Abstract
The nucleation and crystallization behavior of isotactic polypropylene (iPP) induced by zinc tetrahydrophthalate (NA) was investigated by using differential scanning calorimetry, wide-angle X-ray diffraction and polarized optical microscopy. The results show that NA is a highly effective β-nucleating agent, which can significantly increase the relative content of β-crystal (Kβ) for iPP. When the NA mass fraction is 0.10%, the Kβ value reaches a maximum of 0.972. The nonisothermal crystallization process of iPP and iPP/NA blends can be described by Jeziorny equation. The reason for NA to accelerate the crystallization of iPP is to reduce the nucleation barrier and increase the nucleation density and rate of iPP, instead of accelerating the crystal growth rate. The ordered structures of iPP inhibit β-crystallization induced by NA. Meanwhile, the introduction of NA also reduces the α-nucleating activity of the ordered structures. The impact strength and elongation at break of the iPP significantly increased with the addition of NA, while there was no loss in the tensile strength and flexural modulus.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
PaddenJr FJ, Keith HD (1959) Spherulitic crystallization in polypropylene. J Appl Phys 30:1479–1484
Turner-Jones A, Cobbold AJ (1968) The β crystalline form of isotactic polypropylene. J Polym Sci Part C Polym Lett 6:539–546
Kardos JL, Christiansen AW, Baer E (1966) Structure of pressure-crystallized polypropylene. J Polym Sci Part B Polym Phys 4:777–788
Piccarolo S, Saiu M, Brucato V, Titomanlio G (1992) Crystallization of polymer melts under fast cooling. II. High-purity iPP J Appl Polym Sci 46:625–634
Lotz B, Wittmann JC, Lovinger AJ (1996) Structure and morphology of poly(propylenes): a molecular analysis. Polymer 37:4979–4992
Varga J (2002) β-modification of isotactic polypropylene: preparation, structure, processing, properties, and application. J Macromol Sci Part B 41:1121–1171
Lovinger AJ, Chua JO, Gryte CC (1977) Studies on the α and β forms of isotactic polypropylene by crystallization in a temperature gradient. J Polym Sci Part B Polym Phys 15:641–656
Dragaun H, Hubeny H, Muschik H (1977) Shear-induced β-form crystallization in isotactic polypropylene. J Polym Sci Part B Polym Phys 15:1779–1789
Ding Q, Zhang Z, Wang C, Jiang J, Li G, Mai K (2014) Non-isothermal crystallization kinetics and morphology of wollastonite-filled β-isotactic polypropylene composites. J Therm Anal Calorim 115:675–688
Zhang YF, Xin Z (2007) Isothermal crystallization behaviors of isotactic polypropylene nucleated with α/β compounding nucleating agents. J Polym Sci Part B Polym Phys 45:590–596
Su ZQ, Dong M, Guo ZX, Yu J (2007) Study of polystyrene and acrylonitrile-styrene copolymer as special β-nucleating agents to induce the crystallization of isotactic polypropylene. Macromolecules 40:4217–4224
Yang R, Ding L, Chen W, Chen L, Zhang X, Li J (2017) Chain folding in main-chain liquid crystalline polyester with strong π–π interaction: an efficient β-nucleating agent for isotactic polypropylene. Macromolecules 50:1610–1617
Liu JR, Li C, Hu FM (2018) Effect of polystyrenes with different architectures on the β-nucleating efficiency and toughening of isotactic polypropylene. Polym Int 67:506–514
Shi GY, Zhang JY (1981) Study on β crystal polypropylene. Chin Sci Bull 12:731–733
Varga J, Mudra I, Ehrenstein G (1999) Crystallization and melting of β-nucleated isotactic polypropylene. J Therm Anal Calorim 56:1047–1057
Dou Q (2008) Effect of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator and crystallization temperature on the production of β crystal form in isotactic polypropylene. J Appl Polym Sci 107:958–965
Kang J, Peng H, Wang B, Chen Z, Li J, Chen J, Cao Y, Li H, Yang F, Xiang M (2014) Comparative study on the crystallization behavior of β-isotactic polypropylene nucleated with different β-nucleation agents—Effects of thermal conditions. J Appl Polym Sci 131:40115
Tjong SC, Shen JS, Li RK (1996) Morphological behaviour and instrumented dart impact properties of β-crystalline-phase polypropylene. Polymer 37:2309–2316
Varga J, Mudra I, Ehrenstein GW (1999) Highly active thermally stable β-nucleating agents for isotactic polypropylene. J Appl Polym Sci 74:2357–2368
Dou Q (2007) Effect of metallic salts of pimelic acid and crystallization temperatures on the formation of β crystalline form in isotactic poly (propylene). J Macromol Sci Part B Phys 46:1063–1080
Ren X, Zhang Y (2019) Effects of different metal salts of aliphatic dicarboxylic acids on the formation of β-crystalline form in isotactic polypropylene. J Therm Anal Calorim 137:563–573
Zhao S, Gong H, Yu X, Xin Z, Sun S, Zhou S, Shi Y (2016) A highly active and selective β-nucleating agent for isotactic polypropylene and crystallization behavior of β-nucleated isotactic polypropylene under rapid cooling. J Appl Polym Sci 133:43767
Zhao S, Liu K, Zhou S, Shi Y, Xin Z (2017) A novel self-dispersed β nucleating agent for isotactic polypropylene and its unique nucleation behavior and mechanism. Polymer 132:69–78
Zhao S, Qin W, Xin Z, Zhou S, Gong H, Ni Y, Zhang K (2018) In situ generation of a self-dispersed β-nucleating agent with increased nucleation efficiency in isotactic polypropylene. Polymer 151:84–91
Qin W, Xin Z, Pan C, Sun S, Jiang X, Zhao S (2019) In situ formation of zinc phthalate as a highly dispersed β-nucleating agent for mechanically strengthened isotactic polypropylene. Chem Eng J 358:1243–1252
Ren X, Zhang Y, He J, Li Y (2019) Nucleation effect of adipic acid metal salts in isotactic polypropylene. J Therm Anal Calorim 135:3321–3328
Beck HN (1967) Heterogeneous nucleating agents for polypropylene crystallization. J Appl Polym Sci 11:673–685
Strobl GR (2007) The Physics of polymers: concept for understanding their structure and behavior. Springer, Berlin
Liu M, Guo B, Du M, Chen F, Jia D (2009) Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene. Polymer 50:3022–3030
Jones AT, Aizlewood JM, Beckett DR (1964) Crystalline forms of isotactic polypropylene. Die Makromol Chem 75:134–158
Jeziorny A (1978) Parameters characterizing the kinetics of the non-isothermal crystallization of poly (ethylene terephthalate) determined by DSC. Polymer 19:1142–1144
Kissinger HE (1956) Variation of peak temperature with heating rate in differential thermal analysis. J Res Natl Bur Stand 57:217–221
Kang J, Weng G, Chen Z, Chen J, Cao Y, Yang F, Xiang M (2014) New understanding in the influence of melt structure and β-nucleating agents on the polymorphic behavior of isotactic polypropylene. RSC Adv 4:29514–29526
Kang J, Chen Z, Zhou T, Yang F, Chen J, Cao Y, Xiang M (2014) Dynamic crystallization and melting behavior of β-nucleated isotactic polypropylene with different melt structures. J Polym Res 21:384
Kang J, Chen Z, Yang F, Chen J, Cao Y, Weng G, Xiang M (2015) Understanding the effects of nucleating agent concentration on the polymorphic behavior of β-nucleated isotactic polypropylene with different melt structures. Colloid Polym Sci 293:2061–2073
Kang J, Weng G, Chen J, Yang F, Cao Y, Xiang M (2015) Influences of pre-ordered melt structures on the crystallization behavior and polymorphic composition of β-nucleated isotactic polypropylene with different stereo-defect distribution. J Appl Polym Sci 132:42632
Zhang Q, Peng H, Kang J, Cao Y, Xiang M (2017) Effects of melt structure on non-isothermal crystallization behavior of isotactic polypropylene nucleated with α/β compounded nucleating agents. Polym Eng Sci 57:989–997
Fillon B, Lotz B, Thierry A, Wittmann JC (1993) Self-nucleation and enhanced nucleation of polymers. Definition of a convenient calorimetric “efficiency scale” and evaluation of nucleating additives in isotactic polypropylene (α phase). J Polym Sci Part B Polym Phys 31:1395–1405
Fillon B, Thierry A, Wittmann JC, Lotz B (1993) Self-nucleation and recrystallization of polymers. isotactic polypropylene, β phase: β-α conversion and β-α growth transitions. J Polym Sci Part B Polym Phys 31:1407–1424
Balzano L, Rastogi S, Peters G (2011) Self-nucleation of polymers with flow: the case of bimodal polyethylene. Macromolecules 44:2926–2933
Zhang YF, Zhou PZ, Guo LH, Hou H (2017) The relationship between crystal structure and nucleation effect of 1, 3, 5-benzenetricarboxylic acid tris (phenylamide) in isotactic polypropylene. Colloid Polym Sci 295:619–626
Yang R, Ding L, Chen W, Zhang X, Li J (2018) Molecular-weight dependence of nucleation effect of a liquid crystalline polyester β-nucleating agent for isotactic polypropylene. Ind Eng Chem Res 57:6734–6740
Liu JR, Zhu XX (2019) Poly(acrylonitrile–butadiene–styrene) as a special β-nucleating agent on the toughness of isotactic polypropylene. Polymers 11:1894
Acknowledgements
This work was financially supported by the project funded by the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Liu, J., Pan, Y. Nucleation and crystallization behavior of isotactic polypropylene induced by zinc tetrahydrophthalate. Polym. Bull. 79, 4563–4580 (2022). https://doi.org/10.1007/s00289-021-03717-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-021-03717-7