Synthesis and characterization of new polyesters based on 2,5-bis[(4-chloro carboxyanilino) carbonyl] pyridine and aromatic diols

<正>Six new polyesters 7a-f were synthesized through the solution polycondensation reaction of diacid chloride 5 with six aromatic diols 6a-f in N,N-dimethyl acetamide(DMAc) as solvent in the presence of pyridine as base.The polycondensation reaction produced a series of novel polyester containing pyridyl moiety in the main chain in high yields with inherent viscosities between 0.35 and 0.54 dL/g.The resulted polymers were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherent viscosity and solubility tests.Thermal properties of these polymers were investigated by using thermal gravimetric analysis(TGA) and differentional thermal gravimetric(DTG).The glass-transition temperatures of these polyesters were recorded between 130 and 170℃by differential scanning calorimetry(DSC) and the 10%weight loss temperatures were ranging from 390 to 450℃under nitrogen.     

Interfacial Polycondensation in Aqueous and Non-Aqueous Systems

Abstract

Interfacial polycondensation in aqueous and non-aqueous systems has been investigated in order to synthesize various polyamides having functional groups. Rigid aromatic polyamides having pyridine moieties (PPy) were synthesized by interfacial polycondensation using an aqueous system and the solution properties of PPy in concentrated sulfuric acid were investigated in terms of solution viscosity and lyotropic behavior. Interfacial polycondensation in a non-aqueous system using two immiscible solvents was found to be useful for the synthesis of aromatic polyesters and copolyesters.     

Aryudene Polymers. II Synthesis and Characterization of some New Polyesters of Diarylidenecyclopentanone

New polyesters formed by interfacial polycondensation of 2,5-bis(4-hydrox-ybenzylidene)cyclopentanone (I) and 2,5-bis(4-hydroxy-3-methoxybenzyli-dene)cyclopentanone (II) with 4,47prime;-diphenic, isophthaloyl, terephthaloyl, adi-poyl, suberoyl, and sebacoyl dichlorides were obtained. The yield and the values of the reduced viscosity of the produced polyesters were found to be affected by the type of organic phase, the quantitative ratio of organic to aqueous phase, the concentration of the hydrogen chloride acceptor, and the contribution of benzyltriethylammonium chloride as a catalyst. In order to characterize these polymers, the necessary model compounds were prepared from I, II, and benzoyl chloride. The resulting polyesters were confirmed by IR, elemental analysis, viscometry, DTA, DSC measurements, and thermogravi-metric analysis. The crystallinities of all polyesters were examined by x-ray analysis, and the electrical properties of the polyesters were tested.     

Synthesis and characterization of optically active and organosoluble poly(amide-imide)s containing imidazole rings as pendent groups by direct polycondensation

Six new optically active poly(amide-imide)s(PAIs) 6a-f were prepared by direct polycondensation reaction of N-trimelli-tylimido-L-histidine 4 as a chiral diacid with various aromatic diamines 5a-f.Triphenyl phosphite(TPP)/pyridine(Py) in the presence of calcium chloride(CaCl2) and N-methyl-2-pyrrolidone(NMP) were successfully applied to direct polycondensation reaction.The resulting new polymers were in good yields,and had inherent viscosities ranging between 0.29 and 0.41 dL g-1 and were detected with elem...     

Synthesis of polyester by direct polycondensation with triphenylphosphine

Direct polycondensation reactions of various dicarboxylic acids and diols were carried out at room temperature with triphenylphosphine and polyhalo compounds to obtain polyesters in good yield. Reaction conditions including solvent, temperature, concentration of monomer, amount of reagents, and effect of matrix on direct polycondenation were investigated. A combination of triphenylphosphine and hexachloroethane was found to be satisfactory for the polyester synthesis. The addition of matrix polymers such as poly(4-vinylpyridine) in the reaction system enhanced the direct polycondensation reaction, and a polyester with a solution viscosity of 2.24 was obtained from bisphenol A and isophthalic acid under the optimum condition.     

Synthesis and characterization of new unsaturated polyesters and copolyesters containing azo groups in the main chain

A new interesting class of linear unsaturated polyesters based on dibenzylidenecycloalkanones have been synthesized by interfacial polycondensation of 4,4^′-azodibenzoyl chloride or 3,3^′-azodibenzoyl chloride with: 2,5-bis(p-hydroxybenzylidene)cyclopentanone I, 2,6-bis(p-hydroxybenzylidene)cyclohexanone II, 2,6-divanillylidenecyclohexanone III, or 2,7-bis(p-hydroxybenzylidene)cycloheptanone IV at ambient temperature. The copolyesters are also synthesized from the monomers I, II, III or IV with the diacid chlorides. The resulting polyesters and their copolyesters were characterized by elemental analyses, IR spectroscopy and solubility. Additionally, inherent viscosity of the polyesters in the range 0.32-0.86 dL g⁻¹ and the inherent viscosity of the copolyesters in the range 0.28-0.65 dL g⁻¹ were determined. The UV-visible spectra of certain polymers were measured in m-cresol solution and showed a characteristic absorption band at 435-473 nm due to n-π^* transition. The thermal properties of the polymers were evaluated by thermo gravimetric analysis and differential scanning calorimetry measurements and correlated with their structural units. The crystallinity of some polyesters and copolyesters were tested. In addition, the electrical properties of all polyesters and copolyesters were measured.     

Synthesis and thermal characterization of poly(1,3-phenyl octanoate)

Poly(1,3-phenyl octanoate) (polyHPOA) was prepared by melt and solution polycondensation methods from 8-(3-hydroxyphenyl)octanoic acid (HPOA), a novel monomer useful as a chain disruptor in liquid crystalline copolyesters. The melt polycondensation technique gave a polyester of higher inherent viscosity (0.80 dL/g in p-chlorophenol) than that (0.75 and 0.56 dL/g, respectively, for the Ogata method and thionyl chloride/pyridine method in the same solvent) of solution techniques. The solubility of the polyesters was limited to strongly acidic and polar solvents. The polyester was characterized by elemental analysis, IR spectroscopy, WAXD, TGA, isothermal TGA and DTA. x-ray diffraction pattern of the polyesters indicated that it is amorphous in nature. TGA of the polyesters gave a thermal stability of 470°C in nitrogen atmosphere at 50% decomposition. The available thermal data suggest that the polyester undergoes thermal decomposition by a pyrolytic cleavage involving the ester linkage with the formation of ketene and phenol ended groups as intermediates. © 1996 John Wiley & Sons, Inc.     

界面缩聚法制备间苯二甲酰双酚酸酯聚芳酯

以四丁基氯化铵为相转移催化剂,双酚酸甲酯或双酚酸乙酯与间苯二甲酰氯界面缩聚,合成得到了侧链含酯基的聚芳酯.在吡啶、三乙胺、碳酸氢钠、氢氧化钠中选择合适的催化剂,既可以发生聚合反应又不会使双酚酸酯的酯基发生水解.聚合反应在7种溶剂中进行,通过探讨聚合反应机理以解释溶剂对聚合反应产率以及聚合物特性黏数的影响.以二氯甲烷为溶剂,在优化的聚合条件下较高产率地得到了高特性黏数的聚合物.DSC及TGA分析表明,间苯二甲酰双酚酸酯类聚芳酯具有比间苯二甲酰双酚酸好的热稳定性,热分解温度可从200℃提高到300℃.     

Preparation and properties of polyesters derived from 4,4′-sulfonyl dibenzoyl chloride by solution polycondensation

Sulfone-containing polyesters of 18 kinds having inherent viscosities of 1.19–0.16 dL g⁻¹ were prepared derived from 4,4′-sulfonyl dibenzoyl chloride by solution polycondensation from various aromatic and aliphatic diols in nitrobenzene at 82°C. The polyesters were examined with IR spectra, inherent viscosity, x-ray diffraction, solubility, DSC, and TGA. Polyester (PE-7) with the greatest inherent viscosity may reflect that bisphenol A having a electron-releasing group increases nucleophilic properties of the phenolate anion. Diols such as bisphenol AF (PE-13) and brominated diols (PE-4, PE-10, and PE-16) gave less favorable results. The diffractograms showed that all polyesters were essentially amorphous except that obtained from bisphenol S and its derivatives. Almost all polyesters except PE-1 and PE-2 were soluble in DMF, THF, tetrachloroethane and phenol/sym-tetrachloroethane (60/40 by mass) but insoluble in typical organic solvents such as acetone, toluene, and chloroform. These polymers obtained from aromatic bisphenols lost no mass below 309°C, but 10% loss of mass was recorded above 380°C in nitrogen. © 1996 John Wiley & Sons, Inc.     

Preparation and properties of polyesters and copolyesters based on 4-methyl-2,4-bis (p-hydroxyphenyl)-1-pentene

4-Methyl-2,4-bis (p-hydroxyphenyl)-1-pentene (MBHPP) was prepared from thermal cracking of bisphenol A (BPA). Unsaturated polyesters were synthesized from the polycondensation of MBHPP with diacid chlorides. Three synthetic routes—solution, interfacial, and melt polycondensation—were employed. MBHPP-polyesters with higher molecular weights were obtained by the interfacial polycondensation reaction. During the preparation of MBHPP-polysters, the products usually contain some insoluble gel, which is probably caused by the crosslinking reaction of the vinyl groups of MBHPP in the aqueous NaOH. Thus, a modified interfacial polycondensation method was proposed, in which both of the bisphenol MBHPP and diacid chloride were dissolved in organic phase and then the solution was stirred with an aqueous NaOH solution to promote the polycondensation. This method reduced the time of MBHPP present in the alkali and produced polymers with higher inherent viscosity and lower gel fraction. The effects of some variables, such as the nature of porganic solvents and phase transfer agents and the concentration of reactants, on the modified interfacial polycondensation of MBHPP with the mixture of equal parts of isophthaloyl and terephthaloyl chloride [IPC/TPC (50/50)] were investigated in some detail. Copolyesters of mixed bisphenols of BPA/MBHPP with IPC/TPC (50/50) were also prepared and characterized.     

Synthesis and characterization of new optically active copoly(amid-imide)s based on N-phthalimido-L-aspartic acid and aromatic diamines

<正>In this article,six new optically active copoly(amide-imide)s(10a-f) were synthesized through the direct polycondensation reaction of N-phthalimido-L-aspartic acid(4) with 1,5-diamino naphthalene(8),3,4-diamino benzophenone(9) in the presence of therphthahc acid(7),fumaric acid(6) and adipic acid(5) as a second diacid in a medium consisting of N-methyl-2-pyrrolidone,triphenyl phosphite, calcium chloride and pyridine.The resulting copolymers were fully characterized by means of FT-IR spectroscopy,elemental analyses, inherent viscosity,solubility tests and UV-vis spectroscopy.Thermal properties of resulting copolymers(10a-c) containing three different second diacid in the main chain were compared by using TGA and DTG thermograms.     

Phenazasiline-containing polyamides and polyesters

A Phenazasiline ring was incorporated into a polymer backbone by polycondensation of 2,8-dichloroformyl-5,10-dihydro-5-methyl-10,10-diphenylphenazasiline (V) with aromatic diamines or bisphenols, and phenazasiline-containing polyamides and polyesters were obtained. The polyamides were prepared by low-temperature solution polycondensation in N-methyl-2-pyrrolidone (NMP) in the presence of lithium chloride. The polyesters were synthesized by interfacial polycondensation in a mixture of 1,2-dichloroethane and aqueous alkali in the presence of tetrabutylammonium chloride as an accelerator. These reaction conditions gave the corresponding polymers with high viscosities. The phenazasiline-containing polyamides exhibited good solubilities in polar aprotic solvents such as dimethylformamide, dimethylacetamide, and NMP, and also in m-cresol, although the polyesters showed limited solubilities in organic solvents. Under nitrogen, the phenazasiline-containing polyamides and polyesters showed little degradation below 400°C and had good heat resistance.     

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.     

紫外光固化超支化聚酯的合成及性能

以季戊四醇为核,2,2-羟甲基丙酸为臂,采用熔融缩聚法合成并表征了末端含大量羟基的超支化聚酯,其支化度高,黏度低,具有良好的热稳定性.以甲基丙烯酸酐改性超支化聚酯,得到链末端含有C=C的超支化甲基丙烯酸酯,在最佳反应条件下改性反应的转化率可达89%以上.改性后的超支化聚酯表现出更低的黏度,热失重曲线呈现为两段,玻璃态转...     

Synthesis and characterization of sulfone-containing polyesters derived from 4,4′-dicarboxydiphenyl sulfone by direct polycondensation

Several sulfone-containing polyesters having inherent viscosities 0.43-0.19 dL g^?1 were prepared by direct polycondensation of 4,4′-dicarboxydiphenyl sulfone (DCDPS) with various aromatic and aliphatic diols, by p-toluenesulfonyl chloride and N,N′-dimethylformamide in pyridine solution. The polyesters were examined by elementary analysis, IR spectra, inherent viscosity, x-ray diffraction, solubility, DSC, and TGA. The diffraction diagram showed that all polyesters were crystalline except that obtained from bisphenol-A. All polymers were soluble in sulfonic acid (18M), phenol and p-chlorophenol, but not in acetone and toluene. These polymers obtained from aromatic bisphenols lost no mass below 325°C, but 10% loss of mass was recorded above 396°C in nitrogen. DCDPS copolymerized with isophthalic acid (IPA) and bisphenol-A had inherent viscosity up to 0.49 dL g^?1, with relatively narrow distribution of molar mass . © 1995 John Wiley & Sons, Inc.     

Synthesis of aliphatic polyesters containing tetracyanoquinodimethane units by low-temperature polycondensation reactions

The low-temperature solution polycondensation reaction between 1,4-bis-(2′-hydroxy-ethoxy)benzene and adipyl chloride has been studied in N,N-dimethylacetamide. The effect of temperature, concentration, and reaction time on the percent yield and product viscosity has been determined. Optimum conditions were established for the preparation of high molecular weight products and then applied to the synthesis of novel tetracyanoquinodimethane polyesters. Products were characterized by gel permeation chromatography.     

New polymer syntheses. 60. Thermostable polymers of 2-(hydroxyaryl)benzoxazole-5-carboxylic acids

Tristrimethylsilyl-3-amino-4-hydroxybenzoic acid was condensed with various aromatic acetoxy carboxylic acid chlorides in Marlotherms-S® at 20–350°C. Under these conditions formation of an amide group, ring closure to benzoxazole groups and polycondensation occur step by step in a “one-pot procedure”. The crude polyesters were hydrolyzed to yield pure 2-(hydroxyaryl) benzoxazole-5-carboxylic acids which were acetylated and polycondensed. The pure polyesters obtained in this way were characterized by viscosity and DSC measurements, WAXS-powder patterns, and thermogravimetric analyses. The polyester of 2-(4-hydrophenyl) benzoxazole-5-carboxylic acid has a degree of crystallinity > 90% and a short term in thermostability in air up to 500°C.     

Synthesis of aromatic polyesters by direct polycondensation with triphenylphosphine dichloride

Aromatic polyesters of high molecular weights were prepared by the direct polycondensation reaction of dicarboxylic acids and bisphenols or hydroxybenzoic acids with triphenylphosphine dichloride as a new condensing agent. Reaction conditions, including the amount of reagents and the concentration of monomer, solvent, and acid acceptor, were investigated. The aromatic polyester with the solution viscosity of 1.66 dL/g was obtained from bisphenol. A and terephthalic and isophthalic acid in quantitative yield under the optimum condition. The principal advantage of this condensing agent is that, based on the recycling system, recovered triphenylphosphine oxide can be reconverted to the reactive triphenylphosphine dichloride by treating with phosgene or oxalyl chloride.     

A new cardo bisphenol monomer containing pendant azido group and the resulting aromatic polyesters

Expanding on our strategy to synthesize aromatic step‐growth polymers containing pendant clickable azido groups via functional monomer approach, we have now designed and synthesized a new cardo bisphenol, viz., 2‐(2‐azidoethyl)‐3, 3‐bis(4‐hydroxyphenyl) isoindolin‐1‐one (PPH‐N₃). PPH‐N₃ was conveniently synthesized starting from commercially available phenolphthalein by a three‐step route in an overall yield of 65% using simple organic transformations. Aromatic (co)polyesters bearing pendant azido groups were synthesized by low‐temperature solution polycondensation of PPH‐N₃ or different molar ratios of PPH‐N₃ and bisphenol‐A (BPA) with aromatic diacid chlorides in dry dichloromethane in the presence of triethylamine (TEA) as a base. The formation of medium to reasonably high‐molecular‐weight (co)polyesters was evidenced from intrinsic viscosity and number‐average molecular‐weight measurements that were in the range 0.52–0.85 dL/g and 16,700–28,200, respectively. Tough, transparent, and flexible films could be cast from chloroform solutions of these (co)polyesters. (Co)polyesters were characterized using FTIR, ¹H NMR, ¹³C NMR spectroscopy, XRD, and TGA. The thermal curing reaction of (co)polyesters involving decomposition of azido groups was studied by DSC analysis. The chemical modification of a representative copolyester containing pendant azido groups was carried out quantitatively using catalyst‐free azide‐maleimide cycloaddition reaction with two maleimides, namely, N‐methylmaleimide and N‐hexylmaleimide. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1516–1526     

Polymers with Cycloaliphatic Units in the Chain

This paper describes the synthesis and characterization of some polycondensation polymers (poly- and copolyamides, polyesters) which contain cycloaliphatic units in their chains. Syntheses were carried out by a low-temperature polycondensation technique (interfacial and solution), and also by the Yamazaki method in NMP-pyridine solution using triphenylphosphite as the catalyst. The products obtained were characterized by elemental analysis, IR, and x-ray diffraction. Thermoanalytical data have shown very good thermal properties for all products, but especially for the aromatic cycloaliphatic polyamides which were stable up to 400°C.