Lewis acid-mediated double ring-opening reaction of an oligo(spiro- orthocarbonate): A novel class of expanding material

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 43, Issue 21, 2005, Pages 5323-5327

  Hino, Tetsuo ^a   Endo, Takeshi ^a  

^a YAMAGATA UNIVERSITY   (Japan)

Author keywords

Crosslinking; Expanding material; Networks; Oligomers; Volume expansion

Indexed keywords

CROSSLINKING; X RAY DIFFRACTION ANALYSIS;

EXPANDING MATERIALS; LEWIS ACID; NETWORKS;

ORGANIC POLYMERS;

EID: 27944462998     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/pola.20966     Document Type: Article

References (34)

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16. There are a large number of studies on double ring-opening reactions/polymerizations of bicyclic compounds because of their fascinating structure and unique properties. For example:(a)Bailey, W. J; Zheng, Z. F. J Polym Sci Part A: Polym Chem 1991, 29, 437.
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22. Incidentally, we also reported that 6-membered ring cyclic carbonates act as one of expanding monomers, and that the main deriving force of the volume expansion different from that of bicyclic expanding monomer, such as SOCs: Takata, T.; Sanda, F; Ariga, T.; Nemoto, H.; Endo, T. Macromol Rapid Commun 1997, 18, 461.
23. Many applications using expanding monomers have been also investigated: e.g. the volume shrinkage of common polymerizations can be controlled by copolymerization with various amounts of expanding monomers to give the corresponding copolymers, depressing the volume shrinkage (refs. 2(h)(1) and references cited therein). However, all the applications in materials design were inevitably restricted to change from the monomers to the (co)polymers.
24. Although a network formation usually causes volume shrinkage, the resulting networked polymers generally have many significant practical advantages compared with linear polymers, such as rather high mechanical strength and chemical and/or thermal stability: Griskey, R. G. Polymer Process Engineering; Chapman & Hall: New York, 1995.
25. Although a polymer-gel is known as a represented material showing volume change, the volume expansion, which is induced by its swelling, usually causes decrease of its mechanical strength and thermal stability such as Tg: Seymour, R. B.; Carraher, C. E., Jr. Polymer Chemistry, 3rd ed.; Marcel Dekker: New York, 1992.
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28. Several spiro-polymers, which are subclass of ladder polymers, were reported to indicate great rigidity structure (highly crystalline-like materials) because of the lack of its rotational freedom: for example, Makhseed, S.; McKeown, N. B. Chem Commun 1999, 255.
29. Vodak, D. T.; Braun, M.; Lordanidis, L.; Plevert, J.; Stevens, M.; Beck, L.; Spence, J. C. H.; O'Keeffe, M.; Yaghi, O. M. J Am Chem Soc 2002, 124, 4942.
30. A representative synthetic procedure: The white solid of o-SOC (50 mg, 0.35 mmol) was dispersed in dry toluene (1 mL), and then BF3.OEt2 (0.3 mL, 1.59 mmol) was slowly added under Ar. After the mixture was stirred at 100°C for 24 h under Ar, the resulting compound was filtrated and washed with methanol with a Soxhlet extractor. The MeOH-insoluble product was dried in vacuo at 50°C for 48 h to yield 48.5 mg of a pale grayish solid (97%, NP-1).
31. We can not quantitatively estimate the ratio of the ring-opened SOC units at this stage, although it is expected that this ratio strongly relates to degree of the volume expansion.
32. The elemental analysis (EA) result of NP-1 also suggests that the change from o-SOC to NP-1 is based on the double ring-opening structural isomerization, at least partially. Found EA for NP-1: C, 49.95; H, 5.76. Cf. calcd. EA for o-SOC, C6H804: C, 50.00; H, 5.60.
33. We carefully measured the change in volume after the polymerization by a density gradient tube method (refs. 1(b), 2(c)-(1), and references cited therein). The typical measurement method is as follows: At first, the powdered sample was pressed in the shape of a pellet under vacuum. The sample was dipped for a while in aqueous solution containing a surface-active agent in order to remove air bubbles adhering to the sample surface as much as possible, and then the density was measured. In addition, the reproducibility in the present measurement is very sufficient, even with small amount of sample.
34. The chemical stability of NP-1 should be mainly based on the networked structure via the double ring-opening reactions, while that of NP-2 might be predominantly based on the unreacted o-SOC structures. Incidentally, o-SOC has a high chemical stability, because of its ordered structure (see ref. 10).