Novel poly(enamine-ketones) were prepared with inherent viscosities as high as 1.99 dL/g using the Michael-type addition of various diamines to 1,1′-(1,3 or 1,4-phenylene)bis(3-phenyl-2-propyn-1-one) in m-cresol at 60–130°C. Tough, clear, amber films with tensile strengths of 12, 400 psi and tensile moduli of 397, 000 psi were cast from solutions of the polymers in chloroform. The polymers exhibited Tgs as high as 235°C and weight losses of 14% after aging at 232°C in circulating air for 60 h. The synthesis and characterization of several poly(enamine-ketones) are discussed. 相似文献
Poly(enamine-ketones) were prepared by the nucleophilic (Michael-type) addition of various aromatic diamines to 1,1′-(1,3- or 1,4-phenylene)bis(2-propyn-1-one)(1,3 or 1,4-PPO) in m-cresol at 5–23°C. The low molecular weight polymers (inherent viscosity of 0.25 dL/g) exhibited limited solubility in organic solvents. Glass transition temperatures were generally undetectable by differential scanning calorimetry while polymer decomposition temperatures (10% weight loss), as measured by thermogravimetric analysis, were observed from 355 to 419°C. Polymers prepared from 1,4-PPO were semi-crystalline as shown by wide-angle X-ray diffraction. The poly(enamine-ketone) structure was confirmed by matching infrared spectral characteristics of the polymers with those of well-characterized model enamine ketones. 相似文献
Novel polypyrazolinones with inherent viscosities ranging from 0.12 to 0.44 dL/g were prepared by the Michael-type nucleophilic addition-cyclization of various dihydrazines with 3,3′-(1,3- or 1,4-phenylene)bis(ethyl propynoate) (1,3- or 1,4-PEP) and 3,3′-(1,4-phenylene)bis(phenyl propynoate) (1,4-PPhP) in N-methylpyrrolidone (NMP) solution at 25–110°C. The polymers exhibited moderate thermal stability with initial weight loss in air about 200°C and in nitrogen about 300°C (TGA). No apparent Tg′s were observed by DSC analysis. The synthesis and characterization of the polypyrazolinones is discussed. 相似文献
Mesoionic poly(1,1′-(1,3-phenylene)-3,3′-(1,4-phenylene)-bis(5-decyl-2-decylthio-4,6-dioxo-1,3-diazine)) ( 6 ) was prepared by cyclisation of the isothiourea component of poly(1,1′-(1,3-phenylene)-3,3′-(1,4-phenylene)-bis(2-decylisothiourea)) ( 4 ) with decylmalonic acid (5) by use of dicyclohexylcarbodiimide (DCC). Polymer 4 was obtained by polymer analogous alkylation of poly(1,1′-(1,3-phenylene)-3,3′-(1,4-phenylene)-bisthiourea) ( 3 ). For comparison of spectroscopic data, 5-butyl-2-propylthio-4,6-dioxo-1,3-diphenyl-1,3-diazine ( 9 ) was synthesized as low molecular weight model compound. 相似文献
Zinc enolates derived from 1-aryl-2,2-dibromoalkanones reacted with tetramethyl 2,2′-(1,4-phenylenedimethylidene)dimalonate, dimethyl 3,3′-(1,4-phenylene)bis(2-cyanoacrylate), and 2,2′-(1,4-phenylenedimethylidene)bis(malononitrile) to give, respectively, tetramethyl 3,3′-(1,4-phenylene)bis(2-alkyl-2-aroylcyclopropane-1,1-dicarboxylates), dimethyl 3,3′-(1,4-phenylene)bis(2-alkyl-2-aroyl-1-cyanocyclopropane-1-carboxylates), and 3,3′-(1,4-phenylene)bis(2-alkyl-2-aroylcyclopropane-1,1-dicarbonitriles) as a single stereoisomer. 相似文献
Poly[oxy-2,2′-diphenyleneoxyisophthaloyl-b-oxy(2-methyl-1,3-phenylene)oxyterephthaloyl] I, poly[oxy-2,2′-diphenyleneoxyterephthaloyl-b-oxy(2-methyl-1,3-phenylene)oxyterephthaloyl] II, poly(oxy-2,2′-diphenyleneoxyisophthaloyl-b-oxy-2,2′-diphenyleneoxyterephthaloyl) III, poly[oxy-2,2′-diphenyleneoxyterephthaloyl-b-oxy(2-methyl-1,4-phenylene)oxyterephthaloyl] IV, poly[oxy2,2′-diphenyleneoxyterephthaloyl-b-oxy(2-chloro-1,4-phenylene)oxyterephthaloyl] V, poly[oxy-2,2′-diphenyleneoxyterephthaloyl-co-oxy(2-chloro-1,4-phenylene)oxyterephthaloyl] VI, and poly[oxy-2,2′-diphenyleneoxyterephthaloyl-co-oxy(2-methyl-1,4-phenylene)oxyterephthaloyl] VII have been synthesized and characterized. Random copolyester VI appears to form a birefringent fluid phase above the melting temperature. 相似文献
Broad-line NMR spectra have been obtained at 90 MHz in the temperature region 140–530°K for four aromatic polyamides: poly(1,3-phenylene isophthalamide), poly(1,4-phenylene terephthalamide), poly(4,4,-diphenylene terephthalamide), and poly(4,4,-diphenylene isophthalamide). For the latter three materials, a broad-line narrowing process occurs in the 210–370°K region. At temperatures above 340°K a complex line shape is observed for all samples. Possible causes of these processes are discussed, and comparison made with dynamic mechanical results. 相似文献
Low-temperature internal motions of the following polyesters have been investigated by broad line nuclear magnetic resonance: poly(methylene terephthalates) (2–6 methylene groups), poly[1,4-(dimethylene)cyclohexylene terephthalate], poly(diethyleneglycol terephthalate), poly(1,2-propylene terephthalate), poly(1,4-phenylene terephthalate), poly(2,2,3,3,4,4-hexafluoropentamethylene terephthalate), poly[1,4-phenylenebis(dimethyl) siloxane], and poly(2,6-dimethylphenylene oxide). No complex line structure was found for any of the samples. Molecular motions in the polyesters appear to be restricted by polar forces arising from the ester groups. Above—196°C. the line width decreases smoothly with increasing temperatures for all polymers except poly[1,4-(dimethylene)cyclohexylene terephthalate] and poly[1,4-phenylenebis(dimethyl)siloxane]. These two show a definite transition in line width at ?20°C. and +12°C., respectively, caused by the onset of considerable internal motion. At ?196°C. the lattices are rigid except for polymers containing methyl groups: poly(1,2-propylene terephthalate), poly[1,4-phenylenebis(dimethyl) siloxane], and poly(2,6-dimethylphenylene oxide). Internal motion that can be ascribed to be a reorientation of the methyl groups is present at ?196°C. for these three polymers, as is demonstrated by comparison of experimental second moments and those calculated on the basis of various models. 相似文献
A study has been made of end-groups in poly(methyl methacrylate) prepared using benzoyl peroxide as initiator and either 1-(1′-naphthyl)4-phenylbuta-1,3-diene or 1,4-di(1′-naphthyl)buta-1,3-diene as additive. At 60°C, these dienes are 500–600 times as effective as methyl methacrylate in capturing benzoyloxy radicals and more than twice as effective as 1,4-diphenylbuta-1,3-diene. 相似文献
We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols. Four poly(dithioacetal)s(P1-P4) were prepared via the base-catalyzed thiol-yne "click" polyaddition of two dithiols(1,4-butanedithiol(4 S) and 1,5-pentanedithiol(5 S)) and two alkynones(3-butyn-2-one(Y1) and 1-phenyl-2-propyn-1-one(Y2)) at high concentrations. We systematically investigated the base-catalyzed polymerization of 4 S and Y1(for polymer P1) under different conditions, and found that this polymerization was a highly concentration-dependent dynamic system: polymer P1 was formed at high concentration, while seven-membered dithioacetal, 1-(1,3-dithiepan-2-yl) propan-2-one(C1), was obtained at low concentration. The polymerization of 4 S and Y2(for polymer P4)displayed similar polymerization behavior, generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone(C4) at low concentration. On the contrary,polymer P2(from Y1 and 5 S) was exclusively obtained with no formation of eight-membered dithioacetal. The polymerizations of Y1 with 1,2-ethanedithiol(2 S) and 1,3-dimercaptopropane(3 S) only afforded corresponding five-and six-membered dithioacetals, 1-(1,3-dithiolan-2-yl)propan-2-one(C2) and 1-(1,3-dithian-2-yl) propan-2-one(C3). This dynamic behavior of P1 and P4 was attributed to the concentrationdependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by bases.Furthermore, polymers P1 and P4 could be depolymerized into C1 and C4 in yields of 58% and 95%, respectively. The ring-opening polymerization of C1 at high concentration could successfully regenerate polymer P1. Thus, a new type of closed-loop recyclable poly(dithioacetal)s was developed. 相似文献
Two families of ester-type banana monomers are presented, 1,3-phenylene bis{4-[4′-(10-undecenyloxy)benzoyloxy]benzoate}s and 1,3-phenylene bis{[4′-(10-undecenyloxy)]-1,1′-biphenyl-4-carboxylate}s, in which the nature of the substituents on the central phenyl ring and the side arms was varied. The mesophase behavior of the monomers, including B2 and B7 phases, was correlated with their chemical structure and was compared with that of analogous azomethine-type banana mesogens. It is also shown that the banana monomers can be incorporated into new architectures of liquid crystal polymers. 相似文献
A new polycondensation pathway has been developed for the preparation of polyamides at high temperatures. p-Phenylenediamine was converted to N,N-p-phenylene bis(N′,N′-dimethylformamidine) (I), which formed 1–1 and 2–1 salts with terephthalic and adipic acids, respectively: Dicarboxylate salts were polymerizable by heating in bulk or suspension. Low-molecular-weight poly(p-phenyleneterephthalamide) was obtained from N,N-p-phenylene bis(N',N'-dimethylformamidinium) terephthalate above 225°C. The low degree of polymerization was due to terephthalic acid sublimation as well as to the well-known intractability of poly(p-phenyleneterephthalamide). High-viscosity poly(p-phenyleneadipamide) was obtained from N,N-p-phenylene bis(N′,N′-dimethylformamidinum hydrogen adipate) above 200°C. Both salts liberated dimethylformamide (DMF) during polymerization. The adipate salt also released 1 mole of adipic acid during the high-temperature vacuum stage of polymerization. A polycondensation mechanism was proposed for each salt, based on thermal gravimetric analysis (TGA-MS) and infrared (IR) analyses. The hydrolysis of N,N-p-phenylene bis(N',N'-dimethylformamidine), N,N-p-phenylene bis(N',N'-dimethylformamidinium chloride), and the two dicarboxylate salts of (I) was monitored by nuclear magnetic resonance (NMR) at room temperature. The dihydrochloride salt was most resistant to hydrolysis (kH 6.9 × 10?9 sec?1; relative rate 1.0) followed by (I) 7.1, terephthalate salt, 14.9, and adipate salt, 27.2. Both dicarboxylate salts possessed sufficient hydrolytic stability for use as polycondensation monomers 相似文献
Two kinds of aliphatic alternating polyesteramide prepolymers were prepared through melt polycondensation from N,N’-bis(2-hydroxyethyl)-adipamide and adipic acid or sebacic acid. Chain extension of them was conducted with 2,2′-(1,4-phenylene)-bis(2-oxazoline) and adipoyl biscaprolactamate as combined chain extenders. The chain extended polyesteramides (ExtPEAs) were characterized by IR, 1 H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray scattering, tensile test and enzymatic degradation. The results showed that the ExtPEA(4,m)s were mainly constituted with the diester adipamide alternating units. ExtPEA(4,4) and ExtPEA(4,8) had Tm of 83.8℃ and 85.8℃ and initial decomposition temperature above 310.0℃. They crystallized similarly as Nylon-66 did and were flexible thermoplastic materials with tensile strength up to 25.64 MPa and strain at break up to 737%. 相似文献