Direct polycondensation of aromatic dicarboxylic acids and bisphenols with tosyl chloride and N,N-dimethylformamide in pyridine

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 (η_inh = 1.73).     

Direct polycondensation of hydroxybenzoic acids with thionyl chloride in pyridine

The reaction promoted by thionyl chloride and pyridine could selectively activate carboxyl groups of hydroxybenzoic acids to give polyesters of high inherent viscosities up to 3.8. Favorable conditions were studied in terms of the temperatures for the initial reaction with the acids and subsequent aging at room temperature. Copolymers of several combinations of hydroxybenzoic acids with high molecular weights were obtained in quantitative yield by carrying out the polycondensation at 80°C for 3 h. The reaction could also produce high molecular polyesters in a simpler process without the initial activation of dicarboxylic acids by adding a mixture of these monomers to the condensing agent, and a tough film- and fiberforming polymer was obtained from 4,4′-dihydroxyphenylsulfone of low nucleophilicity whose polymer of high molecular weight is difficult to obtain. The process was also successfully applied to the direct copolycondensations of hydroxybenzoic acids, aromatic dicarboxylic acids, and bisphenols to produce polyesters of η_inh up to 5.6.     

Modification of polycondensation of isophthalic and terephthalic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine by the presence of additives

In copolycondensation with 2,2‐bis(4‐hydroxyphenyl)propane (BPP) and bisphenols (BPs) containing various alkylidene linkages, the associative interactions between BP moieties in the resulting oligomers most likely affected the reaction. To modify the interactions to favorably control the reaction, several additives were examined in a two‐stage polycondensation of an equimolar mixture of isophthalic acid and terephthalic acid, first with BPP (50 mol %) and next with additional BPP. Of additives used, diphenylmethane of an equivalent to BPP in the preformed oligomers was most effective. The results are discussed in terms of the distributions of resulting oligomers prepared at 70% extent of reaction. Better results were obtained when the distributions showed profiles similar to the theoretical one calculated on the basis that the reactivity of the oligomers is the same independent of their chain lengths. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 970–975, 2003     

Preparation of aromatic polyesters by direct polycondensation with thionyl chloride in pyridine

Mechanistic features of the reaction with thionyl chloride in pyridine were studied in a model reaction of benzoic acid with p-chlorophenol or aniline. The yields were significantly affected by the amounts of pyridine, favorably by four equivalents, and the nature of pyridine, suggesting that pyridines are not only HCl scavengers, but are also involved in the reaction itself. The reaction was assumed to proceed via a carboxylic sulfinic-anhydride intermediate different from acyl chloride, and the intermediate was found to be not so reactive that it was completely alcoholyzed by the phenol at high temperatures of more than 60°C. The reaction was successfully applied to the preparation of aromatic polyesters of high molecular weights by the direct polycondensation of aromatic dicarboxylic acids and bisphenols in pyridine at 80°C.     

Attempt to investigate the temperature effect on polycondensation from the solution copolyesterification of preformed oligomers and bisphenols with tosyl chloride/dimethylformamide/pyridine

Two‐stage copolycondensations of isophthalic acid/terephthalic acid (50/50) and a bisphenol (BP) first and then a comonomer BP were carried at 80 and 120 °C. BPs were divided into two groups: those with polar substituents and those without polar substituents. The copolycondensation with any combination of BPs proceeded nearly equally well at 80 °C. However, the reaction at 120 °C was retarded differently by the groups of comonomers. For the preformed oligomers from BPs without polar substituents, the temperature did not affect the reaction very much, but the reaction was significantly retarded with BPs containing polar groups. All of the reactions of the oligomers from BPs having polar groups with comonomer BPs, regardless of their substituents, were greatly disturbed by the temperature rising. The results were attributed to the temperature effect on the way in which the oligomers reacted with comonomers due to the interactions between them, and they were examined in terms of the distributions of comonomers determined by ¹H NMR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4556–4562, 2002     

Investigation of polycondensation through the copolycondensation of preformed oligomers and bisphenols by a two‐stage solution reaction with tosyl chloride,dimethylformamide, and pyridine

A two‐stage copolycondensation of an equimolar mixture of isophthalic acid and terephthalic acid first with a bisphenol (BP) and then with another BP was carried out with a tosyl chloride/dimethylformamide/pyridine condensing agent. When the preformed oligomers from a BP with no substituent or a methyl substituent were allowed to react with another BP comonomer containing polar SO₂, CO, or Cl groups, the copolycondensation was significantly promoted. Such effects were absent with the unsubstituted BP and the methyl derivative. In addition, during the reaction of oligomers from BPs with polar groups, a similarly polar BP did not react so effectively, and the unsubstituted BP did not have any effect on the copolycondensation. On the basis of the sequence distributions for the resultant copolymers determined by ¹H NMR, it was likely that the copolycondensation could be promoted when the second comonomers were randomly distributed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4024–4031, 2002     

Preparation of aromatic copolyesteramides by the direct polycondensation with a vilsmeier adduct derived from tosyl chloride and N,N-dimethylformamide

The reaction promoted by Vilsmeier adduct derived from tosyl chloride (TsCl) with N,N-dimethylformamide (DMF) was successfully applied to the preparation of copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, diamines, and bisphenols. The polycondensation was significantly affected by the reaction of activated dicarboxylic acids with bisphenols and diamines. Addition of a mixture of bisphenols and diamines likely caused gelation of the reaction mixtures, resulting in insoluble polymers, especially with high mol % diamines. Stepweise addition of them, however, gave the homogeneous reaction mixtures and copolymers of better solubility. These phenomena were studied in terms of sequence length distribution of polyester units, which was estimated by thermal analyses of the random copolymers prepared under various conditions for the initial reaction with bisphenols.     

Solution polycondensation of isophthalic acid/terephthalic acid and tetrachlorobisphenol A of low polymerizability with tosyl chloride/dimethylformamide/pyridine improved by the introduction of comonomers of smaller sizes

The copolycondensations of a mixture of equal parts of isophthalic acid and terephthalic acid with tetrachlorobisphenol A (TC‐BPA) and various aromatic diol comonomers were performed with a tosyl chloride/dimethylformamide/pyridine condensing agent. The reaction with bisphenols containing nonpolar substituents yielded better results than the reaction with polar groups did. Dihydroxybenzenes smaller in size than bisphenols of two benzene rings, especially chlorohydroquinone and chlororesorcinol, were satisfactorily incorporated and yielded copolymers of high inherent viscosities and weight‐average molecular weights (by gel permeation chromatography). The results of the copolycondensations were examined with sequence distributions in the resultant copolymers by NMR and were well evaluated by the ratio of the length of comonomer unit segments to TC‐BPA unit segments. Homopolycondensation with TC‐BPA in the presence of dichlorobenzenes as additives was also promoted to some extent. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 821–830, 2003     

Polyamide synthesis by the direct polycondensation with phenylphosphonic dichloride in pyridine

The direct polycondensation of isophthalic acid (IPA) and aromatic diamines with a new phosphorus compound, phenylphosphonic dichloride (PPDC), was studied. PPDC could actually react with nearly a two molar amount of carboxyl groups, but more than 75 mol % PPDC with respect to the carboxyl groups of IPA were satisfactorily used in the polycondensation. The initial reaction of IPA with PPDC in pyridine at room temperature and then at 120°C was needed to complete the activation, and the subsequent aminolysis at 120°C for 3 h was most effective. The polyamides of high inherent viscosity were obtained even from weakly basic aromatic diamines, and their values were more than those obtained by the conventional method. In their thermal properties determined by the DTA, they showed T_gs and T_ms higher than those reported before.     

Copolycondensation of various compositions of isophthalic acid and terephthalic acid with hydroquinones or bisphenols by tosyl chloride/dimethylformamide/pyridine

The polycondensation of isophthalic acid (IPA)/terephthalic acid (TPA) with aromatic diols by tosyl chloride/dimethylformamide/pyridine in solution was examined through changes in the IPA/TPA compositions, the kinds of dihydroxyl components, the periods of their addition, and the reaction temperatures. The reaction proceeded favorably at IPA/TPA ratios of 70/30 to 50/50, similarly to an earlier report on the interfacial reaction. The effects of the compositions were significant in the reactions with monosubstituted hydroquinones. The results were examined from distributions of the resulting oligomers prepared at a reaction extent of 0.7, determined by gel permeation chromatography. The reaction producing better results exhibited distributions closer to the theoretical ones. The period of addition also favorably affected the distributions as well as the results of the polycondensation. These results were attributed to the change in the reaction method, in which the diols reacted with the aggregates that formed from the activated IPA and TPA. The change was likely caused by the degree of association of IPA and TPA in the aggregates, on the basis of melting points and IR spectra of mixtures of dimethyl esters of IPA and TPA prepared by the quenching of the aggregates with methanol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2321–2328, 2004     

Direct dehydration polycondensation of lactic acid catalyzed by water‐stable Lewis acids

Poly(L ‐lactic acid) (PLLA) is generally produced by ring‐opening polymerization of (S,S)‐lactide, which is prepared from dehydration polycondensation of lactic acid and successive depolymerization. Results of this study show that scandium trifluoromethanesulfonate [Sc(OTf)₃] and scandium trifluoromethanesulfonimide [Sc(NTf₂)₃] are effective for one‐step dehydration polycondensation of L ‐lactic acid. Bulk polycondensation of L ‐lactic acid was carried out at 130–170 °C to give PLLA with M_n of 5.1 × 10⁴ to 7.3 × 10⁴ (yield 32–60%). The solution polycondensation was performed at 135 °C for 48 h to afford PLLA with M_n of 1.1 × 10⁴ with good yield (90%). In no case did ¹H NMR, specific optical rotation, or DSC measurement confirm racemizations. The catalyst was recovered easily by extraction with water and reused for polycondensation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5247–5253, 2006     

Copolycondensations of bisphenols with aggregates of isophthalic acid and terephthalic acid activated by tosyl chloride/dimethylformamide/pyridine in different manners

A mixture of isophthalic acid (IPA) and terephthalic acid (TPA) was activated by a tosyl chloride/dimethylformamide/pyridine (Py) condensing agent in two steps via the treatment of a mixture of the initially activated IPA/TPA with additional TPA followed by the activation of TPA with the agent. The resulting mixture showed a solubility in Py different from that obtained by the activation of them all at once; the difference might be due to different structures of the aggregates of the activated IPA and TPA at the same composition of the diacids. The structures of the aggregates were evaluated on the basis of melting points and the IR spectra of a mixture of dimethyl esters of IPA and TPA produced by the quenching of the reaction mixtures with methanol. The mixture obtained by two‐step activation showed lower melting points and spectral changes due to enhanced associations of the esters with respect to the mixture prepared by the activation of them all at once. The aggregates were also examined in terms of the distributions of IPA and TPA in thermotropic copolyesters prepared from methylhydroquinone and chlorohydroquinone by their transition temperatures and ¹³C NMR. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3884–3892, 2001     

Telomerization of formamide with butadiene,catalyzed by palladium complexes

Conclusions It was shown that the N-2,7- and N-1,7-octadienylformamides can be obtained by the telomerization of formamide with butadiene using the four-component catalyst Pd²⁺-Ph₃P-AlEt₃-CF₃CO₂H.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khlmicheskaya, No. 3, pp. 703–704, March, 1984.     

Direct polyesterification with thionyl chloride in pyridine improved by a modification of monomer sequences in copolymers

The direct polyesterification with thionyl chloride (SOCl₂) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol % PHB could be obtained by initial reaction of MHB followed by PHB.     

Direct polyesterification with thionyl chloride in pyridine improved by a modification of monomer sequences in copolymers

The direct polyesterification with thionyl chloride (SOCl₂) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol% PHB could be obtained by initial reaction of MHB followed by PHB.     

Direct synthesis of aromatic polyesters by use of a sulfonium salt derived from tosyl chloride and N-methylimidazole

A sulfonium salt derived from tosyl chloride and N-methylimidazole was successfully used as an effective condensing agent for the preparation of high-molecular-weight aromatic polyesters by the direct polycondensation of aromatic dicarboxylic acids and bisphenols. Conditions for the formation of the sulfonium salt and of the reaction of the salt with dicarboxylic acids favorable for the polycondensation were examined. Thermal property of a polymer was investigated in terms of random sequences of monomer in the polymer backbone. Preparation of a polyamide and a polyesteramide was attempted with limited success.