Polycondensation normally proceeds in a step-growth reaction manner to give polymers with a wide range of molecular weights. However, the polycondensation of potassium 2-alkyl-5-cyano-4-fluorophenolate ( 1 ) proceeded at 150°C in a chain polymerization manner from initiator, 4-fluoro-4′-trifluoromethyl benzophenone ( 2 ), to give aromatic polyethers having controlled molecular weights and low polydispersities (Mw/Mn ⩽ 1.2). The resulting polycondensation of 1 had all of the characteristics of living polymerization and displayed a linear correlation between molecular weight and monomer conversion, maintaining low polydispersities. Sulfolane was a better solvent for chain-growth polycondensation of 1 than other aprotic solvents. The polyether from 1 with a low polydispersity showed higher crystallinity than that with a broad molecular weight distribution, obtained by the conventional polycondensation of 1 without 2 . 相似文献
A Vilsmeier adduct derived from arylsulfonyl chlorides and DMF in pyridine was successfully used as a new condensating agent for the synthesis of aromatic polyesters by the direct polycondensation of aromatic dicarboxylic acids and bisphenols and also of hydroxybenzoic acids. Polymers of high molecular weights (M?w = 78,000) with relatively narrow molecular weight distribution (M?w/M?n ≈ 3.0) were prepared by reacting aromatic dicarboxylic acids with the adduct in pyridine, followed by addition of bisphenols. The polycondensation was significantly affected by the amount of DMF, the nature of the arylsulfonyl chlorides, the conditions of initial reaction of the acids with the adduct, and the rate of reaction with bisphenols. The process was adaptable to the direct polycondensation of hydroxybenzoic acids, affording polymers of high molecular weight (ηinh = 1.73). 相似文献
Polycondensation methods greatly influence the molecular weight distribution of poly(hexamethylene sebacamide) (nylon 610) as determined by gel permeation chromatography (GPC). The ratio of weight average molecular weight to number average molecular weight (Mw/Mn) was used as a measure for estimating the molecular weight distribution. The Mw/Mn ratios of nylon 610 obtained from melt, solid phase, and high temperature polycondensation methods were 2 to 3.5, which were expected values for the most probable distribution. However, those for polymers obtained from the direct polycondensation in the presence of triphenylphosphine, interfacial polycondensation and low temperature polycondensation using an acid chloride varied over a wide range from 3.5 to 8.5. The effect of the kind of organic solvents in the interfacial method on the Mw/Mn ratios was especially large, and the molecular weight distribution could be controlled to some extent by selecting an appropriate solvent. 相似文献
Poly-p-benzamide of high molecular weight (ηinh = ~ in H2SO4) was obtained by the direct polycondensation reaction of p-aminobenzoic acid (p-ABA) by means of diphenyl and triaryl phosphites in N-methylpyrrolidone (NMP)-pyridine solution containing lithium and calcium chlorides. Molecular weight of polymer varied with the amount of these salts, showing maximum values at the concentration of about 4 wt-% of LiCl or about 8 wt-% of CaCl2 in the reaction mixture. The reaction temperature at around 80°C gave a polymer of the highest viscosity. The polycondensation reaction was also affected by monomer concentration, solvents, and tertiary amines like pyridine. Similarly, aromatic polyamides with high molecular weight (ηinh values up to 1.34 in H2SO4) were prepared from isophthalic acid and aromatic diamines, whereas terephthalic acid gave only low-viscosity polymers. 相似文献
The size distributions of a number of multifunctional polycondensation systems have been derived from kinetic reaction schemes. The size distribution obtained for a self-condensing multifunctional monomer is equivalent to the classic distributions derived by Flory and Stockmayer, and distribution expressions for mixtures of monomers of different functionalities have also been obtained. Molecular weight expressions have also been calculated for the same systems. In some case, these are exactly the same as those calculated by others, and in some cases the expressions differ from those by others only in the kind of average used for the mean functionality of the mixed monomer systems, but in other cases, the differences are more marked. In gelation, comparison with a number of actual gel point data shows that although the critical point Pcrit for gel formation calculated from Pcrit = 2/f was generally closer to actually measured gel points than when Pcrit = 1(f –1), neither method of calculating Pcrit can be regarded as completely reliable. The cause of the divergence from theory is interpreted in terms of intramolcular reaction, and the nature of this type of reaction is discussed and comparisons made with other gelling systems. 相似文献
Polyterephthalamides of high molecular weight (ηinh up to 1.9) were obtained by the direct polycondensation reaction of terephthalic acid and aromatic diamines in the presence of poly(ethylene oxide) (PEO) with triphenyl phosphite in a N-methylpyrrolidone (NMP)–pyridine solution that contained lithium chloride. The molecular weights of the polymers produced varied with the amount and molecular weight of PEO, which showed maximum values when PEO with a molecular weight of 2.0 × 104?5.0 × 105 was used in a concentration of about 0.5 wt % in the solvent. The polycondensation reaction was significantly affected by the level of pyridine in a mixed solvent of NMP and pyridine and by the concentration of the lithium chloride added. 相似文献
We describe here a new strategy for the synthesis of polymers with highly branched architectures. The strategy involves the synthesis by anionic polymerization of well-defined AB2 polystyrene macromonomers with molecular weights from 3,600 to 94,000 gmol−1, which are then converted via a one-pot polycondensation reaction into high molecular weight, long-chain (hyper)branched architectures. Since the Hyperbranched structures are built up from condensation Macromonomers we have coined the term ‘HyperMac’ to describe these branched polymers. In this paper we report the synthesis of the HyperMacs, the optimal conditions for the polycondensation reaction and some preliminary characterization studies. 相似文献
In this part of the series, the influence of polyfunctional chain transfer agents with transfer constant C ≤ 1 on the molecular weight distribution was studied. The analytical expressions for the number- and weight-average degree of polymerization, and dispersion index were derived by kinetic and statistical methods. The expression for the molecular weight distribution can only be obtained by statistical methods. Some numerical examples on the dependence of distribution parameters as a function of the functionality of transfer agents f and transfer constants are illustrated. A critical value of the chain transfer constant was found to exist, which permits the synthesis of linear (for f = 2) or branched polymers (f > 2) with DP w/DP n approximately equal to 2 during the entire course of the polymerization. 相似文献
Six new optically active poly(amide-imide)s(5a-f) were synthesized through the direct polycondensation reaction of N,N'-(4,4'- diphthaloyl)-bis-L-leucine(3) with six hydantoin derivatives(4a-f).Triphenyl phosphite(TPP)/pyridine in the presence of calcium chloride(CaCl_2) and N-methyl-2-pyrrolidone(NMP) were successfully applied for direct polycondensation.The polycondensation reactions produce a series of new poly(amide-imide)s(5a-f) in high yields,and inherent viscosity between 0.42 and 0.55 dL/g.The re... 相似文献
The direct polycondensation of terephthalic acid and p-phenylenediamine hydrochloride (PPD.2HCl) with thionyl chloride was found to be significantly promoted in N-methylpyrrolidone (NMP) by dissolved CaCl2 and tertiary amines. The inherent viscosity of the polymer obtained varied with the amount of CaCl2 and tertiary amines added. The reaction, when effectively promoted by CaCl2, proceeded homogeneously in the early state of polycondensation, and then resulted in a highly swollen gel. CaCl2 had to be present in the PPD.2HCl/tertiary amines/NMP solution as well as in the TPA/SOCl2/NMP mixture for the polycondensation to proceed to high molecular weight. Complexes of CaCl2, PPD.2HCl, and tertiary amines in NMP similar to the well known complex, CaCl2 · nNH3 (n = 2, 4, 8) was proposed to facilitate the polycondensation. 相似文献
The concentration of water in purified and BaO-dried α-methylstyrene was found to be 1.1 × 10?4M. The radiation-induced bulk polymerization of the α-methylstyrene thus prepared was studied in the temperature range of ?20°C to 35°C. The polymerization rate varied as the 0.55 power of the dose rate. The theoretical molecular weights and molecular weight distribution were calculated from a proposed kinetic scheme and these values were then compared with those found experimentally. The agreement between these two was reasonably close, and therefore it was concluded that, from the molecular weight distribution point of view, the proposed kinetic scheme for the cationic polymerization of α-methylstyrene is an acceptable one. The rate constant for chain transfer to monomer kf changed with temperature and was found to be responsible for the decrease in the molecular weight of the polymer with increase in temperature. kf and kp at 20°C were found to be 0.95 × 104 l./mole-sec and 0.99 × 106 l./mole-sec, respectively. 相似文献
The molecular weight distribution of carefully prepared thermostabilized poly(ethylene terephthalate) was determined immediately after polycondensation in vacuo (P?n = 121) and after the melt was stirred at 280°C for 5.5 hr under nitrogen (P?n = 123). The fractionation was carried out by successive precipitation in liquid phases. The samples were separated into 25 fractions including refractionation. The Flory distribution was observed in all samples. 相似文献
A series of hyperbranched polyurethane-benzyltetrazoles(H-PBTZs) with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A2 type monomer with(4-(1H-tetrazol-5- yl)benzyl)-diethanolamine(TBDEA) as a BB’2 type monomer in the absence of catalyst at different temperatures.The FTIR, and 13C and 1H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole(L-PBTZ).The molecular composition was determined by the reaction selectivity that the isocyanate group reacted with the hydroxyl group in diethanolamine segment or the active hydrogen atom on tetrazole ring.Raising reaction temperature was propitious to the reaction of isocyanate group with the active hydrogen atom on tetrazole ring.The degrees of branching(DB) for H-PBTZs obtained from the 1H-NMR spectra increased with raising reaction temperature.The wider molecular weight distribution of 1.7-2.9 for H-PBTZs was obtained via GPC analysis.TGA results showed that H-PBTZs had high thermal stability compared with L-PBTZ. 相似文献
Summary: Poly(arylene ether amine)s were synthesized by a nucleophilic aromatic substitution polycondensation of bis[4‐fluoro‐3‐(trifluoromethyl)phenyl]amine with several bisphenols. Even though the monomer has an electron‐donating diphenylamine moiety, which normally deactivates a nucleophilic aromatic substitution (SNAr) reaction, the polymerization proceeded by a SNAr reaction to give high‐molecular‐weight polymers. The polymers show good solubility in common organic solvents and have Tgs in the range of 123 °C to 177 °C.
High‐molecular‐weight poly(arylene ether amine)s synthesized by a SNAr reaction with the monomer containing an electron‐donating diphenylamine moiety. 相似文献