A facile synthesis and the polymerization of macrocyclic 1,4-phenylene sulfide (PPS) oligomers

Macromolecules

Volumn 29, Issue 14, 1996, Pages 5050-5053

  Wang, Yi Feng ^a,b   Hay, Allan S ^a  

^a MCGILL UNIVERSITY   (Canada)

^b GENERAL ELECTRIC COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIFFERENTIAL SCANNING CALORIMETRY; GEL PERMEATION CHROMATOGRAPHY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; RING OPENING POLYMERIZATION; SOLUBILITY; SOLVENTS; SULFUR; SYNTHESIS (CHEMICAL); THERMODYNAMIC PROPERTIES; THERMOGRAVIMETRIC ANALYSIS; VISCOSITY;

CYCLIZATION REACTION; HIGH MOLECULAR WEIGHT POLYPHENYLENE SULFIDE; MACROCYCLIC PHENYLENE SULFIDE OLIGOMERS;

OLIGOMERS;

EID: 0030188717     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma9602740     Document Type: Article

References (28)

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12. Ding, Y.; Hay, A. S. Macromolecules, submitted.
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15. (a) Hay, A. S.; Wang, Y.-F. U.S. Patent application 08/ 419,112, 1995.
16. (b) Wang, Y.-F.; Chan, K. P.; Hay, A. S. Macromolecules 1995, 28, 6371. In the patent application, cyclic 1,4-phenylene sulfide oligomers were prepared by the self-condensation reaction of copper(I) p-bromothiophenoxide in quinoline at 195-200°C under high dilution. In a typical reaction, copper(I) p-bromothiophenoxide solid (0.60 g) was periodically added to a quinoline solution (400 mL) at 195-200 °C every 8 h until, overall, 3.60 g (14.31 mmol) of the copper salt was added, to give a final concentration of product of 35.8 mM. This process led to formation of cyclic oligomers containing 4-15 monomeric units in 50% yield. The cyclic oligomers showed a melting point of 217 °C.
17. (a) Miyata, H.; Inoue, H. U.S. Patent 5,384,391, 1995.
18. (b) Ash, C. E.; Laurent, W. A. U.S. Patent 5,440,009, 1995. In both patents, cyclic 1,4-phenylene sulfide oligomers were extracted from PPS. In a typical process, only 1.2 g of cyclic oligomers containing 7-15 monomeric units was obtained from 200 g of PPS. The cyclic oligomers showed a melting point of 260 °C.
19. Wang, Z. Y.; Hay, A. S. Polymer 1992, 33, 1778.
20. The bisthiophenol N-propylcarbamates 2 (a and b) were prepared by treating 4,4′-thiobis[benzenedithiol] and 1,3-benzenedithiol, respectively (both from Aldrich), with a slight excess (20% equivalent) of n-propyl isocyanate in DMF with addition of a few drops of pyridine at room temperature for 1 h. The corresponding carbamates were obtained in high yields (>92%) as crystalline, odorless, and colorless solids which were easily recrystallized from methyl ethyl ketone (MEK).
21. 3, 40 g, 0.4 mol), N,N-dimethylformamide (DMF, 1100 mL), and toluene (150 mL). The mixture was mechanically stirred and heated to reflux under nitrogen. The temperature of the mixture was kept at 150-155 °C by continually removing toluene. A concentrated solution of the reactants 1 (23.825 g, 0.100 mol) and 2a (42.060 g, 0.100 mol) in DMF (150 mL) was then added over 5 h via a syringe pump. After the addition was complete, the reaction mixture was kept under reflux for another 2 h.
22. The GPC analysis was carried out on a Waters 510 HPLC using four phenogel 5 μm columns arranged in series (each 300 mm × 7.8 mm i.d., one linear and three 500 Å). HPLC grade THF containing 0.5 wt/v % LiBr was used as the eluent, with a flow rate of 1.0 mL/min, the UV detector was at 254 nm, and polystyrene standards were used for the calibration.
23. 2 laser light, 3 ns pulse width, 100 μm diameter spot). The MALDI instrument was operated in a positive reflectron mode. The ions produced from each laser shot were accelerated to 20 keV into aim drift region. An external calibration using bovine insulin and angiotension was used; this provides mass accuracy within 0.02% for this instrument.
24. Thermal analyses of macrocyclic oligomers were carried out on Seiko 220 DSC and 220 TGA/DTA instruments under nitrogen (a flow rate of 100 mL/min), with a heating rate of 20 °C/min.
25. Babu, J. R.; Brink, A. E.; Konas, M.; Riffle, J. S. Polymer 1994, 35 (23), 4949.
26. The GPC analysis was carried out as in note 16, except that chloroform was used as the eluent.
27. A typical polymerization procedure is as follows: cyclics 4a (2.0 g) were mechanically mixed with elemental sulfur (6.0 mg) in a 50 mL dry test tube. After sweeping with nitrogen for a few minutes, the test tube was sealed with a septum that was equipped with a nitrogen inlet and outlet. The test tube was then placed into a preheated salt bath at 300 °C for 30 min. The resulting polymer was removed by breaking the test tube.
28. Wang, Y.-F.; Chan, K. P.; Hay, A. S. Macromolecules, in press.