = 0.04–2) were prepared. The copolymers were crosslinked via cyclotrimerization of the nitrilic function, using acid catalysts (chlorosulfonic acid, aluminum chloride) at elevated temperatures. The thermal properties of the crosslinked cyclomatrix polymer were compared to the linear polymer by thermogravimetric analysis and differential scanning calorimetry. When the 4-cyanophenoxy-2,2,2-trifluoroethoxy ratios were less than 0.2, the crosslinked polymers were soluble in polar organic solvents.     

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.     

New poly(amide-imide) syntheses. V. Preparation and properties of poly(amide-imide)s based on the diimide—diacid condensed from 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride

A dicarboxylic acid ( 1 ) bearing two pre-formed imide rings, was prepared from the condensation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.53–1.68 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide—diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these poly(amide-imide)s were in the range of 237–293°C and the 10% weight loss temperatures were above 508°C in nitrogen. © 1993 John Wiley & Sons, Inc.     

Chemical Reactions on Polymers. II. Modification of Diene Polymers with Triazolinediones via the Ene Reaction

A wide variety of polymers and copolymers of 1,3-dienes have been modified at low temperatures via the ene reaction with 4-substituted l,2,4-triazoline-3,5-diones. The resulting modified polymers were characterized via infrared spectroscopy, nuclear magnetic resonance, intrinsic viscosity, gel-permeation chromatography, differential scanning calorimetry, solubility tests, and tensile measurements. Physical properties measurements support the postulate that the highly polar pendant urazole groups contribute inter molecular and intramolecular hydrogen-bonding interactions and thus impart to the modified polymers thermoplastic elastomer properties. Changes in the solubility character, thermal behavior, and tensile properties of the modified polymers are in accord with this postulate. Since the association between molecules is physical in nature, the modified polymers remain soluble in appropriate solvents. They also show dramatic decreases in molecular size; for example, the average molecular size of polymers at 1% modification is about one tenth that of the unmodified polymer due to intramolecular interactions, a size reduction of the same order of magnitude as that of chemically crosslinked polymers. Poly-1,2-butadiene, when modified to the extent of 5%, gave values for elongation to break, Young's modulus, and tensile strength twice those for the parent polymer, while tensile recoveries were > 90%.     

Heat-resistant pyridine-based poly(ether-ester)s: Synthesis, characterization and properties

A pyridine-based diacid was synthesized via nucleophilic substitution reaction of 4-hydroxy benzoic acid with 2,6-dichloropyridine in the presence of potassium carbonate. The diacid was characterized using FT-IR and 1H-NMR spectroscopic methods and also with elemental analysis. Polycondensation reaction of the diacid with different diols including 1,4-dihydroxy benzene, 1,5-dihydroxy naphthalene, bis-phenol A and bis-phenol-P resulted in preparation of pyridine-based poly(ether-ester)s. The polymers were characterized and their physical and thermal properties including inherent viscosity, molecular weight, solubility, thermal stability, thermal behavior and crystallinity were studied. They revealed high heat-resistance and improved solubility in polar solvents. Structure-property relations for the prepared polyester were also studied.     

Synthesis, characterization and constitutional isomerism study of new aromatic polyamides containing pendant groups based on asymmetrically substituted meta-phenylene diamines

Four new aromatic polyamides containing pendant groups were synthesized by low temperature interfacial polycondensation of two asymmetrically substituted diamine monomers, namely, 4-[4-(1-methyl-1-phenylethyl) phenoxy]-1,3-diamino benzene and 4-{4-[(4-methylphenyl) sulphonyl]phenoxy}-1,3-diamino benzene with two aromatic diacid chlorides, namely isophthaloyl chloride and terephthaloyl chloride. Inherent viscosities of polyamides were in the range 0.64-0.72 dL/g indicating formation of medium molecular weight polymers. The weight average molecular weights and number average molecular weights, determined by gel permeation chromatography (polystyrene standard), were in the range 54,500-65,000 and 19,750-27,000, respectively. The constitutional isomerism of synthesized polyamides was investigated by ¹H and ¹³C NMR spectroscopy, where as the constitutional order was calculated from ¹H NMR spectroscopy and was found to be in the range 0.35-0.37. Polyamides containing pendant groups were essentially amorphous and were soluble in polar aprotic solvents such as N, N-dimethyl acetamide, N-methyl-2-pyrrolidone, N, N-dimethyl formamide and dimethyl sulfoxide. Polyamides exhibited glass-transition temperature in the range 237-254 °C. The initial decomposition temperature, determined by TGA in nitrogen atmosphere, of polyamides was in the range 371-410 °C indicating their good thermal stability.     

New silicon-containing heterocyclic polyimides

New aromatic polyimides and polyamide-imides with phenylquinoxaline rings and dimethylsilane units have been synthesized by solution polycondensation reaction of aromatic diamines containing phenylquinoxaline units with bis(3,4-dicarboxyphenyl)-dimethylsilane dianhydride, or with a diacid chloride resulting from the reaction of this dianhydride with p-aminobenzoic acid. These polymers were easily soluble in organic solvents, such as N-methylpyrrolidinone and dimethylacetamide, and showed high thermal stability with decomposition temperature being above 440°C and glass transition temperature in the range of 245-285°C. Very thin coatings were deposited from polymer solutions onto silicon wafers and exhibited smooth, pinhole-free surface in atomic force microscopy investigations. Some of these polymers showed blue fluorescence in solution and films, with a maximum in the range of 415-425 nm.     

Poly(1,3,4-oxadiazole-amide)s containing pendent imide groups

A series of new poly(1,3,4-oxadiazole-amide)s containing pendent imide groups has been synthesized by solution polycondensation of aromatic diamines containing preformed 1,3,4-oxadiazole rings with two diacid chlorides containing imide rings. These polymers were also prepared by the reaction of the same diacid chlorides with p-aminobenzhydrazide which were subsequently cyclodehydrated in solid state. The polymers were soluble in polar amidic solvents and some of them gave transparent flexible films by casting from solutions. They showed high thermal stability with decomposition temperatures above 400°C and glass transition temperatures in the range of 245–327°C. They had low dielectric constants, in the range of 3.32–3.94, and good tensile properties.     

Synthesis and properties of thermally stable and optically active novel wholly aromatic polyesters containing a chiral pendent group

5-(2-Phthalimidyl-3-methyl butanoylamino)isophthalic acid (5), as a novel diacid monomer containing phthalimide and flexible chiral groups, was prepared by the reaction of 2-phthalimidyl-3-methyl butyric acid chloride (4) with 5-aminoisophthalic acid (5AIPA) in dry N,N-dimethylacetamide (DMAc). A series of novel polyesters (PE)s containing phthalimide group was prepared by the reaction of diacid monomer 5 with several aromatic diols via direct polyesterification with the tosyl chloride/pyridine/dimethylformamide (DMF) system as a condensing agent. The resulting new polymers were obtained in good yields with inherent viscosities ranging between 0.37 and 0.61 dL g⁻¹ and were characterized with FT-IR, ¹H NMR, elemental and thermogravimetric analysis techniques. These polymers are readily soluble in amide type solvents such as DMAc, DMF, 1-methyl-2-pyrrolidone, hexamethyl triaminophosphine, dimethyl sulfoxide and protic solvents such as sulfuric acid. Thermogravimetric analysis showed that the 10% weight loss temperature in a nitrogen atmosphere was more than 345 °C, which indicates that the resulting PEs have a good thermal stability as well as excellent solubility.     

Oligomeric polyaromatic ether-ketone-sulfones with acetylenic end groups. X

Two new oligomeric polyaromatic ether-ketone-sulfones with acetylenic end groups have been synthesized. These acetylene-terminated oligomers are soluble in common organic solvents and can be cured under thermal conditions to give the crosslinked polymers which do not soften below 240°C. In the case of oligomer which is incorporated with terephthaloyl chloride, the cured polymer shows almost no penetration below 400°C. Isothermal aging studies show that the cured polymers are stable in circulating air at 300°C with less than 10% weight loss in 3 days.     

新型氯取代含杂萘联苯结构可溶性聚芳酰胺的合成、表征和性能

以类双酚单体4-(3-氯-4-羟基-苯基)-2H-二氮杂萘-1-酮(DHPZ-OC)和对氯苯腈为原料进行亲核取代反应合成二腈化合物4-[3-氯-4-(4-氰基苯氧基)苯基]-2-(4-氰基苯基)二氮杂萘-1-酮(),然后在碱性(KOH)条件下进行水解制得了一种新型的含氯取代杂萘联苯结构的芳香二酸,4-[3-氯-4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮().用新二酸与各种芳香二胺进行直接缩合聚合制得了一系列新型氯取代含杂萘联苯结构的聚芳酰胺,特性粘度可达1.23dL/g.用FTIR和¹HNMR研究了新型二酸单体及聚合物的结构.该类聚芳酰胺均可溶解于NMP,DMAc和DMSO等极性有机溶剂中,并且可浇铸成透明韧性膜,其玻璃化转变温度在291～332℃之间,10%的热失重温度在460℃以上.     

Synthesis of phosphorus-containing polyurethanes without use of isocyanates

Phosphorus-containing polyurethanes were synthesized by reacting phosphonic acid diesters (RO)₂P(O)X (X = H, CH₃, Ph) with hydroxycarbamates. These phosphorus-containing polyurethanes were characterized by a combination of molecular-weight determination (GPC) and NMR spectroscopy. The thermal stability of the polymers was evaluated by a combination of TGA and DTA techniques. These polymers are readily soluble in highly polar solvents like DMF and DMSO. The phosphorus-containing polyurethanes are water soluble. © 1996 John Wiley & Sons, Inc.