Condensative chain polymerization in solid-liquid phase. Synthesis of polyesters with a defined molecular weight and a narrow molecular weight distribution by polycondensation [4]

Journal of the American Chemical Society

Volumn 121, Issue 49, 1999, Pages 11573-11574

  Yokozawa, Tsutomu ^a   Suzuki, Hideto ^a  

^a KANAGAWA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ESTER DERIVATIVE;

CHEMICAL REACTION; CHEMICAL STRUCTURE; LETTER; LIQUID; MOLECULAR WEIGHT; POLYMERIZATION; REACTION ANALYSIS; SOLID; SYNTHESIS;

EID: 0033573105     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993224u     Document Type: Letter

References (34)

1. For a recent review, see: Fischer, M.; Vögtle, F. Angew. Chem., Int. Ed. 1999, 38, 885.
2. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
3. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
4. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
5. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
6. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
7. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
8. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
9. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
10. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
11. For examples of stepwise synthesis of linear oligomers, see: (a) Zhang, J.; Moore, J. S.; Xu, Z.; Aguirre, R. A. J. Am. Chem. Soc. 1992, 114, 2273. (b) Young, J. K.; Nelson, J. C.; Moore, J. S. J. Am. Chem. Soc. 1994, 116, 10841. (c) Nelson, J. C.; Young, J. K.; Moore, J. S. J. Org. Chem. 1996, 61, 8160. (d) Godt, A.; Ziener, U. J. Org. Chem. 1997, 62, 6137. (e) Jones, L., II; Schumm, J. S.; Tour, J. M. J. Org. Chem. 1997, 62, 1388. (f) Schumm, J. S.; Pearson, D. L.; Tour, J. M. Angew. Chem., Int. Ed. 1994, 33, 1360. (g) Pearson, D. L.; Tour, J. M. J. Org. Chem. 1997, 62, 1376. (h) Pearson, D. L.; Schumm, J. S.; Tour, J. M. Macromolecules 1994, 27, 2348. (i) Sadighi, J. P.; Singer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 4960. (j) Huang, S.; Tour J. M. J. Am. Chem. Soc. 1999, 121, 4908.
12. Possible condensative chain polymerizations are shown by the polycondensations of alkali 4-halothiophenoxide and sodium 4-halobenzenesulfinate, respectively, although the polymerization mechanisms are not exactly clear because of insolubility of polymers. See: (a) Lenz, R. W.; Handlovits, C. E.; Smith, H. A. J. Polym. Sci. 1962, 58, 351. (b) Robello, D. R.; Ulman, A.; Urankar, E. Macromolecules 1993, 26, 6718.
13. Possible condensative chain polymerizations are shown by the polycondensations of alkali 4-halothiophenoxide and sodium 4-halobenzenesulfinate, respectively, although the polymerization mechanisms are not exactly clear because of insolubility of polymers. See: (a) Lenz, R. W.; Handlovits, C. E.; Smith, H. A. J. Polym. Sci. 1962, 58, 351. (b) Robello, D. R.; Ulman, A.; Urankar, E. Macromolecules 1993, 26, 6718.
14. Yokozawa, T.; Horio, S. Polym. J. 1996, 28, 633.
15. Mita, I.; Stepto, R. F. T.; Suter, U. W. Pure Appl. Chem. 1994, 66, 2483.
16. Yokozawa, T.; Shimura, H. J. Polym. Sci. Polym. Chem. Ed. 1999, 37, 2607.
17. For reviews, see: (a) Imai, Y. J. Macromol. Sci. Chem. 1981, A15, 833. (b) Imai, Y. J. Synth. Org. Chem. Jpn. 1984, 42, 1095. (c) Tagle L. H. In Handbook of Phase Transfer Catalysis; Sasson, Y., Neumann, R., Eds.; Blackie Academic & Professional: London, 1997; p 200.
18. For reviews, see: (a) Imai, Y. J. Macromol. Sci. Chem. 1981, A15, 833. (b) Imai, Y. J. Synth. Org. Chem. Jpn. 1984, 42, 1095. (c) Tagle L. H. In Handbook of Phase Transfer Catalysis; Sasson, Y., Neumann, R., Eds.; Blackie Academic & Professional: London, 1997; p 200.
19. For reviews, see: (a) Imai, Y. J. Macromol. Sci. Chem. 1981, A15, 833. (b) Imai, Y. J. Synth. Org. Chem. Jpn. 1984, 42, 1095. (c) Tagle L. H. In Handbook of Phase Transfer Catalysis; Sasson, Y., Neumann, R., Eds.; Blackie Academic & Professional: London, 1997; p 200.
20. For examples of the polycondensation of alkali bromomethylbenzoates, see: (a) Cameron. G. G.; Buchan, G. M.; Law, K. S. Polymers 1981, 22, 558. (b) Inoki, M.; Akutsu, F.; Kitayama, Y.; Kasashima, Y.; Naruchi, K. Polym. J. 1996, 28, 1103. For an example of the polycondensation of bromomethylbenzoic acids using triethylamine, see: Pinkus, A. G.; Subramanyam, R.; Hariharan, R. J. Macromol. Sci., Pure Appl. Chem. 1992, A29, 1031.
21. For examples of the polycondensation of alkali bromomethylbenzoates, see: (a) Cameron. G. G.; Buchan, G. M.; Law, K. S. Polymers 1981, 22, 558. (b) Inoki, M.; Akutsu, F.; Kitayama, Y.; Kasashima, Y.; Naruchi, K. Polym. J. 1996, 28, 1103. For an example of the polycondensation of bromomethylbenzoic acids using triethylamine, see: Pinkus, A. G.; Subramanyam, R.; Hariharan, R. J. Macromol. Sci., Pure Appl. Chem. 1992, A29, 1031.
22. For examples of the polycondensation of alkali bromomethylbenzoates, see: (a) Cameron. G. G.; Buchan, G. M.; Law, K. S. Polymers 1981, 22, 558. (b) Inoki, M.; Akutsu, F.; Kitayama, Y.; Kasashima, Y.; Naruchi, K. Polym. J. 1996, 28, 1103. For an example of the polycondensation of bromomethylbenzoic acids using triethylamine, see: Pinkus, A. G.; Subramanyam, R.; Hariharan, R. J. Macromol. Sci., Pure Appl. Chem. 1992, A29, 1031.
23. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
24. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
25. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
26. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
27. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
28. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
29. For examples of polycondensation with PTC involving the reaction of alkali carboxylates with alkyl halides, see: (a) Ueda, M.; Sakai, N.; Imai, Y. Koubunshi Ronbunshu 1981, 38, 443. (b) Cameron, G. G.; Law, K. S. Polymers 1981, 22, 272. (c) Kielkiewica, J.; Kuran, W.; Pogorzelska, B. Makromol. Chem. Rapid Commun. 1981, 2, 255. (d) Rokichi, G.; Kielkiewicz, J.; Marciniak, B. Polimery 1982, 27, 374. (e) Kuran, W.; Rokicki, G.; Kielkiewicz, J. Polish Patent PL 122 553; Chem. Abstr. 1986, 101, 73283h. (f) Klemm, D.; Geschwend, G. Makromo. Chem. Rapid Commun. 1988, 9, 431. (g) Hurduc, N.; Bordieanu, V.; Simionescu, C. Polym. Bull. 1992, 28, 639.
30. The polymerization of 1 was carried out in the presence of 10 mol % of 2 in various kinds of solvent (toluene, diethyl ether, THF, dichloromethane, chloroform, and aceton) and the polymerization in acetone yielded the polymer having the narrowest polydispersity.
31. Polymer model compound, 4′-nitrobenzyl 4-bromomethyl-3-n-octyl-oxybenzoate was reacted with 5 equiv of 4-methoxyphenol in the presence of 4.5 equiv of potassium hydroxide in dichloromethane and water containing a catalytic amount of tetrabutylammonium bromide as a phase transfer catalyst for 24 h to give the corresponding 4-methoxyphenyl ether in 99% yield (HPLC yield) without hydrolysis of the ester linkage of the polymer model compound.
32. n (NMR) = 4480.
33. This polymerization behavior was observed in the polymerization of the same monomer in an aqueous-organic biphasic system using PTC. See: Hiyama N.; Suzuki, H.; Yokozawa, T. Polym. Prepr. Jpn. 1999, 48, 307.
34. 0 ratios were 20 or above, the polymers having the molecular weights close to the calculated values were obtained as well as oligomers without the initiator 2 unit.