Comparative Investigation of the Migration Behavior of Two Stearate Acid Scavengers from Ziegler-Natta Polypropylene into Water during Autoclaving Treatment

Xin-Rao Zhang; Fu-Shan Wang; Xin Wang; Yan Gao; Hong-Xing Zhang; Zhi-Qin Liu; Jia-Chun Feng

doi:10.1007/s10118-024-3213-6

Your Location：

Home >

Browse articles >

Comparative Investigation of the Migration Behavior of Two Stearate Acid Scavengers from Ziegler-Natta Polypropylene into Water during Autoclaving Treatment

RESEARCH ARTICLE | Updated：2024-12-31

- Comparative Investigation of the Migration Behavior of Two Stearate Acid Scavengers from Ziegler-Natta Polypropylene into Water during Autoclaving Treatment
- Chinese Journal of Polymer Science Vol. 43, Issue 1, Pages: 90-100(2025)
- Affiliations：
  
  a.State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
  b.Lanzhou Petrochemical Corporation of PetroChina, Lanzhou 730060, China
- Author bio：
  
  jcfeng@fudan.edu.cn
- Funds：
- DOI：10.1007/s10118-024-3213-6
  CLC： M
- Published：01 January 2025，
  
  Published Online：21 October 2024，
  
  Received：24 January 2024，
  
  Revised：18 July 2024，
  
  Accepted：2024-07-31
- Accepted：
Scan QR Code
Zhang, X. R.; Wang, F. S.; Wang, X.; Gao, Y.; Zhang, H. X.; Liu, Z. Q.; Feng, J. C. Comparative investigation of the migration behavior of two stearate acid scavengers from Ziegler-Natta polypropylene into water during autoclaving treatment. Chinese J. Polym. Sci. 2025, 43, 90–100

XIN-RAO ZHANG, FU-SHAN WANG, XIN WANG, et al. Comparative Investigation of the Migration Behavior of Two Stearate Acid Scavengers from Ziegler-Natta Polypropylene into Water during Autoclaving Treatment. [J]. Chinese journal of polymer science, 2025, 43(1): 90-100.
Zhang, X. R.; Wang, F. S.; Wang, X.; Gao, Y.; Zhang, H. X.; Liu, Z. Q.; Feng, J. C. Comparative investigation of the migration behavior of two stearate acid scavengers from Ziegler-Natta polypropylene into water during autoclaving treatment. Chinese J. Polym. Sci. 2025, 43, 90–100 DOI： 10.1007/s10118-024-3213-6.

XIN-RAO ZHANG, FU-SHAN WANG, XIN WANG, et al. Comparative Investigation of the Migration Behavior of Two Stearate Acid Scavengers from Ziegler-Natta Polypropylene into Water during Autoclaving Treatment. [J]. Chinese journal of polymer science, 2025, 43(1): 90-100. DOI： 10.1007/s10118-024-3213-6.

摘要

The migration of the two commonly used acid scavengers

calcium stearate and zinc stearate

from the plates of a Z-N polypropylene into water during autoclaving were comparatively investigated. It was found that these two acid scavengers exhibited significantly different migration behaviors.

Abstract

Although Ziegler-Natta (Z-N) polyolefins have been widely used as raw materials to produce pharmaceutical or food packaging

the migration of acid scavengers

an additive usually introduced in Z-N polyolefins

from the packaging to its contents has not been reported. In this work

the migration of the two most used acid scavengers

calcium stearate (CaSt

) and zinc stearate (ZnSt

)

from a Z-N polypropylene random copolymer (PPR) into water during autoclaving at 121 °C were comparatively investigated. It was found that

for PPR plates containing 0.1 wt% CaSt

or ZnSt

(PPR-0.1CaSt

PPR-0.1ZnSt

respectively)

the concentration of migrated calcium ion into water increased with autoclaving time

while that of zinc ion was much lower at same treatment durations and did not show a significant increase with treatment time. Interestingly

after removing all plates and acidification treatment

a considerable amount of stearic acid was detected in sterilized water for PPR-0.1ZnSt

but no such significant stearic acid was detected in sterilized water for PPR-0.1CaSt

. Based on the structural evolution of the two soaps upon heating

possible mechanisms for the different migration behavior of CaSt

and ZnSt

from PPR into water during autoclaving treatment were proposed. Our results suggest that the migration issue of acid scavengers is worthy of attention in pharmaceutical packaging materials produced from Z-N polyolefins.

关键词

Keywords

Zinc stearateCalcium stearateZiegler-Natta polyolefinAutoclaving treatmentMigration

references

Yue, Y.; Yi, J.; Wang, L.; Feng, J. Toward a more comprehensive understanding on the structure evolution and assembly formation of a bisamide nucleating agent in polypropylene melt.Macromolecules2020,53, 4381−4394..

Shen, S.; Bao, R.; Liu, Z.; Yang, W.; Xie, B.; Yang, M. Unique crystallization behaviors of isotactic polypropylene in the presence of MWCNT supportedβnucleating agent: lower temperature T(αβ)-T(βα) interval and fast cooling preferred formation of β crystals.Polymer2016,95, 26−35..

Ye, C.; Liu, Z.; Li, J.; Ni, Y.; Xin, Z.; Zhao, S. Effect of calcium stearate and a fluoroelastomer on the flowability of UHMWPE/HDPE composites and the underlying mechanism.J. Polym. Res.2022,30, 7..

Sun, T.; Chen, F.; Dong, X.; Zhou, Y.; Wang, D.; Han, C. Shear-induced orientation in the crystallization of an isotactic polypropylene nanocomposite.Polymer2009,50, 2465−2471..

Ma, P.; Yu, Q.; Shen, T.; Dong, W.; Chen, M. Strong synergetic effect of fibril-like nucleator and shear flow on the melt crystallization of poly(l-lactide).Eur. Polym. J.2017,87, 221−230..

Ferrara, G.; Bertoldo, M.; Scoponi, M.; Ciardelli, F. Diffusion coefficient and activation energy of Irganox 1010 in poly(propylene-co-ethylene) copolymers.Polym. Degrad. Stabil.2001,73, 411−416..

Al Salloum, H.; Saunier, J.; Tfayli, A.; Yagoubi, N. Studying DEHP migration in plasticized PVC used for blood bags by coupling Raman confocal microscopy to UV spectroscopy.Mater. Sci. Eng., C2016,61, 56−62..

Saunier, J.; Mazel, V.; Paris, C.; Yagoubi, N. Polymorphism of Irganox 1076: Discovery of new forms and direct characterization of the polymorphs on a medical device by Raman microspectroscopy.Eur. J. Pharm. Biopharm.2010,75, 443−50..

Bernard, L.; Cueff, R.; Chagnon, M. C.; Abdoulouhab, F.; Décaudin, B.; Breysse, C.; Kauffmann, S.; Cosserant, B.; Souweine, B.; Sautou, V. Migration of plasticizers from PVC medical devices: development of an infusion model.Int. J. Pharm.2015,494, 136−145..

Dazzi, A.; Saunier, J.; Kjoller, K.; Yagoubi, N. Resonance enhanced AFM-IR: a new powerful way to characterize blooming on polymers used in medical devices.Int. J. Pharm.2015,484, 109−114..

Faessler, D.; McCombie, G.; Biedermann, M.; Felder, F.; Subotic, U. Leaching of plasticizers from polyvinylchloride perfusion lines by different lipid emulsions for premature infants under clinical conditions.Int. J. Pharm.2017,520, 119−125..

Saunier, J.; Mazel, V.; Aymes-Chodur, C.; Yagoubi, N. Blooming of Irganox 3114® antioxidant onto a medical grade elastomer. Impact of the recrystallization conditions on the antioxidant polymorphism, on the film wettability and on the antioxidant leachability.Int. J. Pharm.2012,437, 89−99..

Tipton, D. A.; Lyle, B.; Babich, H.; Dabbous, M. K. In vitro cytotoxic and anti-inflammatory effects of myrrh oil on human gingival fibroblasts and epithelial cells.Toxicol. In Vitro2003,17, 301−310..

Sautou-Miranda, V.; Levadoux, E.; Groueix, M. T.; Chopineau, J. Compatibility of propofol diluted in 5% glucose with glass and plastics (polypropylene, polyvinylchloride) containers.Int. J. Pharm.1996,130, 251−255..

Briot, T.; Vrignaud, S.; Lagarce, F. Stability of micafungin sodium solutions at different concentrations in glass bottles and syringes.Int. J. Pharm.2015,492, 137−140..

Kang, K.; Chang, Y.; Choi, J. C.; Park, S.-J.; Han, J. Migration study of butylated hydroxytoluene and Irganox 1010 from polypropylene treated with severe processing conditions.J. Food Sci.2018,83, 1005−1010..

Sherman Jr., R. L.; Kern, K. E. Acid Scavengers for Polyethylene. In M. A. Spalding and A. M. Chatterjee (Eds.),Handbook of Industrial Polyethylene and Technology, Scrivener Publishing LLC, Cincinnati, 2018 , 793−820..

Zhang, G.; Nam, C.; Chung, T. C. M.; Petersson, L.; Hillborg, H. Polypropylene copolymer containing cross-linkable antioxidant moietieswith long-term stability under elevated temperature conditions.Macromolecules2017,50, 7041−7051..

Allen, N. S.; Liauw, C. M.; Reyes, A.; Edge, M.; Johnson, B.; Keck-Antoine, K. Color inhibition of phenolic antioxidants in Ziegler-Natta polyethylene. I.In-situpolymer studies.J. Vinyl Addit. Techn.2009,15, 12−19..

Kresta, J.; Majer, J. Effect of titanium compounds on thermooxidative properties of stabilized polypropylene.J. Appl. Polym. Sci.1969,13, 1859−1871..

Allen, N. S.; Edge, M.; Hussain, S. Perspectives on yellowing in the degradation of polymer materials: inter-relationship of structure, mechanisms and modes of stabilisation.Polym. Degrad. Stabil.2022,201, 109977..

Nouman, M.; Saunier, J.; Jubeli, E.; Yagoubi, N. Additive blooming in polymer materials: consequences in the pharmaceutical and medical field.Polym. Degrad. Stabil.2017,143, 239−252..

Földes, E. Transport of small molecules in polyolefins. II. Diffusion and solubility of irganox 1076 in ethylene polymers.J. Appl. Polym. Sci.1993,48, 1905−1913..

Xu, A.; Roland, S.; Colin, X. Physico-chemical analysis of a silane-grafted polyethylene stabilised with an excess of Irganox 1076®. Proposal of a microstructural model.Polym. Degrad. Stabil.2021,183, 109453..

Schwope, A.; Till, D.; Ehntholt, D.; Sidman, K.; Whelan, R.; Schwartz, P.; Reid, R. Migration of BHT and Irganox 1010 from low-density polyethylene (LDPE) to foods and food-simulating liquids.Food Chem. Toxicol.1987,25, 317−326..

Moisan, J. Y. Diffusion des additifs du polyethylene—I: influence de la nature du diffusant.Eur. Polym. J.1980,16, 979−987..

Bertoldo, M.; Ciardelli, F.; Ferrara, G.; Scoponi, M. Effect of the structure of reactor poly(propylene-co-ethylene) blends on the diffusion coefficient and activation energy of a conventional antioxidant.Macromol. Chem. Phys.2003,204, 1869−1875..

Kim, H.; Lee, K.; Jung, J.; Sin, H.; Lee, H.; Jang, D.; Lee, S.; Lim, K.; Choi, D. Comparison of migration and cumulative risk assessment of antioxidants, antioxidant degradation products, and other non-intentionally added substances from plastic food contact materials.Food Packag. Shelf Life2023,35, 101037..

Khajavi, M.; Mohammadi, R.; Ahmadi, S.; Farhoodi, M.; Abedi, A. S. Evaluating the potential of nanoparticles for controlling zinc stearate release from low-density polyethylene into food simulants.Packag. Technol. Sci.2019,32, 175−183..

Wang, M.; Wu, P.; Sengupta, S.; Chadhary, B.; Cogen, J.; Li, B. Investigation of water diffusion in low-density polyethylene by attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis.Ind. Eng. Chem. Res.2011,50, 6447−6454..

Hou, L.; Feng, K.; Wu, P.; Gao, H. Investigation of water diffusion process in ethyl cellulose-based films by attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis.Cellulose2014,21, 4009−4017..

Lu, Y.; Miller, J. Carboxyl stretching vibrations of spontaneously adsorbed and LB-transferred calcium carboxylates as determined by FTIR internal reflection spectroscopy.J. Colloid Interface Sci.2002,256, 41−52..

Langley, W. D.; Rosenbaum, M. G.; Rosenbaum, M. M. The solubility of calcium stearate in solutions containing bile and in water.J. Biol. Chem.1932,99, 271−278..

Vold, R.; Grandline, J.; Vold, M. Polymorphic transformations of calcium stearate and calcium stearate monohydrate.J. Colloid Sci.1948,3, 339−361..

Dubinsksaya, V. A.; Polyakov, N. A.; Suponitskii, Y. L.; Dement’eva, N. N.; Bykov, V. A. Studies of moisture exchange between stearic acid, calcium stearate, and magnesium stearate.Pharm. Chem. J.2010,44, 89−93..

Hermans, J.; Zuidgeest, L.; Iedema, P.; Woutersen, S.; Keune, K. The kinetics of metal soap crystallization in oil polymers.Phys. Chem. Chem. Phys.2021,23, 22589−22600..

Hermans, J.; Helwig, K.; Woutersen, S.; Keune, K. Traces of water catalyze zinc soap crystallization in solvent-exposed oil paints.Phys. Chem. Chem. Phys.2023,25, 5701−5709..

Kimura, F.; Umemura, J.; Takenaka, T. FTIR-ATR studies on Langmuir-Blodgett films of stearic acid with 1-9 monolayers.Langmuir1986,2, 96−101..

Hermans, J.; Helwig, K. The identification of multiple crystalline zinc soap structures using infrared spectroscopy.Appl. Spectrosc.2020,74, 1505−1514..

Zhang, X.; Wei, F.; Wang, Z.; Li, G.; Yang, S.; Feng, J. Comparative investigation ofthe structural evolution of zinc stearate and calcium stearate in a polypropylene random copolymer upon heating and cooling.Polymer2023,267, 125646..

Byelov, D.; Panine, P.; de Jeu, W. H. Shear-induced smectic order in isotactic polypropylene revisited.Macromolecules2007,40, 288−289..

Hermans, J.; Baij, L.; Koenis, M.; Keune, K.; Iedema, P.; Woutersen, S. 2D-IR spectroscopy for oil paint conservation: elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers.Sci. Adv. 2019, 5, eaaw3592..

Andor, J.; Berkesi,O.; Dreveni, I.; Varga, E. Physical and chemical modification of zinc carboxylate-containing lubricants by molecular structure changes.Lubr. Sci.1999,11, 115−134..

Berkesi, O.; Dreveni, I.; Andor, J. A.; Mink, J. FT-IR studies on the formation of tetrazinc long straight-chain (even-numbered C6-C18) μ4-oxo-hexa-μ-carboxylates from the corresponding bis(carboxylato)zinc compounds.Inorg. Chim. Acta1992,195, 169−173..

Xu, A.; Roland, S.; Colin, X. Physico-chemical characterization of the blooming of Irganox 1076® antioxidant onto the surface of a silane-crosslinked polyethylene.Polym. Degrad. Stabil.2020,171, 109046..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Role of Hydrodynamic Interactions in the Deformation of Star Polymers in Poiseuille Flow

Effect of a Hybrid Zinc Stearate-Silver System on the Properties of Polylactide and Its Abiotic and the Biotic Degradation and Antimicrobial Activity Thereof

Related Author

Xiao-Fei Tian

Zhen-Yue Yang

Li-Jun Liu

Ji-Zhong Chen

Michal Machovsky

Gabriela Jandíková

Petra Stoplova

Antonio Di Martino

Related Institution

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

University of Chinese Academy of Sciences

Centre of Polymer Systems, University Institute, Tomas Bata University in Zlin, tr. Tomas Bati 5678, Zlin760 01, Czech Republic

⁰