Handbook of Solvents - George Wypych - ChemTech - Ventech!

13.3 Effects of organic solvents on phase-transfer catalysis 821
Reaction conditions Polymer yield
Catalyst % [η], dLg -1 * State
NB BTEAC 92.2 0.19 solution
Solvent b
Data obtained from Liaw and Chang; 59 a Polymerization was carried out with bisphenol S (5.00 mmol) and TCF
(7.50 mmol) in the organic solvent (37.5 mL) and water (30 mL) in the presence of catalyst (3.15 mmol) and sodium
hydroxide (28.5 mmol) at room temperature for 2 h. b Abbreviations: DCM, dichloromethane; TCM, tetrachloromethane;
DCE, 1,2-dichloroethane; NB, nitrobenzene. *Measured at a concentration of 0.5 gdL -1 in DMF at
25 o C
Another type of polysulfide (XIII) was synthesized by the two-phase
polycondensation of bis-(3-chloroacryloy)benzenes (XIa and XIb) with
4,4’-oxybisbenzenethiol (XII). The polycondensation was carried out in a chloroform-water
system at room temperature with some phase transfer catalysts.
[13.3.15]
Table 13.3.18 shows the results of polycondensation. The polysulfides having inherent
viscosities above 0.5 dLg -1 were readily obtained from two bis(2-chloroacryloyl)benzene
with or without use of phase transfer catalysts. These activated dichlorides are highly
reactive, almost comparable to ordinary dicarboxylic acid chlorides. The use of catalysts,
such as DC-18-C-6, was not essential to this type of polycondensation for producing high
molecular weight of polysulfides XIII.
Table 13.3.18. Synthesis of polysulfides XIII in organic solvent-water system a
Dichloride Solvent Catalyst Reaction time, min Polymer, [η], dLg -1 *
XIa chloroform none 15 0.21
XIa chloroform none 60 0.61
XIa chloroform DC-18-C-6 10 0.62
XIa chloroform TBAC 60 0.72
XIa dichloromethane DC-18-C-6 60 0.55
XIb chloroform none 60 0.55
XIb dichloromethane none 15 0.42
XIb dichloromethane DC-18-C-6 15 0.51
Data obtained from Imai; 41 a Reaction conditions: 2.5 mmol of XI, 2.5 mmol of XII, 0.05 mmol of catalyst, 5 mL of
solvent, 5 mL of 1.01 M KOH at 15 o C under nitrogen, *Measured at a concentration of 0.5 gdL -1 in concentrate sulfuric
acid at 30 o C