Коллектив авторов - Международная молодежная научная школа «Школа научно-технического творчества и концептуального проектирования» Страница 8

2. Okamoto, M. Mater. Sci. Tech. Lond. 2006, 22, 756-779.

3. Ray, S. S.; Okamoto, M. Prog. Polym. Sci. 2003, 28, 1539-1641.

4. Alexandre, M.; Dubois, P. Mat. Sci. Eng. R. 2000, 28, 1-63.

5. Ma, J.; Xu, H.; Ren, J.H.; Yu, Z.Z.; Mai, Y.W. Polymer 2003, 44, 46194624.

6. Akat, H.; Tasdelen, M. A.; Du Prez, F.; Yagci, Y. Eur. Polym. J. 2008, 44, 1949-1954.

7. Nese, A.; Sen, S.; Tasdelen, M. A.; Nugay, N.; Yagci, Y. Macromol. Chem. Phys. 2006, 207, 820-826.

8. Yenice, Z.; Tasdelen, M. A.; Oral, A.; Guler, C.; Yagci, Y. J. Polym. Sci. Polym. Chem. 2009, 47, 2190-2197.

9. Oral, A.; Tasdelen, M. A.; Demirel, A. L.; Yagci, Y. Polymer 2009, 50, 3905-3910.

10. Oral, A.; Tasdelen, M. A.; Demirel, A. L.; Yagci, Y. J. Polym. Sci. Polym. Chem. 2009, 47, 5328-5335.

11. Usuki, A.; Kojima, Y.; Kawasumi, M.; Okada, A.; Fukushima, Y.; Kurauchi, T.; Kamigaito, O. J. Mat. Res. 1993, 8, 1179-1184.

12. Bottcher, H.; Hallensleben, M. L.; Nuss, S.; Wurm, H.; Bauer, J.; Behrens, P. J. Mat. Chem. 2002, 12, 1351-1354.

13. Zhao, H. Y.; Argoti, S. D.; Farrell, B. P.; Shipp, D. A. J. Polym. Sci. Polym. Chem. 2004, 42, 916-924.

14. Zhao, H.Y.; Farrell, B.P.; Shipp, D.A. Polymer 2004, 45, 4473-4481.

15. Wang, Y. P.; Pei, X. W.; Liu, X. J.; Kun, Y.; Zhang, D. X.; Li, Q. L.; Wang, Y. F. Polym. Comp. 2005, 26, 465-469.

16. Datta, H.; Bhowmick, A. K.; Singha, N. K. J. Polym. Sci. Polym. Chem. 2008, 46, 5014-5027.

17. Datta, H.; Singha, N.K.; Bhowmick, A.K. Macromolecules 2008, 41, 50-57.

18. Oral, A.; Shahwan, T.; Guler, C. J. Mat. Res. 2008, 23, 3316-3322.

19. Behling, R. E.; Williams, B. A.; Staade, B. L.; Wolf, L. M.; Cochran, E. W. Macromolecules 2009, 42, 1867-1872.

20. Karesoia, M.; Jokinen, H.; Karalainen, E.; Pulkkinen, P.; Torkkeli, M.; Soininen, A.; Ruokolainen, J.; Tenhu, H. J. Polym. Sci. Polym. Chem. 2009, 47, 3086-3097.

21. Weimer, M. W.; Chen, H.; Giannelis, E. P.; Sogah, D. Y. J. Am. Chem. Soc. 1999, 121, 1615-1616.

22. Konn, C.; Morel, F.; Beyou, E.; Chaumont, P.; Bourgeat-Lami, E. Macromolecules 2007, 40, 7464-7472.

23. Salem, N.; Shipp, D. A. Polymer 2004, 46, 8573-8581.

24. Zhang, B. Q.; Pan, C. Y.; Hong, C. Y.; Luan, B.; Shi, P. J. Macromol. Rapid Commun. 2006, 27, 97-102.

25. Ding, P.; Zhang, M.; Gai, J.; Qu, B.J. J. Mat. Chem. 2007, 17, 11171122.

26. Samakande, A.; Sanderson, R. D.; Hartmann, P. C. Eur. Polym. J. 2009, 45, 649-657.

27. Kubies, D.; Pantoustier, N.; Dubois, P.; Rulmont, A.; Jerome, R. Macromolecules 2002, 35, 3318-3320.

28. Lepoittevin, B.; Pantoustier, N.; Devalckenaere, M.; Alexandre, M.; Kubies, D.; Calberg, C.; Jerome, R.; Dubois, P. Macromolecules 2002, 35, 8385-8390.

29. Viville, P.; Lazzaroni, R.; Pollet, E.; Alexandre, M.; Dubois, P. J. Am. Chem. Soc. 2004, 126, 9007-9012.

30. Di, J. B.; Sogah, D. Y. Macromolecules 2006, 39, 5052-5057.

31. Messersmith, P. B.; Giannelis, E. P. Chem. Mat. 1993, 5, 1064-1066.

32. Messersmith, P. B.; Giannelis, E. P. J. Polym. Sci. Polym. Chem. 1995, 33, 1047-1057.

33. Yoonessi, M.; Toghiani, H.; Daulton, T. L.; Lin, J. S.; Pittman, C. U. Macromolecules 2005, 38, 818-831.

34. Yoonessi, M.; Toghiani, H.; Kingery, W. L.; Pittman, C. U. Macromolecules 2004, 37, 2511-2518.

35. Yoonessi, M.; Toghiani, H.; Pittman, C. U. J. Appl. Polym. Sci. 2006, 102, 2743-2751.

36. Tasdelen, M. A.; Van Camp, W.; Goethals, E.; Dubois, P.; Du Prez, F.; Yagci, Y. Macromolecules 2008, 41, 6035-6040.

37. Zhou, Q. Y.; Fan, X. W.; Xia, C. J.; Mays, J.; Advincula, R. Chem. Mat. 2001, 13, 2465-2467.

38. Fan, X. W.; Zhou, Q. Y.; Xia, C. J.; Cristofoli, W.; Mays, J.; Advincula, R. Langmuir 2002, 18, 4511-4518.

SYNTHESIS OF MACROMOLECULAR PHOTOINITIATORS AND THEIR EFFECTS ON PHOTOINDUCED FREE RADICAL POLYMERIZATION

Photoinduced free radical polymerization is a widely used technology with a wide range of industrial applications such as curing of coatings on various materials, adhesives, printing plates, inks, electronics and photoresist and has recently been recognized as also having great potential in the biomedical fields [1]. In the development of photopolymerization, photoinitiator systems play a very important role since even the most reactive acrylate monomers hardly polymerize when exposed to the pure form of UV light [2]. Free radical photoinitiators can be classed as α-cleavage (Type I) and H-abstraction (Type II) initiators. Type II photoinitiators are the most studied free radical photoinitiators. The most widely used free radical Type II photoinitiators include benzophenone and derivatives, thioxanthones, benzyl, quinines while alcohols, ethers, amines and thiols are used as hydrogen donors [3-6]. Thioxanthones are among one of the most widely used bimolecular photoinitiators in vinyl polymerization because of their absorption characteristics at near UV-vis range and whose triplet excited states readily react with hydrogen donors such as amine, alcohol, ether, acid or thiol functional compounds (Scheme 1) thereby producing initiating radicals [49].

Low molecular weight photoinitiators have a main drawback in that their photolysis products might migrate onto the coating surface and may create yellowing and unpleasant odors with serious problems of contamination. Therefore, much effort has been spent on the development of polymeric photoinitiators, which have some advantages such as low migration, reduced yellowing, higher reactivity and low volatility with respect to low molecular weight analogues.

Scheme 1. Photoinitiation mechanism of thioxanthone in the presence of a coinitiator.

Polymeric Photoinitiators: Polymeric photoinitiators have attracted much attention in the past years, for they combine the properties of polymers with those of low molecular weight photoinitiators [10-26]. Solubility and miscibility problems, often observed with coatings containing low molecular weight photoinitiators, do not occur with the polymeric ones since polymers are easily miscible with the resin to be cured as well as with the final cured film. Moreover, odor and toxicity problems do not occur with macrophotoinitiators owing to the low volatility of the large molecules. The low migration tendency of polymeric photoinitiators and of photoproducts means that cured coatings are less prone to yellowing [27-31].

Macrophotoinitiators possessing chromophoric groups either in the main chain or as pendant groups can be prepared in two ways: (i) synthesis and polymerization of monomers with photoreactive groups or (ii) introduction of photoactive groups into polymer chains (Scheme 2). In the latter case, macrophotoinitiators were synthesized either by using functional initiators and terminators in a particular polymerization or by reacting functional groups of a preformed polymer with other functional groups of low molecular weight compounds also possessing photoreactive groups. Macrophotoinitiators, analogues to the low molecular weight photoinitiators, are divided into two classes, according to their radical generation mechanism, namely cleavage type (type I) and hydrogen abstraction type (type II) macrophotoinitiators.

Scheme 2. Preparing the “Side Chain” and “In Chain” polymeric photoinitiators according to different pathways.

[1] N.S. Allen, Ed., Photopolymerization and Photoimaging Science and Technology Elsevier Applied Science, London, 1987.

[2] J.P. Fouassier, Photoinitiation, Photopolymerization and Photocuring, Hanser, Munich, 1995.

[3] N.S. Allen, F. Catalina, J.L. Mateo, R. Sastre, Photochemistry of novel water-soluble para-substituted benzophenone photoinitiators – a photocalorimetric and photoreduction study, J. Photochem. Photobiol. A: Chem. 44 (1988), pp. 171-177.

[4] N.S. Allen, S.J. Hardy, A.F. Jacobine, D.M. Glaser, B. Yang, D. Wolf, F. Catalina, S. Navaratnam, B.J. Parsons, Photochemistry and photopolymerization activity of perester derivatives of benzophenone, J. Appl. Polym. Sci. 42 (1991), pp. 1169-1178.

[5] J.P. Fouassier, Photochemistry and UV Curing: New Trends,Research Signpost, 2006.

[6] L. Cokbaglan, N. Arsu, Y. Yagci, S. Jockusch, and N.J. Turro, 2Mercaptothioxanthone as a novel photoinitiator for free radical polymerization, Macromolecules 36 (2003), pp. 2649–2653.

[7] M. Aydin, N. Arsu, Y. Yagci, One-component bimolecular photoinitiating systems, 2-Thioxanthone acetic acid derivatives as photoinitiators for free radical polymerization, Macromol. Rapid Commun. 24 (2003), pp. 718-723.

[8] D.K. Balta, N. Arsu, Y. Yagci, S. Jockusch, N.J. Turro, Thioxanthoneanthracene: a new photoinitiator for free radical polymerization in the presence of oxygen, Macromolecules 40 (2007), pp. 4138–4141.

[9] M. Aydin, N. Arsu, Y. Yagci, S. Jockusch, and N.J. Turro, Mechanistic study of photoinitiated free radical polymerization using thioxanthone thioacetic acid as one-component type II photoinitiator, Macromolecules 38 (2005), pp. 4133–4138.

[10] X. Jiang, J. Yin, Dendritic macrophotoinitiator containing thioxanthone and coinitiator amine, Macromolecules 37 (2004), pp. 78507853.

[11] X. Jiang, H. Xu, J. Yin, Copolymeric dendritic macrophotoinitiators, Polymer 46 (2005), pp. 11079–11084.

[12] X. Jiang, H. Xu, J. Yin, Polymeric amine bearing side-chain thioxanthone as a novel photoinitiator for photopolymerization, Polymer 45 (2004), pp. 133-140.

[13] Jiang X, Yin J, Study of macrophotoinitiator containing in-chain thioxanthone and coinitiator amines, Polymer 45 (2004), pp. 5057-5063.

[14] X. Jiang, J. Yin, Water-soluble polymeric thioxanthone photoinitiator containing glucamine as coinitiator, Macromol. Chem. Phys. 209 (15), pp. 1593-1600.

[15] X. Jiang, J. Yin, Polymeric photoinitiator containing in-chain thioxanthone and coinitiator amines, Macromol. Rapid Commun. 25 (2004), pp. 748–752.

[16] X. Jiang, J. Yin, Copolymeric photoinitiators containing in-chain thioxanthone and coinitiator amine for photopolymerization, J. Appl. Polym. Sci. 94 (2004), pp. 2395–2400.

[17] J. Wei, H. Wang, X. Jiang, J. Yin, Effect on photopolymerization of the structure of amine coinitiators contained in novel polymeric benzophenone photoinitiators, Macromol. Chem. Phys. 207 (2006), pp. 1752-1763.

[18] H. Wang, J. Wei, X. Jiang, J. Yin, Highly efficient sulfur-containing polymeric photoinitiators bearing side-chain benzophenone and coinitiator amine for photopolymerization, J. Photochem. Photobiol. A: Chem. 186 (2007) 106-114.

[19] H. Wang, J. Wei, X. Jiang, J. Yin, Novel chemical-bonded polymerizable sulfur-containing photoinitiators comprising the structure of planar N-phenylmaleimide and benzophenone for photopolymerization, Polymer 47 (2007), pp. 4967-4975.

[20] H. Wang, J. Wei, X. Jiang, J. Yin, Novel polymerizable sulfurcontaining benzophenones as free-radical photoinitiators for photopolymerization, Macromol Chem. Phys. 207 (2006), pp. 1080-1086.

[21] R.S. Davidson, The chemistry of photoinitiators – some recent developments, J.Photochem. Photobiol.A: Chem. 73 (1993), pp. 81-96.

[22] C. Carlini, L. Angiolini, Polymeric photoinitiators, Radiat Curing Polym. Sci. Tech. 2 (1993), pp. 283-320.

[23] G. Temel, N. Arsu, Y. Yagci, Polymeric side chain thioxanthone photoinitiator for free radical polymerization, Polymer Bulletin 57 (2006), pp. 51-56.

[24] B. Gacal, H. Akat, D.K. Balta, N. Arsu, Y. Yagci, Synthesis and characterization of polymeric thioxanthone photoinitatiors via double click reactions, Macromolecules 41 (2008), pp. 2401-2405.

[25] F. Karasu, N. Arsu, Y. Yagci, 2-Mercapto thioxanthone as a chain transfer agent in free-radical polymerization: A versatile route to incorporate thioxanthone moieties into polymer chain-ends, J. Appl. Polym. Sci. 103 (2007), pp. 3766-3770.

[26] G. Temel, N. Arsu, One-pot synthesis of water soluble polymeric photoinitiator via thioxanthonation and sulfonation process, J. Photochem. Photobiol. A: Chem. (2008), in press.

[27] S.P. Pappas, UV Curing Science and Technology, Technology Marketing Corp., Norwalk, CT, 1978.

[28] J.P. Fouassier, Photoinitiation, Photopolymerization and Photocuring, Hanser, Munich, 1995.

[29] K. Dietliker, Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints Vol. III, SITATechnology Ltd, London, 1991.

[30] R.S. Davidson, Exploring the Science, Technology and Applications of UV and EB Curing, SITA Technology Ltd., London, 1999.

[31] M.K. Mishra, & Y. Yagci, Handbook of radical vinyl polymerization, Marcel Dekker, New York, 1998, Chapter 7, p. 233.

ОЦЕНКА ПОДВИЖНОСТИ МАКРОМОЛЕКУЛЯРНЫХ ЦЕПЕЙ ФТОРСОДЕРЖАЩЕГО ПОЛИЭТИЛЕНТЕРЕФТАЛАТА ПО ДАННЫМ ДИФФЕРЕНЦИАЛЬНОЙ СКАНИРУЮЩЕЙ КАЛОРИМЕТРИИ

Применение полиэтилентерефталата (ПЭТ) для производства материалов широкого профиля использования требует универсальных способов его стабилизации, что не достигается в настоящее время существующими органическими и минеральными модификаторами [Брукс Д., Джайлз Дж. Производство упаковки из ПЭТ: Пер. с англ. Под ред. О.Ю. Сабсая. СПб.: 2006. 368 с.]. Поли- и перфторированные соединения для этих целей представляют несомненный интерес, поскольку позволяют добиваться существенного улучшения ряда свойств (термо-, свето-, износостойкость, гидролитическая устойчивость) гетероцепных полимеров уже при малом их содержании (10-3 ÷ 5 % масс. [Кудашев С.В. Влияние полифторированных модификаторов на структуру и свойства гетероцепных полимеров: Автореф. канд. дис. Волгоград, 2011. 24 с.].

Цель работы – оценка подвижности макромолекулярных цепей ПЭТ-гранулята, модифицированного фторсодержащими уретанами (ФУ), методом дифференциальной сканирующей калориметрии (ДСК, калориметр Netzsch DSC 204 F1 Phoenix, Германия).

Так подвижность структурных единиц макромолекулярной цепи ПЭТ оценивается коэффициентами температурных переходов [1, 2]:

1) α-переход – связан с уменьшением подвижности структурных единиц макромолекул вследствие начала кристаллизации;