Abstract
The main results related to the mesophase formation in the different isotactic polypropylene (iPP) copolymers are reviewed in this chapter. It is shown that fast scanning calorimetry (FSC) is mandatory for analyzing the process at the lower comonomer contents. On the contrary, the cooling rates required for the relatively high contents fall in the typical range of conventional DSC experiments, so that the mesophase development can be much more easily investigated (although there is an obvious decrease of the degree of order). Additionally, diffraction experiments under real time conditions (by means of synchrotron radiation) are also examined, which are used for establishing the specific character of the phases implicated. The main conclusion is that the cooling rates necessary for obtaining the mesomorphic state decrease progressively with increasing counit content, although important differences are reported depending on the comonomer type. Thus, it is shown that the content and size of the counit are influencing in a different way the rate of mesophase development and the transition temperatures. FSC experiments for studying the corresponding crystallization and mesophase rates of formation under isothermal conditions on iPP and copolymers are also reviewed.
Keywords
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Keller A, Hikosaka M, Rastogi S, Toda A, Barham PJ, Goldbeckwood G (1994) An approach to the formation and growth of new phases with application to polymer crystallization - Effect of finite-size, metastability, and Ostwald rule of stages. J Mater Sci 29:2579–2604
Keller A, Cheng SZD (1998) The role of metastability in polymer phase transitions. Polymer 39:4461–4487
Cheng SZD, Zhu L, Li CY, Honigfort PS, Keller A (1999) Size effect of metastable states on semicrystalline polymer structures and morphologies. Thermochim Acta 332:105–113
Strobl G (2000) From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: a major route followed in polymer crystallization? Eur Phys J E 3:165–183
Strobl G (2006) Crystallization and melting of bulk polymers: new observations, conclusions and a thermodynamic scheme. Prog Polym Sci 31:398–442
Fernandez-Blazquez JP, Perez-Manzano J, Bello A, Perez E (2007) The two crystallization modes of mesophase forming polymers. Macromolecules 40:1775–1778
Noel C, Navard P (1991) Liquid-crystal polymers. Prog Polym Sci 16:55–110
Finkelmann H, Rehage G (1984) Liquid-crystal side-chain polymers. Adv Polym Sci 60–1:97–172
Bello A, Perena JM, Perez E, Benavente R (1994) Thermotropic liquid-crystal polyesters derived from 4,4'-biphenyldicarboxylic acid and oxyalkylene spacers. Macromol Symp 84:297–306
Martinez-Gomez A, Perez E, Bello A (2010) Polymesomorphism and orientation in liquid crystalline poly(triethylene glycol p, p'-bibenzoate). Colloid Polym Sci 288:859–867
Djezzar K, Penel L, Lefebvre JM, Seguela R, Germain Y (1998) Tensile drawing of ethylene/vinyl-alcohol copolymers. Part 1. Influence of draw temperature on the mechanical behaviour. Polymer 39:3945–3953
Penel L, Djezzar K, Lefebvre JM, Seguela R, Fontaine H (1998) Tensile drawing of ethylene vinyl alcohol copolymers: II. Investigation of the strain-induced mesomorphic structure. Polymer 39:4279–4287
Cerrada ML, Benavente R, Perez E, Perena JM (2000) The effect of orientation on the morphology and viscoelastic response of vinyl alcohol-ethylene copolymers. Macromol Chem Phys 201:1858–1868
Cerrada ML, Benavente R, Perez E, Perena JM (2001) The effect of tensile drawing on the structure and relaxation processes in vinyl alcohol-ethylene copolymers. Polymer 42:3127–3138
Cerrada ML, Fauth F, Fernandez-Blazquez JP, Perez E (2010) Structural changes induced by deformation in an ethylene-(vinyl alcohol) copolymer: simultaneous measurements of uniaxial stretching and in situ wide-angle X-ray scattering. Polym Int 59:1141–1147
Vittoria V, Guadagno L, Comotti A, Simonutti R, Auriemma F, De Rosa C (2000) Mesomorphic form of syndiotactic polypropylene. Macromolecules 33:6200–6204
Grasruck M, Strobl G (2003) Crystallization of s-polypropylene from the glassy state: indications for a multistage process. Macromolecules 36:86–91
Slichter WP, Mandell ER (1958) Molecular motion in polypropylene, isotactic and atactic. J Appl Phys 29:1438–1441
Miller RL (1960) On the existence of near-range order in isotactic polypropylenes. Polymer 1:135–143
Hosemann R, Wilke W (1968) Lattice imperfections in polyethylene. Makromol Chem 118:230–249
McAllister PB, Carter TJ, Hinde RM (1978) Structure of quenched form of polypropylene. J Polym Sci, Part B: Polym Phys 16:49–57
Grebowicz J, Lau SF, Wunderlich B (1984) The thermal properties of polypropylene. J Polym Sci Polym Symp 71:19–37
Corradini P, Derosa C, Guerra G, Petraccone V (1989) Comments on the possibility that the mesomorphic form of isotactic polypropylene is composed of small crystals of the beta-crystalline form. Polymer Comm 30:281–285
Lotz B, Kopp S, Dorset D (1994) An original crystal structure of polymers with ternary helices. Comptes Rendus De L Academie Des Sciences Serie Ii 319:187–192
Arranz-Andres J, Benavente R, Perez E, Cerrada ML (2003) Structure and mechanical behavior of the mesomorphic form in a propylene-b-poly(ethylene-co-propylene) copolymer and its comparison with other thermal treatments. Polym J 35:766–777
Auriemma F, De Rosa C, Corradini P (2005) Solid mesophases in semicrystalline polymers: structural analysis by diffraction techniques. Adv Polym Sci 181:1–74
Corradini P, Auriemma F, De Rosa C (2006) Crystals and crystallinity in polymeric materials. Acc Chem Res 39:314–323
Brückner S, Meille SV, Petraccone V, Pirozzi B (1991) Polymorphism in isotactic polypropylene. Prog Polym Sci 16:361–404
Bruckner S, Meille SV (1989) Non-parallel chains in crystalline gamma-isotactic polypropylene. Nature 340:455–457
Lotz B, Wittmann JC, Lovinger AJ (1996) Structure and morphology of poly(propylenes): a molecular analysis. Polymer 37:4979–4992
Hikosaka M, Sato N, Hasegawa M, Seto T (1973) Formation of oriented isotactic polypropylene gamma-form crystal through alpha-gamma-transition. Jpn J Appl Phys 12:1293
Varga J (1992) Supermolecular structure of isotactic polypropylene. J Mater Sci 27:2557–2579
Meille SV, Ferro DR, Bruckner S, Lovinger AJ, Padden FJ (1994) Structure of beta-isotactic polypropylene - a long-standing structural puzzle. Macromolecules 27:2615–2622
Dorset DL, McCourt MP, Kopp S, Schumacher M, Okihara T, Lotz B (1998) Isotactic polypropylene, beta-phase: a study in frustration. Polymer 39:6331–6337
Phillips PJ, Mezghani K (1996) Polypropylene, isotactic (polymorphism). In: Salamone JC (ed) The polymeric materials encyclopedia, vol 9. CRC Press, Boca Raton, FL, p 6637
Natta G, Corradini P (1960) Structure and properties of isotactic polypropylene. Il Nuovo Cimento Series 10 15:40–51
Turner-Jones A, Aizlewood JM, Beckett DR (1964) Crystalline forms of isotactic polypropylene. Makromol Chem 75:134–158
Cerrada ML, Polo-Corpa MJ, Benavente R, Perez E, Velilla T, Quijada R (2009) Formation of the new trigonal polymorph in iPP-1-hexene copolymers. Competition with the mesomorphic phase. Macromolecules 42:702–708
Krache R, Benavente R, Lopez-Majada JM, Perena JM, Cerrada ML, Perez E (2007) Competition between alpha, beta, and gamma polymorphs in beta-nucleated metallocenic isotactic polypropylene. Macromolecules 40:6871–6878
Vittoria V (1986) Investigation of the structure of isotactic polypropylene via transport properties. J Polym Sci, Part B: Polym Phys 24:451–455
Russo R, Vittoria V (1996) Determination of intrinsic birefringence of smectic phase in isotactic polypropylene. J Appl Polym Sci 60:955–961
K-h N, Odaka K (2009) Influence of structural organization on tensile properties in mesomorphic isotactic polypropylene. Polymer 50:4080–4088
Brucato V, Piccarolo S, La Carrubba V (2002) An experimental methodology to study polymer crystallization under processing conditions. The influence of high cooling rates. Chem Eng Sci 57:4129–4143
Perez E, Gomez-Elvira JM, Benavente R, Cerrada ML (2012) Tailoring the formation rate of the mesophase in random propylene-co-1-pentene copolymers. Macromolecules 45:6481–6490
Vittoria V (1986) Investigation of the structure of isotactic polypropylene via transport properties. J Polym Sci, Part B: Polym Phys 24:451–455
Okane WJ, Young RJ, Ryan AJ, Bras W, Derbyshire GE, Mant GR (1994) Simultaneous SAXS/WAXS and DSC analysis of the melting and recrystallization behavior of quenched polypropylene. Polymer 35:1352–1358
Zia Q, Androsch R, Radusch H-J, Piccarolo S (2006) Morphology, reorganization and stability of mesomorphic nanocrystals in isotactic polypropylene. Polymer 47:8163–8172
Mileva D, Androsch R, Zhuravlev E, Schick C, Wunderlich B (2011) Isotropization, perfection and reorganization of the mesophase of isotactic polypropylene. Thermochim Acta 522:100–109
Zhuravlev E, Schick C (2010) Fast scanning power compensated differential scanning nano-calorimeter: 1. The device. Thermochim Acta 505:1–13
Mathot V, Pyda M, Pijpers T, Vanden Poel G, van de Kerkhof E, van Herwaarden S et al (2011) The Flash DSC 1, a power compensation twin-type, chip-based fast scanning calorimeter (FSC): first findings on polymers. Thermochim Acta 522:36–45
Vanden Poel G, Istrate D, Magon A, Mathot V (2012) Performance and calibration of the Flash DSC 1, a new, MEMS-based fast scanning calorimeter. J Therm Anal Calorim 110:1533–1546
Bosq N, Guigo N, Zhuravlev E, Sbirrazzuoli N (2013) Nonisothermal crystallization of polytetrafluoroethylene in a wide range of cooling rates. J Phys Chem B 117:3407–3415
Mileva D, Androsch R, Zhuravlev E, Schick C (2009) Temperature of melting of the mesophase of isotactic polypropylene. Macromolecules 42:7275–7278
De Santis F, Adamovsky S, Titomanlio G, Schick C (2006) Scanning nanocalorimetry at high cooling rate of isotactic polypropylene. Macromolecules 39:2562–2567
De Santis F, Adamovsky S, Titomanlio G, Schick C (2007) Isothermal nanocalorimetry of isotactic polypropylene. Macromolecules 40:9026–9031
Androsch R, Di Lorenzo ML, Schick C, Wunderlich B (2010) Mesophases in polyethylene, polypropylene, and poly(1-butene). Polymer 51:4639–4662
Poon B, Rogunova M, Hiltner A, Baer E, Chum SP, Galeski A et al (2005) Structure and properties of homogeneous copolymers of propylene and 1-hexene. Macromolecules 38:1232–1243
Gahleitner M, Jaaskelainen P, Ratajski E, Paulik C, Reussner J, Wolfschwenger J et al (2005) Propylene-ethylene random copolymers: comonomer effects on crystallinity and application properties. J Appl Polym Sci 95:1073–1081
Lopez-Majada JM, Palza H, Guevara JL, Quijada R, Martinez MC, Benavente R et al (2006) Metallocene copolymers of propene and 1-hexene: the influence of the comonomer content and thermal history on the structure and mechanical properties. J Polym Sci, Part B: Polym Phys 44:1253–1267
Palza H, López-Majada JM, Quijada R, Pereña JM, Benavente R, Pérez E et al (2008) Comonomer length influence on the structure and mechanical response of metallocenic polypropylenic materials. Macromol Chem Phys 209:2259–2267
Arranz-Andres J, Pena B, Benavente R, Perez E, Cerrada ML (2007) Influence of isotacticity and molecular weight on the properties of metallocenic isotactic polypropylene. Eur Polym J 43:2357–2370
Polo-Corpa MJ, Benavente R, Velilla T, Quijada R, Perez E, Cerrada ML (2010) Development of the mesomorphic phase in isotactic propene/higher alpha-olefin copolymers at intermediate comonomer content and its effect on properties. Eur Polym J 46:1345–1354
Poon B, Rogunova M, Chum SP, Hiltner A, Baer E (2004) Classification of homogeneous copolymers of propylene and 1-octene based on comonomer content. J Polym Sci, Part B: Polym Phys 42:4357–4370
De Rosa C, Auriemma F, De Ballesteros OR, Resconi L, Carnurati I (2007) Tailoring the physical properties of isotactic polypropylene through incorporation of comonomers and the precise control of stereo and regioregularity by metallocene catalysts. Chem Mater 19:5122–5130
Mileva D, Androsch R, Cavallo D, Alfonso GC (2012) Structure formation of random isotactic copolymers of propylene and 1-hexene or 1-octene at rapid cooling. Eur Polym J 48:1082–1092
Spaleck W (2000) In: Scheirs J, Kaminski W (eds) Metallocene-based polyolefins: preparation, properties and technology. Wiley, New York, p 425
Pasquini N (2005) Polypropylene Handbook. Carl Hanser Verlag, Munich
Arranz-Andres J, Parrilla R, Cerrada ML, Perez E (2013) Mesophase formation in random propylene-co-1-octene copolymers. Macromolecules 46:8557–8568
Lotz B, Ruan J, Thierry A, Alfonso GC, Hiltner A, Baer E et al (2006) A structure of copolymers of propene and hexene isomorphous to isotactic poly(1-butene) form I. Macromolecules 39:5777–5781
De Rosa C, Dello Iacono S, Auriemma F, Ciaccia E, Resconi L (2006) Crystal structure of isotactic propylene-hexene copolymers: the trigonal form of isotactic polypropylene. Macromolecules 39:6098–6109
De Rosa C, Auriemma F, Corradini P, Tarallo O, Dello Iacono S, Ciaccia E et al (2006) Crystal structure of the trigonal form of isotactic polypropylene as an example of density-driven polymer structure. J Am Chem Soc 128:80–81
De Rosa C, Auriemma F, Talarico G, de Ballesteros OR (2007) Structure of isotactic propylene-pentene copolymers. Macromolecules 40:8531–8532
De Rosa C, de Ballesteros OR, Auriemma F, Di Caprio MR (2012) Crystal structure of the trigonal form of isotactic propylene-pentene copolymers: an example of the principle of entropy-density driven phase formation in polymers. Macromolecules 45:2749–2763
Stagnaro P, Costa G, Trefiletti V, Canetti M, Forlini F, Alfonso GC (2006) Thermal behavior, structure and morphology of propene/higher 1-olefin copolymers. Macromol Chem Phys 207:2128–2141
Stagnaro P, Boragno L, Canetti M, Forlini F, Azzurri F, Alfonso GC (2009) Crystallization and morphology of the trigonal form in random propene/1-pentene copolymers. Polymer 50:5242–5249
Perez E, Cerrada ML, Benavente R, Gomez-Elvira JM (2011) Enhancing the formation of the new trigonal polymorph in isotactic propene-1-pentene copolymers: determination of the X-ray crystallinity. Macromol Res 19:1179–1185
Garcia-Penas A, Gomez-Elvira JM, Perez E, Cerrada ML (2013) Isotactic poly(propylene-co-1-pentene-co-1-hexene) terpolymers: synthesis, molecular characterization, and evidence of the trigonal polymorph. J Polym Sci, Part A: Polym Chem 51:3251–3259
Boragno L, Stagnaro P, Forlini F, Azzurri F, Alfonso GC (2013) The trigonal form of i-PP in random C3/C5/C6 terpolymers. Polymer 54:1656–1662
Choi CH, White JL (2000) Correlation and modeling of the occurrence of different crystalline forms of isotactic polypropylene as a function of cooling rate and uniaxial stress in thin and thick parts. Polym Eng Sci 40:645–655
Cavallo D, Azzurri F, Floris R, Alfonso GC, Balzano L, Peters GW (2010) Continuous cooling curves diagrams of propene/ethylene random copolymers. The role of ethylene counits in mesophase development. Macromolecules 43:2890–2896
Cavallo D, Portale G, Balzano L, Azzurri F, Bras W, Peters GW et al (2010) Real-time WAXD detection of mesophase development during quenching of propene/ethylene copolymers. Macromolecules 43:10208–10212
Perez E, Zucchi D, Sacchi MC, Forlini F, Bello A (1999) Obtaining the gamma phase in isotactic polypropylene: effect of catalyst system and crystallization conditions. Polymer 40:675–681
De Rosa C, Auriemma F, Di Girolamo R, Romano L, De Luca MR (2010) A new mesophase of isotactic polypropylene in copolymers of propylene with long branched comonomers. Macromolecules 43:8559–8569
Mileva D, Androsch R (2012) Effect of co-unit type in random propylene copolymers on the kinetics of mesophase formation and crystallization. Colloid Polym Sci 290:465–471
Mileva D, Androsch R, Radusch H-J (2008) Effect of cooling rate on melt-crystallization of random propylene-ethylene and propylene-1-butene copolymers. Polym Bull 61:643–654
Mileva D, Androsch R, Zhuravlev E, Schick C (2009) Critical rate of cooling for suppression of crystallization in random copolymers of propylene with ethylene and 1-butene. Thermochim Acta 492:67–72
Mileva D, Zia Q, Androsch R, Radusch H-J, Piccarolo S (2009) Mesophase formation in poly(propylene-ran-1-butene) by rapid cooling. Polymer 50:5482–5489
Mileva D, Androsch R, Funari SS, Wunderlich B (2010) X-ray study of crystallization of random copolymers of propylene and 1-butene via a mesophase. Polymer 51:5212–5220
Mileva D, Androsch R, Zhuravlev E, Schick C, Wunderlich B (2011) Formation and reorganization of the mesophase of random copolymers of propylene and 1-butene. Polymer 52:1107–1115
Mileva D, Cavallo D, Gardella L, Alfonso GC, Portale G, Balzano L et al (2011) In situ X-ray analysis of mesophase formation in random copolymers of propylene and 1-butene. Polym Bull 67:497–510
Cavallo D, Gardella L, Alfonso GC, Mileva D, Androsch R (2012) Effect of comonomer partitioning on the kinetics of mesophase formation in random copolymers of propene and higher alpha-olefins. Polymer 53:4429–4437
Jeon K, Palza H, Quijada R, Alamo RG (2009) Effect of comonomer type on the crystallization kinetics and crystalline structure of random isotactic propylene 1-alkene copolymers. Polymer 50:832–844
Arranz-Andres J, Suarez I, Benavente R, Perez E (2011) Characterization and properties of ethylene-propylene copolymers synthesized with homogeneous and supported metallocene catalyst in the whole range of compositions. Macromol Res 19:351–363
Ruiz-Orta C, Alamo RG (2012) Morphological and kinetic partitioning of comonomer in random propylene 1-butene copolymers. Polymer 53:810–822
Cavallo D, Zhang L, Portale G, Alfonso GC, Janani H, Alamo RG (2014) Unusual crystallization behavior of isotactic polypropylene and propene/1-alkene copolymers at large undercoolings. Polymer 55:3234–3241
Androsch R, Monami A, Kucera J (2014) Effect of an alpha-phase nucleating agent on the crystallization kinetics of a propylene/ethylene random copolymer at largely different supercooling. J Cryst Growth 408:91–96
Acknowledgements
The financial support of MICINN and MINECO (Projects MAT2010-19883 and MAT2013-47972-C2-1-P, respectively) is gratefully acknowledged. Mr. A. García-Peñas is also grateful to MICINN for his FPI predoctoral grant. The synchrotron experiments were performed in the CRG beamline BM16 of the ESRF and in beamline BL11-NCD at ALBA Synchrotron Light Facility with the collaboration of BM16-ESRF and ALBA staff, respectively. The support from MICINN and MINECO for performing these measurements is also acknowledged.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer International Publishing Switzerland
About this chapter
Cite this chapter
Pérez, E., García-Peñas, A., Arranz-Andrés, J., Gómez-Elvira, J.M., Cerrada, M.L. (2016). Mesophase Formation in Isotactic Polypropylene Copolymers. In: Schick, C., Mathot, V. (eds) Fast Scanning Calorimetry. Springer, Cham. https://doi.org/10.1007/978-3-319-31329-0_16
Download citation
DOI: https://doi.org/10.1007/978-3-319-31329-0_16
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-31327-6
Online ISBN: 978-3-319-31329-0
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)