Abstract
A film iodinated at solution state before casting (BIBC film) and a film iodinated after casting (BIAC film) were prepared by casting an aqueous solution of poly(vinyl alcohol) (PVA) including I2/KI and boric acid, and by successively soaking the PVA film in aqueous solutions of boric acid and I2/KI, respectively. The boric acid-induced and I2/KI-induced weight gains relative to the PVA were 3, 5, 7, and 10%, and 3, 5, 10, and 20%, respectively. The effects of boric acid and iodine on the crystallinity and drawability of the films were investigated. Although the crystalline structure of the BIAC films was not affected by boric acid, the boric acids in the PVA solution containing I2/KI may have formed intra-molecular cross-links on the PVA chain to accelerate the formation of the PVA–iodine complex evenly, and subsequently interrupt the PVA crystallization through the BIBC film formation to render the resultant film slightly crystalline or practically amorphous. This occurred even at a much lower I2/KI-induced weight gain (20%) than the minimum weight gain (125%) at which the iodinated at solution state before casting film without boric acid indicated a practically amorphous state. The maximum draw ratio of the films generally decreased with increasing boric acid content, which was mainly attributed to the increase of the extended segments of the PVA chains in the amorphous region due to the cross-links formed with the boric acids. The maximum draw ratios of the BIBC films tended to decrease more severely than those of the BIAC films.
Similar content being viewed by others
References
Haisa M, Itami H (1957) X-ray diffraction study of the polyvinyl alcohol iodine system. J Phys Chem 61:817–818
Imai K, Matsumoto M (1961) The effect of stereoregularity on the poly(vinyl alcohol)–iodine reaction. J Polym Sci 55:335–342
Heyde ME, Rimai L, Killponen RG, Gill D (1972) Resonance-enhanced Raman spectra of iodine complexes with amylose and polyvinyl alcohol, and of some iodine-containing trihalides. J Am Chem Soc 94:5222–5227
Inagaki F, Garada I, Shimanouchi T, Tasumi M (1972) The resonance raman spectrum of the poly(vinyl alcohol)–iodine complex. Bull Chem Soc Jpn 45:3384–3388
Hayashi S, Kobayashi M, Shirai H, Hojo N (1979) Temperature effect of color complex of poly(vinyl alcohol) with iodine–iodine. J Polym Sci Polym Lett Ed 17:91–93
Teitelbaum RC, Ruby SL, Marks TJ (1980) A resonance raman/iodine mossbauer investigation of the starch–iodine structure. Aqueous solution and iodine vapor preparations. J Am Chem Soc 102:3322–3328
Hayashi S, Hirai Y, Hojo N (1982) Blue complex formation of poly(vinyl acetate) with iodine–iodide. J Polym Sci Polym Lett Ed 20:69–73
Choi YS, Oishi Y, Miyasaka K (1991) X-ray study on the structure of the poly(vinyl alcohol)–iodine complex. Polym J 23:977–981
Pricard JG, Akntolar DA (1972) Complexation of polyvinyl alcohol with iodine: analytical precision and mechanism. Talanta 19:877–888
Hass HC (1973) In: Finch CA (ed) Polyvinyl alcohol, chap 19. Willey, New York
Zwick MM (1965) Poly(vinyl alcohol)–iodine complexes. J Appl Polym Sci 9:2393–2424
Zwick MM (1966) The blue complexes of iodine with poly(vinyl alcohol) and amylase. J Polym Sci A 4:1642–1644
Shibayama M, Sato M, Kimura Y, Fujiwara H, Nomura S (1988) 11B n.m.r. study on the reaction of poly(vinyl alcohol) with boric acid. Polymer 29:336–340
Nielson LE (1962) Mechanical properties of polymers. Reinhold, New York, p 168
Sakurada I (1985) Polyvinyl alcohol fibers. Marcel Dekker, New York and Basel, p 85
Finch CA (1973) Polyvinyl alcohol—properties and applications. John Wiley & Sons, London, p 217
Toyoshima K (1968) Properties and applications of polyvinyl alcohol. (C. A. Finch Ed.) Monograph No. 30. Society of Chemical Industry, London, p 154
Yin Y, Li J, Liu Y, Li Z (2005) Starch crosslinked with poly(vinyl alcohol) by boric acid. J Appl Polym Sci 96:394–1397
Yokota T, Kimura Y (1984) A peculiar temperature-dependent behavior of iodine species at the formation of chromophore between iodine and aqueous poly(vinyl alcohol). Markromol Chem 185:749–755
Yokota T, Kimura Y (1985) Iodine–poly(vinyl alcohol) interactions 2, anomalous slow quenching of the chromophore after extraction of tree iodine with carbon tetrachloride. Markromol Chem 186:549–557
Yokota T, Kimura Y (1986) Iodine–poly(vinyl alcohol) interactions 3, treatment of the blue-colored solution with anion exchange resin to separate the cage species of iodine. Markromol Chem Rapid Commun 7:249–253
Yokota T, Kimura Y (1989) Iodine–poly(vinyl alcohol) interactions 4, stoichiometry of iodine/iodide in the polyiodide ion bound in the cage of poly(vinyl alcohol). Markromol Chem Rapid Commun 190:939–950
Kojima Y, Furuhata K, Miyasaka K (1985) Sorption and permeation of iodine in water-swollen poly(vinyl alcohol) membranes and iodine complex formation. J Appl Polym Sci 30:1617–1628
Hirai T, Okazaki A, Hayashi S (1986) Effect of sequence distribution of poly(vinyl alcohol–vinyl acetate) on the coloring reaction with iodine. J Appl Polym Sci 32:3919–3928
Bunn CW (1948) Crystal structure of polyvinyl alcohol. Nature 161:929–930
Rundle RE, Foster JF, Baldwin RR (1944) On the nature of the starch–iodine complex. J Am Chem Soc 66:2116–2120
Finch CA (1973) Polyvinyl alcohol—properties and applications. John Wiley & Sons, London, p 41
Sakurada I (1985) Polyvinyl alcohol fibers. Marcel Dekker, New York and Basel, p 146
Choi YS, Miyasaka K (1993) Structure of poly(vinyl alcohol)–iodine complex formed in the amorphous phase of poly(vinyl alcohol) films. J Appl Polym Sci 48:313–317
Shibayamaa M, Hiroyukia Y, Hidenobua K, Hiroshia F, Shunjia N (1988) Sol–gel transition of poly(vinyl alcohol)–borate complex. Polymer 29:2066–2071
Noguchi H, Jodai H, Yamaura K, Matsuzawa S (1998) Formation of poly(vinyl alcohol)–iodine complex in aqueous solution: a SEM study of the freeze-dried substances. Polym Int 47:428–432
Choi YS, Oishi Y, Miyasaka K (1990) Change of poly(vinyl alcohol) crystal lattice by iodine sorption. Polym J 22:601–608
Oishi Y, Yamamoto H, Miyasaka K (1987) Structure of poly(vinyl alcohol)–iodine complex in water swollen film. Polym J 19:1261–1268
Billmeyer FW Jr (1964) Textbook of polymer science. Interscience, New York, p 225
Shin EJ, Lee YH, Choi SC (2004) Study on the structure and processibility of the iodinated poly(vinyl alcohol). I. Thermal analyses of iodinated poly(vinyl alcohol) films. J Appl Polym Sci 91:2407–2415
Shin EJ, Lee YH, Choi SC (2005) Structure and processability of iodinated poly(vinyl alcohol). II. Drawability of iodinated films. J Appl Polym Sci 95:1209–1214
Shin EJ, Lee YH, Choi SC (2006) Structure and processability of iodinated poly(vinyl alcohol) (III)-structure of films iodinated in solution before casting. J Appl Polym Sci 101:3497–3502
Shin EJ, Lee YH, Choi SC (2008) Structure and processability of iodinated poly(vinyl alcohol). IV. Drawability of the films iodinated at solution before casting. J Appl Polym Sci 108:34–38
Kim WS, Lee KB, Matsumoto K (1989) A study on the drawing and rupture of uniaxial stretched polyvinyl alcohol film in water. J Korean Soc Cloth Text 13:427–436
Lyoo WS, Kim SS, Ghim HD, Kim JP, Kwon IC, Lee CJ (2002) Preparation and characterization of iodinated poly(vinyl alcohol). Micrifibril Macromol Symp 180:125–131
Kim SS, Woo HL, Lyoo WS (2004) A study on the preparation of poly(vinyl alcohol) polarizing film. J Korean Soc Dye Finish 16:19–25
Song DH, Yoo HY, Lee JJ, Kim JP (2006) Polarizing films based on oriented poly(vinyl alcohol)–dichroic dyes. Mol Cryst Liq Cryst 445:65–70
Yoo HY (2004) Study on manufacture and characteristics of highly durable PVA polarizing film with dichroic azo dyes. Master thesis, Seoul University
Miyazaka K (1993) PVA–iodine complexes—formation, structure, and properties. Adv Polym Sci 108:91–129
Wang HH, Shyr TW, Hu MS (1999) The elastic property of polyvinyl alcohol gel with boric acid as a crosslinking agent. J Appl Polym Sci 74:3046–3052
Takamiya H, Tanahashi Y, Matsuyama T, Tanigami T, Yamaura K, Matsuzawa S (1993) On the poly(vinyl alcohol)–iodine complexes. J Appl Polym Sci 50:1807–1813
Ohishi K, Itadani T, Hayashi T, Nakai T, Horii F (2010) Role of boric acid in the formation of poly(vinyl alcohol)–iodine complexes in undrawn films. Polymer 51:687–693
Okada N, Sakurada I (1958) X-ray studies on the reaction between polyvinyl alcohol and boric acid. Kobushi Kagaku 15:491–496
Acknowledgment
This paper was supported by Dong-A University Research Fund in 2007 (2007-001-02-045).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Woo, J.Y., Shin, E.J. & Lee, Y.H. Effect of boric acid treatment on the crystallinity and drawability of poly(vinyl alcohol)–iodine complex films. Polym. Bull. 65, 169–180 (2010). https://doi.org/10.1007/s00289-010-0279-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-010-0279-9