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Synthesis of Polyesters by Direct Polycondensation with Picryl Chloride

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Synthesis of Polyesters by Direct Polycondensation with Picryl Chloride Polymer Journal, Vol. 14, No.8, pp 643-648 (1982) Synthesis of Polyesters by Direct Polycondensation with Picryl Chloride Hozumi TANAKA, Yuki IWANAGA, Guo-chuang Wu, Kohei SANUI, and Naoya OGATA Department of Chemistry, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102, Japan (Received April 3, 1982) ABSTRACT: The polycondensation reaction of various dicarboxylic acids and diols such as terephthalic acid and ethylene glycol occurred at room temperature in pyridine in the presence of picryl chloride to give polyesters in high yield. Reaction conditions, basic solvents, temperatures, concentrations of monomer, and amount of picryl chloride were investigated. A combination of picryl chloride and pyridine was found to be satisfactory for the polyester synthesis. The polycondensation reaction possibly proceeds through the formation of an active ester from picryl­ ic acid and carboxylic acid, followed by esterification with hydroxyl group. Yields of polyester from 2,5-pyridinedicarboxylic acid and 1,10-decanediol by this direct polycondensation reached up to 89%, and the solution viscosity of the polyester was approximately 1.0 under optimum reaction conditions. The polyester obtained from terephthalic acid and I ,5-pentanediol had a higher solution viscosity than those from various combinations of dicarboxylic acids and diols. Aliphatic dicarboxylic acid such as adipic acid yielded polyester having a lower solution vis­ cosity than aromatic dicarboxylic acid. KEY WORDS Direct Polycondensation I Polyester I Picryl Chloride Pyridine I Terephthalic Acid I 2,5-Pyridinedicarboxylic Acid 1 Diols Bisphenol A I Polyester synthesis is generally carried out at dicarboxylic acids and aromatic diols at tempera­ elevated temperatures above 200°C under high vac­ tures above l oooc in the presence of triphenyl­ uum in order to eliminate volatile products and phosphine in pyridine. It was recently found10 that thus shift the equilibrium towards the formation of aromatic polyesters can be obtained in a quanti­ polymer. On the other hand, various routes are tative yield under mild conditions by reacting m­ available for the synthesis ofpolyamides under mild hydroxybenzoic acid in the presence of triphenyl­ conditions1 - 6 by which polycondensation can be phosphine with poly-halo compounds such as enhanced using active monomers such as acid hexachloroethane in a pyridine solution. It was chlorides7 or activated esters. 8 Very few reports reported in the previous paper11 that polyamides have been published on the synthesis of polyesters and polyesters were formed in the presence of picryl under mild conditions. chloride under mild conditions. Various polyesters It was previously reported9 that aromatic poly­ were prepared by the synthesis method shown be­ esters can be obtained by heating a mixture of low, using picryl chloride as a condensation agent. N02 Ho- R- OH + HOOC- R I -·COOH + o2 N-v-Cl N02 -(0-R-OCO-R'-COt + Py.HCl + in Pyridine 643 0\ Table I. Synthesis of polyester with picryl chloride at room temperature Monomer Picryl Pyridine NMP" Time Yield amount chloride Reaction Monomer phase cm3 cm3 h mol mol % Hooc-Q-cooH BPAc 0.002 0.005 10 0 20 Homo 90 0.50 Hooc-o-cooH BPA 0.002 0.005 !Od 0 15 Homo 0 Hooc-Q-cooH HO(CH 2 ) 40H 0.002 0.005 10 0 5 Homo 64 0.17 Hooc-()-cooH HO(CH 2 ) 40H 0.002 0.005 10d 0 15 Hetero 0 aooc-Q-cooH HO(CH 2 ) 40H 0.002 0.005 2 8 18 Homo 0 ;t HOOC-0- COOH HO(CH 2 ) 20H 0.002 0.005 10 0 18 Homo 47 0.13 ...., z)> HOOc-Q-coOH HO(CH ) 0H 0.002 0.005 10 0 18 Homo 83 0.45 2 6 )> HOOC-0-COOH Ho--<tj)-oa 0.002 0.005 10 0 18 Homo 82 0.35 f2.. aooc-Q-cooa HO(CH 2 ) 40H 0.002 0.005 10 0 18 Hetero 80 0.09 Hooc-Q-cooa BPA 0.002 0.005 10 0 15 Hetero 59 0.10 HOOC(CH2 ) 4COOH HO(CH 2 ) 40H 0.002 0.005 10 0 17 Homo 100 0.03 "0 0 HOOC(CH 2 ) 4COOH BPA 0.002 0.005 10 0 17 Homo 53 0.10 Q"a ..., 0.004 0.005 10 0 13 Homo "';-< HOOC-o-OH 19 0.04 <0 :- • N-Methyl-2-pyrrolidone. b 0.1 g/10cm3 in m-cresol at 30oC. z ' Bisphenol A. 9 d Triethylamine. "00 ::0 00 N Synthesis of Polyesters This paper describes the investigation of the was added to remove the solvent, by-products and optimum reaction conditions for the synthesis of unreacted monomers from the polymer which was polyesters from various dicarboxylic acids and then isolated by filtration. The polyesters from 2,5- diols, where the polycondensation of 2,5-pyridine­ pyridinedicarboxylic acid and 1,5-pentanediol or dicarboxylic acid and I, 10-decanediol is empha­ 1,9-nonanediol were separated in ether since these sized. polyesters dissolve in acetone. The polymer was repeatedly washed with water, EXPERIMENTAL followed by low boiling point solvents such as acetone, methanol or ether which are poor solvents Picryl chloride and other aromatic halo­ for the polyesters. compounds of special grade purity were used as Solution viscosities of the polyesters were de­ purchased. Solvents were purified by conventional termined in m-cresol, while those obtained when procedrues. The general procedure used for the using terephthalic acid and ethylene glycol were synthesis of polyester from 2,5-pyridinedicarboxylic measured in a mixed solvent of phenol and acid and 1, 10-decanediol is as follows: tetrachloroethane (1/1) at 30°C. 0.002 mol of 2,5-pyridinedicarboxylic acid and 1,10-decanediol was dissolved in 10cm3 of pyridine RESULTS AND DISCUSSION and then 0.005 mol of picryl chloride was added to the solution with stirring at room temperature. As Table I summarizes the results of the synthesis of soon as picryl chloride was added, an exothermic the polyesters from various dicarboxylic acids and reaction took place and the solution took on an diols by direct polycondensation in the presence of orange color. The entire reaction proceeded in a picryl chloride. This table shows that polyesters homogeneous phase; when terephthalic acid was were obtained in good yield from 2,5-pyridine­ used, all the reactions proceeded in a heterogeneous dicarboxylic acid (2,5-PDC) and bisphenol A or 1,4- phase. After a given period of time, excess acetone cyclohexanediol, while the combination of aliphatic Table II. Direct polycondensation of terephthalic acid or 2,5-pyridine dicarboxylic acid with various diols at room temperature" Monomer Polymer Time HOOC-R-COOH HO+CH2)n0H h Yield/% IJ,v/Cb R n -o- 2 15 33 0.05 3 15 85 0.12 4 15 84 0.19 5 15 86 0.19 6 15 87 0.43 9 14 57 0.33 10 14 95 0.22 12 16 77 0.22 2 18 47 0.13 -Q- 3 16 73 0.33 4 16 75 0.53 5 16 79 0.45 6 16 78 0.56 9 16 36 0.17 10 16 89 0.72 12 16 77 0.63 • Amount of monomer=0.002 mol; amount of picryl chloride=0.005 mol; solvent, 10cm3 of pyridine. b 0.1 g/1 0 cm3 in m-cresol at 30°C. Polymer J., Vol. 14, No. 8, 1982 645 H. TAN AKA et a/. dicarboxylic acid and diols failed to give satisfac­ picryl chloride in pyridine. The solution viscosity of tory results in terms of the solution viscosities. the polyester reached a constant value within 30 min When triethylamine was used in place of pyridine, and the growing reaction was completed with 1 h no polymer was obtained. The polycondensation of even at room temperature. m-hydroxybenzoic acid resulted in a lower yield Figure 2 indicates the effect of the amount of than that of 2,5-PDC and ethylene glycol. picryl chloride to the monomer on the poly­ Table II shows the results of the poly­ condensation of 2,5-PDC and 1,10-decanediol. The condensation of aliphatic diols of various methylene solution viscosity of the resulting polyesters in­ units with terephthalic acid or 2,5-PDC at room creased with increasing amounts of picryl chloride, temperature. reaching a value of0.9 and the optimum molar ratio Solution viscosities reached a maximum value of of picryl chloride to the monomer was found to be 0.58 when 1,5-pentanediol was used along with terephtha1ic acid, and those of the polyesters de­ creased with increasing chain length of the meth­ 1.0 100 ylene units in diols. On the other hand, 2,5-PDC 0 u yielded polyesters with aliphatic diols in good yield. 'Q b.)' b. 2- The solution viscosities, which increased almost in "'"""' 0 proportion to the number of methylene units of '"' "0 0 u to diols, obtained a value of 0.72 except when using >-'" > 0.5 6 50 1,9-nonanediol. The fluctuation in the solution vis­ c 0 !;;.'" cosity of these polyesters may possibly have been 0 ) 0 0. 0 caused by solvent affinity of the polyesters in py­ U> ridine, thus terminating chain growth by the pre­ cipitation of the polyesters out of the reaction phase. Since the polyester obtained when using 1.0 1.5 2.0 terephthalic acid and ethylene glycol apparently did Ratio of Picryl chloride to Monomer not dissolve in pyridine, the solution viscosity was Figure 2. Effect of amount of picryl chloride on poly­ as low as 0.05. condensation of 2,5-pyridinedicarboxylic acid with I, 10- Figure I indicates the rate of the poly­ decanediol at room temperature: Amount of condensation of 2,5-PDC with 1,10-decanediol monomer= 0.002 mol; time= I h.
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