Skip to main content

Advertisement

Log in

Interrelationship between feeding profiles and chains composition-morphology-mechanical properties for forced composition copolymers synthesized by redox initiation

  • ORIGINAL PAPER
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

A semicontinuous emulsion copolymerization via redox initiation (tetramethylenediamine with potassium persulfate) is used to show how, by variations in the comonomers feeding profile, substantial modifications can be obtained in the composition of the copolymer chains that are formed along the reaction, which in turn modifies in a significant manner the morphology and mechanical properties of the materials. That is, changing the comonomers feeding profile and building a histogram for the composition distribution of the synthesized copolymer chains, changes in mechanical properties can be explained along with changes in morphology. Styrene and n-butyl acrylate 50/50 w/w were used to prepare the copolymers. To study the effect of the aforementioned changes caused by the feeding profiles, three pairs of feeding profiles were considered; the “A profiles” were selected to promote different composition histograms, whereas the “B profiles” represent modified “A profiles”. Global conversion was determined by gravimetry and the global copolymer composition along conversion by 1H NMR. Stress–strain tests and dynamic-mechanical analysis were performed to evaluate their mechanical properties. An equivalent statistical copolymer was the reference material. Using redox initiation, the results show for a semicontinuous process, that a fast reaction at low temperature is very convenient. In addition, the interrelation analysis for feeding profiles-histogram-morphology-mechanical properties performance, allows for the first time, the understanding of copolymers mechanical performance as a whole, which can be used as a basis to ease their tailored design.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Robeson LM (2007) Chapter 2. Hanser publishers, Fundamentals of Polymer Blends. Polymer Blends

    Google Scholar 

  2. Mok MM, Kim J, Wong CL, Marrou SR, Woo DJ, Dettmer CM, Nguyen ST, Ellison CJ, Shull KR, Torkelson JM (2009) Glass transition breadths and composition profiles of weakly, moderately, and strongly segregating gradient copolymers: Experimental results and calculations from self-consistent mean-field theory. Macromolecules 42(20):7863–7876. https://doi.org/10.1021/ma9009802

    Article  CAS  Google Scholar 

  3. Chalykh AE, Nikulova UV, Shcherbina AA (2015) Phase equilibria in a polystyrene-poly(butyl acrylate) system. Polym Sci Ser A 57(4):445–451. https://doi.org/10.1134/S0965545X15040069

    Article  CAS  Google Scholar 

  4. Okubo M, Murakami Y, Fujiwara T (1996) Formation mechanism of anomalous “golf ball-like” composite polymer particles by seeded emulsion polymerization. Colloid Polym Sci 274(6):520–524. https://doi.org/10.1007/BF00655226

    Article  CAS  Google Scholar 

  5. Jasinski F, Teo VL, Kuchel RP, Mballa MM, Thickett SC, Brinkhuis RH, Weaver W, Zetterlund PB (2017) Synthesis and characterisation of gradient polymeric nanoparticles. Polym Chem 8(3):495–499. https://doi.org/10.1039/C6PY02062C

    Article  CAS  Google Scholar 

  6. Ott H, Abetz V, Altstädt V (2001) Morphological Studies of Poly (styrene)-block-poly (ethylene-co-butylene)-block-poly (methyl methacrylate) in the Composition Region of the “Knitting Pattern” Morphology. Macromolecules 34(7):2121–2128. https://doi.org/10.1021/ma0017079

    Article  CAS  Google Scholar 

  7. Zhang Z, He Z, Bi S, Asare-Yeboah K (2020) Phase segregation controlled semiconductor crystallization for organic thin film transistors. J Sci Adv Mater Dev 5(2):151–163. https://doi.org/10.1016/j.jsamd.2020.05.004

    Article  Google Scholar 

  8. Mok MM, Kim J, Torkelson JM (2007) Gradient copolymers with broad glass transition temperature regions: Design of purely interphase compositions for damping applications. J Polym Sci, Part B: Polym Phys 46(1):48–58. https://doi.org/10.1002/polb.21341

    Article  CAS  Google Scholar 

  9. Guo Y, Gao X, Luo Y (2015) Mechanical properties of gradient copolymers of styrene and n-butyl acrylate. J Polym Sci, Part B: Polym Phys 53(12):860–868. https://doi.org/10.1002/polb.23709

    Article  CAS  Google Scholar 

  10. Guo Y, Zhang J, Xie P, Gao X, Luo Y (2014) Tailor-made compositional gradient copolymer by a many-shot RAFT emulsion polymerization method. Polym Chem 5(10):3363–3371. https://doi.org/10.1039/C4PY00003J

    Article  CAS  Google Scholar 

  11. Jasso-Gastinel CF, Reyes-González I, López-Ureta LC, González-Ortiz LJ, Manero-Brito O (2006) Mechanical Performance of Styrene-2-Ethylhexyl Acrylate Polymers Synthesized by Semicontinuous Emulsion Polymerization Varying Feed Composition. Int J Polym Anal Charact 11(5):383–402. https://doi.org/10.1080/10236660600803940

    Article  CAS  Google Scholar 

  12. Arnez-Prado AH, González-Ortiz LJ, Aranda-García FJ, Jasso-Gastinel CF (2012) The variation of comonomers feeding profile to design the distribution of chains composition for the optimization of the mechanical properties in copolymer systems. e-Polymers 12(1). https://doi.org/10.1515/epoly.2012.12.1.814

  13. Jasso-Gastinel CF (2017) Chapter 8. Gradients in Homopolymers, blends, and copolymers. In Modification of Polymer Properties, Elsevier: Oxford, UK, 185–210.

  14. Jasso-Gastinel CF, Arnez-Prado AH, Aranda-García FJ, Sahagún-Aguilar LO, Toral LD, Fernando A, Hernández-Hernández ME, González-Ortiz LJ (2017) Tailoring Copolymer Properties by Gradual Changes in the Distribution of the Chains Composition Using Semicontinuous Emulsion Polymerization. Polymers 9(2):72–83. https://doi.org/10.3390/polym9020072

    Article  CAS  PubMed Central  Google Scholar 

  15. Núñez-Pérez FA, González-Ortiz LJ, Lopez-Dellamary TFA, Jasso-Gastinel CF (2012) Enhancement of Mechanical Properties of Emulsion Copolymers by Gradual Variation in Feed Composition. I: Effect of Particle Size in the Butyl Acrylate-Styrene System. Int. J. Polym. Anal. Charact. 17(6): 417–427. https://doi.org/10.1080/1023666X.2012.668656

  16. Rivera-Gálvez FJ, González-Ortiz LJ, López-Manchado MA, Hernández-Hernández ME, Jasso-Gastinel CF (2019) A Methodology Towards Mechanical Properties Optimization of Three-Component Polymers by the Gradual Variation of Feed Composition in Semi-Continuous Emulsion-Free Radical Polymerization. Polymers 11(12):2125–2138. https://doi.org/10.3390/polym11122125

    Article  CAS  PubMed Central  Google Scholar 

  17. Jasso-Gastinel CF, López-Ureta LC, González-Ortiz LJ, Reyes-González I, López-Dellamary TFA, Manero-Brito O (2007) Synthesis and characterization of styrene-butyl acrylate polymers, varying feed composition in a semicontinuous emulsion process. J Appl Polym Sci 103(6):3964–3971. https://doi.org/10.1002/app.25265

    Article  CAS  Google Scholar 

  18. Jinnai H, Yoshida H, Kimishima K, Funaki Y, Hirokawa Y, Ribbe AE, Hashimoto T (2001) Observation of fine structure in bicontinuous phase-separated domains of a polymer blend by laser scanning confocal microscopy. Macromolecules 34(15):5186–5191. https://doi.org/10.1021/ma010190d

    Article  CAS  Google Scholar 

  19. Lyngaae-Jørgensen J, Utracki LA (2003) Structuring polymer blends with bicontinuous phase morphology. Part II. Tailoring blends with ultralow critical volume fraction. Polymer 44(5): 1661–1669. https://doi.org/10.1016/S0032-3861(02)00867-4

  20. Jasso-Gastinel CF, Rivera-Gálvez, FJ, Gonzalez-Ortiz LJ (2018) Process for obtaining three component polymeric materials with oriented variable composition, synthesized by sequential copolymerizations in a semibatch reactor with gradient feed. Patent WO/2018/16799.

  21. Van Doremaele GH, Schoonbrood HA, Kurja J, German AL (1992) Copolymer composition control by means of semicontinuous emulsion copolymerization. J Appl Polym Sci 45(6):957–966. https://doi.org/10.1002/app.1992.070450603

    Article  Google Scholar 

  22. Alb AM, Reed WF (2009) Online monitoring of molecular weight and other characteristics during semibatch emulsion polymerization under monomer starved and flooded conditions. Macromolecules 42(21):8093–8101. https://doi.org/10.1021/ma901434w

    Article  CAS  Google Scholar 

  23. Kohut‐Svelko N, Pirri R, Asua JM, Leiza JR (2009) Redox initiator systems for emulsion polymerization of acrylates. J. Polym. Sci. Part. A: Polymer Chemistry, 47(11): 2917–2927. https://doi.org/10.1002/pola.23362

  24. Sarac AS (1999) Redox polymerization. Prog Polym Sci 24(8):1149–1204. https://doi.org/10.1016/S0079-6700(99)00026-X

    Article  CAS  Google Scholar 

  25. Huang H, Zhang H, Li J, Cheng S, Hu F, Tan B (1998) Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature-preparation and polymerization of miniemulsion. J Appl Polym Sci 68(2):2029–2039. https://doi.org/10.1002/(SICI)1097-4628(19980620)68:12%3c2029::AID-APP17%3e3.0.CO;2-W

    Article  CAS  Google Scholar 

  26. Pan Z, Lv Y, Chen Y, Qian X (2020) Enhanced strength and self-healing properties of CA-Mg2/PVA IPN hydrogel used for shot-membrane waterproofing materials. J Polym Res 27(5):1–11. https://doi.org/10.1007/s10965-020-02105-5

    Article  CAS  Google Scholar 

  27. Kuo CY, Don TM, Lin YT, Hsu SC, Chiu WY (2019) Synthesis of pH-sensitive sulfonamide-based hydrogels with controllable crosslinking density by post thermo-curing. J Polym Res 26(1):18–27. https://doi.org/10.1007/s10965-018-1672-6

    Article  CAS  Google Scholar 

  28. Ferry JD (1980) Chapter 13. The Plateau and Terminal Zones in Uncross-Linked Polymers. Viscoelastic properties of polymers. John Wiley & Sons, New York, 366–403.

  29. Alam MM, Jack KS, Hill DJ, Whittaker AK, Peng H (2019) Gradient copolymers–Preparation, properties and practice. Eur Polymer J 116:394–414. https://doi.org/10.1016/j.eurpolymj.2019.04.028

    Article  CAS  Google Scholar 

  30. Karaky K, Derail C, Reiter G, Billon L (2008) Tuning the surface/bulk properties by the control of the amphiphilic profile in gradient copolymer. Macromolecular symposia Weinheim: WILEY-VCH Verlag 267(1):31–40. https://doi.org/10.1002/masy.200850706

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Francisco Javier Rivera Gálvez thanks CONACyT for the scholarship during the Ph.D. Program, and all authors thank the Universidad de Guadalajara and Institute of Polymer Science and Technology, ICTP-CSIC for the financial support to carry out the experimental research.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Carlos Federico Jasso-Gastinel.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rivera-Gálvez, F.J., López-Manchado, M.Á., González-Ortiz, L.J. et al. Interrelationship between feeding profiles and chains composition-morphology-mechanical properties for forced composition copolymers synthesized by redox initiation. J Polym Res 28, 206 (2021). https://doi.org/10.1007/s10965-021-02502-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-021-02502-4

Keywords

Navigation