İZOTAKTİK POLİPROPİLEN LİFLERİNİN YAPISAL KARAKTERİZASYONUNDA İNFRA-RED SPEKTROSKOPİ YÖNTEMİNİN KULLANIMI

İzotaktik polipropilen lifleri eriyikten çekme yöntemi ile 2500 m/dak ile 4250 m/dak arasındaki sarma hızlarında üretilmiştir. Üretim parametrelerinin kristalinite ve taktisite gibi yapısal parametrelerine etkisi infra-red ve yoğunluk ölçümleri ile araştırılmıştır. Numuneler ayrıca eriyik akış indisi ölçümleri ile karakterize edilmiştir. Infra-red eğri analizi hassas pik parametreleri ile sonuçlanmış olup elde edilen pik parametreleride taktisite ve kristalinite oranlarının hesaplanmasında kullanılmıştır. İzotaktisite ve ataktisite oranları 998, 841 ve 973 cm-1 IR piklerinin pik yükseklik oranlarının kullanımı ile elde edilmiştir (A998/A973, A841/A973). A841/A973 oranı ile elde edilen izotaktisite oranları A998/A973 oranından elde edilen değerlerden genel olarak daha fazla bulunmuştur. İzotaktisite oranları 3000 m/dak üretim hızından sonra artma eğilimi ataktisite oranları ise azalma eğilimi göstermektedir. Yoğunluk ve infra-red yöntemlerinden elde edilen kristalinite oranları karşılaştırılmıştır. Genel olarak, infra-red spektroskopi yönteminden elde edilen kristalinite oranlarıi yoğunluk esaslı kristalinite oranlarından daha fazla bulunmuştur

Anahtar Kelimeler:

İsotaktik polipropilen lifi, İnfra-red spektroskopi, Yoğunluk, Kristalinite, Taktisite

THE USE OF INFRARED-SPECTROSCOPY TECHNIQUE FOR THE STRUCTURAL CHARACTERIZATION OF ISOTACTIC POLYPROPYLENE FIBRES

Isotactic polypropylene (iPP) fibres were produced by melt spinning method with take-up speeds between 2500 m/min and 4250 m/min. The effect of production parameters on structural parameters such as crystallinity and tacticity is investigated using infra-red spectroscopy together with density measurements. Samples were also characterized using Melt Flow Index (MFI) measurements. Curve fitting of IR spectra yielded accurate peak parameters which are in turn used in the evaluation of tacticity and fractional crystallinity values. Evaluation of isotacticity and atacticity fractions were performed using the absorbance ratios of the IR bands at 998, 841 and 973 cm-1 (A998/A973, A841/A973). Isotacticity fractions evaluated from A841/A973 are generally found to be higher than that evaluated from the ratio of A998/A973. Isotacticity fractions show an increasing trend after about the extrusion speed of 3000 m/min whereas atacticity fractions decrease accordingly. Crystallinity fractions obtained from density and infra-red spectroscopy methods are compared. In general, crystallinity fractions obtained from IR-spectroscopy are found to be slightly higher than the density based crystallinity fractions

Keywords:

Isotactic polypropylene fibre, Infra-red spectroscopy, Density, Crystallinity, Tacticity,

PDF

___

1. Sheehan W. C. and Cole T. B., 1964,″Production of Super-Tenacity Polypropylene Filaments″, J. Appl. Polymer. Sci., 8, pp.2359-2388.
2. Fung P. Y. F., Orlando E., and Carr S. H., 1973, ″Development of Stress-Crystallized Morphology During Melt-Spinning of Polypropylene Fibers″, Polym. Eng. Sci., 13(4), pp295-299.
3. Kitao T., Ohya S., Furukawa J., and Yamashita S., 1973, ″Orientation of Polymer Molecules during Melt Spinning. 11. Orientation of Crystals in As-Spun Polyolefin Fibers″, J. Polym. Sci. Poly. Phys, 11, pp1091-1109.
4. Spruiell J. E. and White J. L., 1975, ″Structure Development During Polymer Processing: Studies of the Melt Spinning of Polyethylene and Polypropylene Fibers″ Polym. Eng. Sci., 15(9), pp660-667.
5. Nadella H. P., Henson M. M., Spruiell J. E., and White J. L., 1977, ″Melt Spinning of Isotactic Polypropylene: Structure Development and Relationship to Mechanical Properties″, J. Appl. Polym. Sci., 21, pp3003-3022.
6. Minoshima W., White J. L., and Spruiell J. E., 1980, ″ Experimental Investigations of the Influence of Molecular Weight Distribution on Melt Spinning and Extrudate Swell Characteristics of Polypropylene ″, J. Appl. Polym. Sci., 25, pp287-306.
7. Shimizu J., Watanabe A., and Toriumi K., 1974, ″The High Speed Spinning by Using an air jet nozzle″, Sen-i Gakkaishi, 30(2), ppT53-T60.
8. Shimizu J., Torid K., and Tamai K., 1977, ″High Speed Melt Spinning of Isotactic Polypropylene″, Sen-i Gakkaishi, 33(6), ppT208-T260.
9. Shimizu J., Tonumi K., and Imai Y., 1979, ″High Speed Melt Spinning of Isotactic Polypropylene″, Sen-i Gakkaishi, 35(10), ppT405-T412.
10. Shimizu J., Okui N., and Imai Y., 1980,″High Speed Melt Spinning of Isotactic Polypropylene″, Sen-i Gukkuishi, 36(4), ppT166-T174.
11. Lu F. M. and Spruiell J. E., 1987, ″The Influence of Resin Characteristics on the High Speed Melt Spinning of Isotactic Polypropylene. I. Effect of Molecular Weight and Its Distribution on Structure and Mechanical Properties of As-Spun Filaments ″, J.Appl. Polym. Sci., 34(4), pp1521- 1539.
12. Lu F. M. and Spruiell J. E., 1987,″The Influence of Resin Characteristics on the High Speed Melt Spinning of Isotactic Polypropylene. II. On-Line Studies of Diameter, Birefringence, and Temperature Profiles″, J.Appl. Polym. Sci., 34(4), pp1541-1556.
13. Lu F. M. and Spruiell J. E., 1993, ″The Role of Crystallization Kinetics in the Development of the Structure and Properties of Polypropylene Filaments″, J. Appl. Polym. Sci., 49, pp623-631.
14. Misra S., Lu F. M., Spruiell J. E., and Richeson G. C., 1995, ″Influence of Molecular Weight Distribution on the Structure and Properties of Melt-Spun Polypropylene Filaments″, J.Appl.Polym.Sci., 56(13), pp1761-1779
15. Spruiell J. E., Lu F.-M., Ding Z., and Richeson G., 1996, ″The Influence of Isotacticity, Ethylene Comonomer Content, and Nucleating Agent Additions on the Structure and Properties of Melt- Spun lsotactic Polypropylene Filaments″, J.Appl.Polym.Sci. 62(11), pp1965-1975.
16. Wang I.C., Dobb M.G., Tomka J.G., 1995,"Polypropylene Fibres: An Industrially Feasible Pathway to High Tenacity", J.Text.Inst., 86(3), pp383–392.
17. Wang I.C., Dobb M.G., Tomka J.G., 1996," Polypropylene Fibres: Exploration of Conditions Resulting in High Tenacity", J.Text.Inst., 87(1), pp1-12.
18. Suzuki A., Narusue S., 2004, ″Isotactic Polypropylene Micro.ber Prepared by Carbon Dioxide Laser-Heating″, J.App.Poly.Sci., 92, pp1534–1539.
19. Suzuki A., Narusue S., 2006, ″ Isotactic Polypropylene Micro.ber Prepared by Continuous Laser-Thinning Method″, J.App.Poly.Sci., 99, pp27–31.
20. Natta G. and Corradini P., 1960,"Structure and Properties of Isotactic Polypropylene", Nuovo Cimento, 15, pp40-51.
21. G. Natta, 1955, ″ Une Nouvelle Classe de Polymeres d’α-Olefines ayant une Régularité de Structure Exceptionnelle”, J.Poly.Sci., 16, pp143-154.
22. Natta G., Pino P., Corradini P., Danusso F., Mantica E., Mazzanti G., Moraglio G., 1955, ″Crystalline High Polymers of α-olefins″, J. Am. Chem. Soc., 77 (6), pp1708–1710.
23. http://www.piketech.com/technical/crystal-selection-ATR.html, Accessed on 19th July 2010
24. Hindeleh A.M., Johnson D.J., and Montague P.E., 1983, ‘Fibre Diffraction Methods’, ACS Symp. No. 141 (Eds. A.D. French and K.H. Gardner), American Chemical Society, Washington DC, p. 149-181.
25. Tadokoro H., Kobayashi M., Ukita M., Yasufuku K., Murahashi S., Torii T., 1965,"Normal Vibrations of the Polymer Molecules of Helical Conformation: Isotactic Polypropylene and Its Deuteroderivatives", J.Chem. Phys., 4, pp1432–1449.
26. Ozzetti R.A., Filho A.P.D.O., Schuchardt U., Dalmo M., 2002, ″Determination of Tacticity in Polypropylene by FTIR with Multivariate Calibration″, J.App.Poly.Sci., 85, pp734–745
27. Burfield D.R. and Loi P.S. T., 1988, ″The Use of Infrared Spectroscopy for Determination of Polypropylene Stereoregularity″, J.App.Poly.Sci., 36, pp279-293
28. Karacan I., Taraiya A.K., Bower D.I., Ward I.M., 1993, ″Characterization of orientation of one- way and two-way drawn isotactic polypropylene films″, Polymer, 34(13). pp2691-2701.
29. Painter P.C., Watzek M. and Koenig J.L., 1977, ″ Fourier transform infra-red study of polypropylene″, Polymer, Volume 18, 18(11), pp1169-1172.
30. Karacan I., 1999, ″Structure-Property relationships in polypropylene fibres″, Polypropylene: A-Z guide, Ed. J. Karger-Kocsis, Kluwer Academic Publishers, pp 783-789.
31. Karacan I. and Wang I-C., 1997, ″Structural studies of isotactic polypropylene fibres″, Tekstil ve Mühendis, 11(55-56), pp3-16.
32. Zerbi G., Gussoni M. and Ciampelli F., 1967, ″Structure of liquid isotactic polypropylene from its vibrational spectrum″, Spectrochimica Acta. Part A: Mol.Spec., 23(2). pp301-311.
33. Kissin Yu.V. and Rashina L.A., 1976,″Regularity bands in the IR spectra of C3H6-C3D6 copolymers″, Eur.Poly.J., 12, p p757-759.
34. Zerbi G., Ciampelli F., and Zamboni V., 1963, ″Classification of Crystallinity Bands in the Infrared Spectra of Polymers″, J.Poly.Sci. Part C: Polym.Symp., 7(1), pp141-151.
35. T. Miyamoto, H. Inagaki, 1969, ″Structural and Steric Isomerism of Polypropylenes″, J. Polym. Sci., A-2, 7, pp963-981.
36. Kobayashi M., Akita K., and Tadokoro H., 1968, ″ Infrared Spectra and Regular Sequence Lengths in lsotactic Polymer Chains″, Die Makromolekulare Chemie, 118, pp324-342.
37. Zhu, D. Yan, H. Yao, P. Zhu, 2000, ″In situ FTIR spectroscopic study of the regularity band and partial-order melts of isotactic poly(propylene)″, Macromol.Rapid.Comm., 21.pp354-357.
38. Minoshima, W., White J.L., and Spruiell, J.E., 1980, "Experimental Investigation of the Influence of Molecular Weight Distribution on the Rheological Properties of Polypropylene Melts", Polym. Eng.Sci., 20(17), pp1166-1176.
39. Jasse B., Koenig J.L., 1979,″Orientational Measurements in Polymers Using Vibrational Spectroscopy″, J.Macromol.Sci.-Rev.Macromol.Chem., C17(1), pp61-135.