Polyesterification of aromatic dicarboxylic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine promoted by the improvement of the difficult solubility of the activated diacids with lithium chloride

The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004     

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     

Random copolycondensation of isophthalic acid/terephthalic acid with bisphenols by tosyl chloride/dimethylformamide/pyridine in terms of the monomer reactivity ratios of bisphenols

The random copolycondensation of isophthalic acid/terephthalic acid with various combinations of bisphenols (M₁ and M₂) with a tosyl chloride/dimethylformamide/pyridine condensing agent was carried out to investigate the effects of the monomer reactivity ratios, r₁′ and r₂′, on the reaction, like r₁ and r₂ in radical copolymerization. The ratios were calculated from the probabilities of finding an M₂ unit next to an M₁ unit and of finding an M₁ unit next to an M₂ unit, which were determined by an NMR analysis of the resultant copolymers. They were discussed with respect to the inherent viscosities (molecular weights) of the resultant copolymers. There was a fairly good relationship between r₁′ and r₂′ and the inherent viscosity values of the copolymers, indicating that copolycondensation could be facilitated by a combination of bisphenols; the lowering of r₁′ and r₂′ was indicative of random distributions in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3908–3915, 2003     

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     

The effect of compositions and combinations of the reactants upon the copolycondensation of isophthalic acid/terephthalic acid with a combination of hydroquinones and bisphenols by tosyl chloride/dimethylformamide/pyridine

Copolycondensation of isophthalic acid (IPA)/terephthalic acid (TPA) with various combinations of 2,2‐bis(4‐hydroxyphenyl)propane (BPA) and hydroquinones (HQs) or bisphenols (BPs) was conducted to study the effects of the compositions of IPA/TPA and of BPA/HQs or BPA/BPs upon the reaction. Different from homopolycondensation of each of diol components examined where most of the reaction was facilitated by lower contents of IPA at about 70 mol %, the copolycondensation was influenced by a combination of diol components. With chlorohydroquinone (ClHQ) or bis(4‐hydroxyphenyl)sulfone (BPS) having a polar chlorine or sulfonyl substituent, the reaction proceeded most satisfactorily at IPA/TPA = 30/70, whereas it was IPA/TPA = 50/50 for the reaction with nonpolar methyl substituted methylhydroquinone (MeHQ). The reaction with 2,2‐bis(3,5‐dichloro‐4‐hydroxyphenyl)propane (TC‐BPA), despite having polar chlorine substituents in TC‐BPA, was not affected by IPA/TPA compositions. Alternatively, from the viewpoint of the compositions of diol components, the reactions containing 30–50 mol % of HQs or BPS yielded better results except for the reaction of IPA/TPA = 70/30, in which higher contents of MeHQ was more favorable. On the basis of sequence distributions of diol components in the resultant copolymers determined by NMR, compositions of IPA/TPA or diol components and combinations of the diols producing random copolymers yielded better results in copolycondensation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1100–1106, 2004     

Two‐stage copolycondensation of preformed oligomers with bisphenols by tosyl chloride/dimethylformamide/pyridine from distributions of resulting oligomers determined by a combination of gel permeation chromatography and NMR

A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (n_x‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation n_x (mol %) = n_x (% mol by GPC) × n₀ (mol % by NMR)/n₀ (% mol by GPC), where n_x (% mol) = n_x (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004     

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     

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     

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     

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).     

Additional evidence of possible structural effect of diol units in preformed oligoesters on solution copolycondensation with x,y‐dihydroxytoluenes and their isomers promoted by tosyl chloride/dimethylformamide/pyridine

A two‐stage copolycondensation of a mixture of equal parts of isophthalic acid and terephthalic acid was conducted using a tosyl chloride/dimethylformamide/pyridine condensing agent. In the initial stage x,y‐dihydroxytoluenes (x,y‐DHTs) or 2,4‐dihydroxyethylbenzene (2,4‐DHEB) was used and in the next stage isomeric DHTs or the DHEB was used. The results were examined in terms of how the reaction of the resulting oligomers with the next monomers proceeded, which was evaluated from distributions of the next monomers in the resultant copolymers as determined by ¹H NMR. A structurally selective reaction was observed. The preformed oligomers from symmetrically substituted 3,5‐DHT reacted randomly with similarly substituted 2,6‐DHT or asymmetric 2,4‐DHEB, but those from 2,4‐DHEB reacted selectively with both of 3,5‐ and 2,6‐DHT. In the reactions of the oligomers from 2,6‐DHT, they reacted randomly with 2,6‐DHT but selectively with 2,4‐DHEB. Such selective reactions were also observed in the reaction of p‐isomeric 2,5‐DHT with the oligomers prepared from 3,5‐ or 2,6‐DHT. When the monomers were copolymerized simultaneously instead of stepwise, they distributed randomly in the resultant copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5687–5694, 2004     

Polycondensation of aromatic dicarboxylic acids and bisphenols with a new tosyl chloride/triphenylphosphine oxide/pyridine condensing agent

A new condensing agent comprised of tosyl chloride (TsCl) and triphenylphosphine oxide (TPPO) in pyridine was very effective for the preparation of polyesters of aromatic dicarboxylic acids and bisphenols with higher molecular weight than those obtained from TsCl/dimethylformamide in pyridine. Among the phosphorus compounds examined TPPO was most effective, and the reaction using half an equivalent with respect to the carboxyl groups yielded the most favorable results at temperatures of more than 100°C.     

Possible structural effect of a′,b′‐dihydroxyacetophenone units in the preformed oligoesters upon copolycondensation with isomeric c′,d′‐dihydroxyacetophenones by TsCl/dimethylformamide/pyridine

A two‐stage copolycondensation of a mixture of equal parts of isophthalic acid and terephthalic acid first with a′,b′‐dihydroxyacetophenone (a′,b′‐DHAP) and then with isomeric c′,d′‐DHAP was examined at 60 and 80 °C. A structurally selective reaction was observed. At 80 °C, the preformed oligomers from symmetrically substituted 2′,6′‐DHAP reacted better with similarly substituted 2′,6′‐ or 3′,5′‐DHAP to give the copolymers of significantly higher inherent viscosity values than from the reaction with asymmetrically substituted 2′,4′‐DHAP, whereas at 60 °C they did almost equally well with any c′,d′‐DHAP. Similarly, the reaction of oligomers from 2′,4′‐DHAP with asymmetrically substituted 2′,4′‐DHAP or 2,4‐dihydroxybenzophenone yielded better results than those from the reaction with 2′,6′‐ or 3′,5′‐DHAP at both temperatures. The copolycondensations with comonomers of the structure independent of DHAPs were not affected by the preformed oligomers from DHAPs. The results are discussed in terms of the distributions of resulting oligomers determined by gel permeation chromatography. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 616–623, 2003     

Morphology of poly(p‐oxybenzoyl) crystal prepared by direct polycondensation of p‐hydroxybenzoic acid with p‐toluenesulfonyl chloride in pyridine

Poly(p‐oxybenzoyl) (POB) crystals were prepared with the reaction‐induced crystallization of oligomers during the direct polycondensation of p‐hydroxybenzoic acid (HBA) with p‐toluenesulfonyl chloride (TsCl) and N,N‐dimethylformamide in pyridine. Sheaflike lozenge‐shaped POB crystals were obtained, of which the longer diagonal was 7.0–8.0 μm. The influence of the polymerization condition on the morphology was examined to optimize the preparative condition for the crystals exhibiting the clearest habit, and the favorable condition was determined as the molar ratio of TsCl to HBA of 1.3 and polymerization concentration of 3.0%. The crystals possessed extremely high crystallinity and outstanding thermal stability. The formation mechanism of the crystal was proposed as follows. When the number‐average degree of polymerization of the oligomers exceeded a critical value of about 4, they were precipitated to form the hexagonal lamellae. The crystals were grown very quickly to lozenge‐shaped crystal through screw dislocation with the continuous precipitation of oligomers from the solution. Finally, the further polymerization occurred in the precipitated crystal with developing polymer‐chain packing. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3275–3282, 2003     

Effect of association of dicarboxylic acids activated by TsCl/DMF/pyridine upon the copolycondensation with bisphenols

When a mixture of terephthalic acid (TPA) and various dicarboxylic acids was activated by tosyl chloride (TsCl)/dimethyl‐ formamide (DMF)/pyridine (Py), the resulting mixture became dissolved in Py, although the activated TPA was insoluble even at 120 °C. The temperature at which the mixture became soluble was varied with their compositions and the structure of diacids. Mixing the separately activated TPA and isophthalic acid (IPA) also improved the solubility of the activated TPA to some extent. The interesting phenomena were attributed to associations of the activated diacids through the dipole–dipole interactions between the carbonyl groups. The structures of associates were estimated in terms of transition temperatures of the thermotropic IPA/TPA‐methylhydroquinone and IPA/TPA‐chlorohydroquinone copolymers. The transition temperatures were significantly affected by the temperature of polycondensation, the preparative procedures of a mixture of the activated diacids, and several additives. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 196–201, 2001     

Reaction of phenylacetylene with Ti(OR)4?AlEt3 and V(acac)3?AlEt3: Cyclotrimerization versus chain oligomerization

The polymerization of phenylacetylene with the microheterogeneous Ti(OR)₄? AlEt₃ and homogeneous vanadium acetylacetonate/aluminum triethyl Ziegler–Natta catalyst systems was analyzed. The effects of some cocatalysts (e.g., pyridine and phenylacetylide) and the solvent, temperature, and time were analyzed. Both catalyst systems produced poly(phenylacetylene) (PPA) and a 1,2,4‐triphenylbenzene (1,2,4‐TPB)/1,3,5‐triphenylbenzene (1,3,5‐TPB) cyclotrimer mixture in various molar ratios. The titanium catalyst showed the lowest PPA/triphenylbenzene ratio. The 1,2,4‐TPB/1,3,5‐TPB molar ratio decreased with increasing PPA. On the basis of the spectroscopic data, PPA had a cis–transoidal stereoregular structure. The molecular mass of PPA was determined with vapor pressure osmometry and gel permeation chromatography. A mechanism for the polymerization reaction versus cyclotrimerization was proposed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1228–1237, 2005     

Determination of phthalic,terephthalic, and isophthalic acids in the presence of each other by gas chromatography

A procedure was developed for the simultaneous determination of phthalic acid isomers; the procedure includes the preparation of diisoamyl esters by reaction with isoamyl alcohol in a benzene solution in the presence of sulfuric acid with the distillation of an azeotrope mixture of benzene with water, the neutralization of acid with triethylamine, and the separation of esters by gas-liquid chromatography on a steel column (1 m × 3 mm) filled with Chromaton N-AW-HMDS with 5% Apiezon L in the temperature programming mode with flame-ionization detection. The time of separation is 13 min. The time of the sample preparation step is 2–2.5 h. The lower determination limit is 20 ng. The procedure allows the determination of phthalic acids in the concentration range from 0.02 to 2 mg/L in liquid samples and from 0.03 to 3 mg/m³ in air.     

Preparation and characterization of novel polyaryloxydiphenylsilanes with high glass transition temperature by melt polycondensation of dianilinodiphenylsilane with bisphenols

Novel polyaryloxydiphenylsilanes with reduced viscosities of 0.31–0.65 dL/g were obtained by the melt polycondensation of dianilinodiphenylsilane with three bisphenols, 2,2-bis (4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 3 (4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol, and 9,9-bis (4-hydroxyphenyl) fluorene, at 200–320°C in vacuo. These polymers are all amorphous and readily soluble in a wide variety of organic solvents such as chlorinated and aromatic hydrocarbons, cyclic ethers, and polar aprotic solvents. Because of their bulky and/or rigid ring structures, polyaryloxydiphenylsilanes containing diphenylhexafluoropropane, phenylindane, and diphenylfluorene units in the main chain have high glass transition temperatures of 106, 112, and 172°C, respectively. They are thermally stable showing almost no weight loss up to 350°C in air. Colorless, transparent, but brittle films are obtained from these polymers by solution casting. Ultraviolet transmission is sharply cut off by these polyaryloxydiphenylsilane films at ca. 300 nm, and the cut-off wavelength depends on the bisphenols used.