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pH-induced conformational changes of comb-like polycarboxylate investigated by experiment and simulation

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Abstract

Four types of polycarboxylate ether (PCE) polymers with consistent backbone length and side-chain (poly(ethylene glycol) monomethyl ether methacrylate MAA-M2000) length but different ratios of acrylic acid (AA) to methacrylic acid (MAA) were synthesized. The ratio of the methyl group would directly affect the backbone stiffness and hydrophobicity of the PCE. Laser light scattering (LLS) and molecular dynamic (MD) simulations were used to investigate the conformations of PCE at various pH values. It was found that the conformation of PCE remained more extended with the decrease of ratio of the backbone methyl group, which resulted in a low exposed extent of carboxylic groups on the backbone at the same ionization degree. The complexation of the carboxylic oxygen atoms of PCE with Ca2+ indicated that the differences of the complexing capacity resulted from the differences in the spatial distribution of carboxylic groups, which depended on the solution conformation of PCE molecules.

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References

  1. Bergaya F, Lagaly G (2006) General introduction: clays, clay minerals, and clay science. Dev Clay Sci 1:1–18

    Article  CAS  Google Scholar 

  2. Hotta Y, Yilmaz H, Shirai T, et al. (2008) State of the dispersant and particle surface during wet-jet milling for preparation of a stable slurry. J Am Ceram Soc 91:1095–1101

    Article  CAS  Google Scholar 

  3. Chu LW, Prakash KN, Tsai MT, et al. (2008) Dispersion of nano-sized BaTiO3 powders in nonaqueous suspension with phosphate ester and their applications for MLCC. J Eur Ceram Soc 28:1205–1212

    Article  CAS  Google Scholar 

  4. Pringuet A, Pagnoux C, Videcoq A, et al. (2008) Granulating titania powder by colloidal route using polyelectrolytes. Langmuir 24:10702–10708

    Article  CAS  Google Scholar 

  5. Kiennemann J, Pagnoux C, Chartier T, et al. (2004) Influence of impurities on dispersion properties of bayer alumina. J Am Ceram Soc 87:2175–2182

    Article  CAS  Google Scholar 

  6. Collepardi M (1998) Admixtures used to enhance placing characteristics of concrete. Cem Concr Compos 20:103–112

    Article  CAS  Google Scholar 

  7. Kreppelt F, Weibel M, Zampini D, et al. (2002) Influence of solution chemistry on the hydration of polished clinker surfaces-a study of different types of polycarboxylic acid-based admixtures. Cem Concr Res 32:187–198

    Article  CAS  Google Scholar 

  8. Lim GG, Hong SS, Kim DS, et al. (1999) Slump loss control of cement paste by adding polycarboxylic type slump-releasing dispersant. Cem Concr Res 29:223–229

    Article  CAS  Google Scholar 

  9. Plank J, Bassioni G (2007) Adsorption of carboxylate anions on a CaCO3 surface. Z Naturforsh B 62:1277–1284

    CAS  Google Scholar 

  10. Yoshioka K, Sakai E, Daimon M, et al. (1997) Role of steric hindrance in the performance of superplasticizers for concrete. J Am Ceram Soc 80:2667–2671

    Article  CAS  Google Scholar 

  11. Yamada K, Takahashi T, Hanehara S, et al. (2000) Effects of the chemical structure on the properties of polycarboxylate-type superplasticizer. Cem Concr Res 30:197–207

    Article  CAS  Google Scholar 

  12. Kirby GH, Lewis JA (2004) Comb polymer architecture effects on the rheological property evolution of concentrated cement suspensions. J Am Ceram Soc 87:1643–1652

    Article  CAS  Google Scholar 

  13. Ran Q, Somasundaran P, Miao C, et al. (2010) Adsorption mechanism of comb polymer dispersants at the cement/water interface. J Dispers Sci Technol 31:790–798

    Article  CAS  Google Scholar 

  14. Dalas F, Nonat A, Pourchet S, et al. (2015) Tailoring the anionic function and the side chains of comb-like superplasticizers to improve their adsorption. Cem Concr Res 67:21–30

    Article  CAS  Google Scholar 

  15. Reese J, Plank J (2011) Adsorption of polyelectrolytes on calcium carbonate—which thermodynamic parameters are driving this process? J Am Ceram Soc 94:3515–3522

    Article  Google Scholar 

  16. Madsen F, Peppas NA (1999) Complexation graft copolymer networks: swelling properties, calcium binding and proteolytic enzyme inhibition. Biomaterials 18:1701–1708

    Article  Google Scholar 

  17. Fantinel F, Rieger J, Molnar F, et al. (2004) Complexation of polyacrylates by Ca2+ ions. Time-resolved studies using attenuated total reflectance Fourier transform infrared dialysis spectroscopy. Langmuir 20:2539–2542

    Article  CAS  Google Scholar 

  18. Wang X, Ye X, Zhang G (2015) Investigation of pH-induced conformational change and hydration of poly (methacrylic acid) investigated by analytical ultracentrifugation. Soft Matter 11:5381–5388

    Article  Google Scholar 

  19. Wu C, Zhou S (1995) Laser light scattering study of the phase transition of poly (N-isopropylacrylamide) in water. 1. Single chain. Macromolecules 28:8381–8387

    Article  CAS  Google Scholar 

  20. Chung YT, Huang CI (2012) Ion condensation behavior and dynamics of water molecules surrounding the sodium poly (methacrylic acid) chain in water: a molecular dynamics study. J Chem Phys 136:124903

    Article  Google Scholar 

  21. Tong K, Song X, Sun S, et al. (2014) Molecular dynamics study of linear and comb-like polyelectrolytes in aqueous solution: effect of Ca2+ ions. Mol Phys 112:2176–2183

    Article  CAS  Google Scholar 

  22. Heinz H, Vaia RA, Farmer BL, et al. (2008) Accurate simulation of surfaces and interfaces of face-centered cubic metals using 12-6 and 9-6 Lennard-Jones potentials. J Phys Chem C 112:17281–17290

    Article  CAS  Google Scholar 

  23. Laguecir A, Ulrich S, Labille J, et al. (2006) Size and pH effect on electrical and conformational behavior of poly (acrylic acid): simulation and experiment. Eur Polym J 42:1135–1144

    Article  CAS  Google Scholar 

  24. Sonnenberg L, Parvole J, Borisov O, et al. (2006) AFM-based single molecule force spectroscopy of end-grafted poly (acrylic acid) monolayers. Macromolecules 39:281–288

    Article  CAS  Google Scholar 

  25. Bulo RE, Donadio D, Laio A, et al. (2007) “Site binding” of Ca2+ ions to polyacrylates in water: a molecular dynamics study of coiling and aggregation. Macromolecules 40:3437–3442

    Article  CAS  Google Scholar 

  26. Lee H, Boyce JR, Nese A, et al. (2008) pH-induced conformational changes of loosely grafted molecular brushes containing poly (acrylic acid) side chains. Polymer 49:5490–5496

    Article  CAS  Google Scholar 

  27. Geffroy C, Foissy A, Persello J, et al. (1999) Surface complexation of calcite by carboxylates in water. J Colloid Interface Sci 211:45–53

    Article  CAS  Google Scholar 

  28. Dobrynin AV, Rubinstein M (2005) Theory of polyelectrolytes in solutions and at surfaces. Prog Polym Sci 30:1049–1118

    Article  CAS  Google Scholar 

  29. Pergushov DV, Buchhammer HM, Lunkwitz K (1999) Effect of a low-molecular-weight salt on colloidal dispersions of interpolyelectrolyte complexes. Colloid Polym Sci 277:101–107

    Article  CAS  Google Scholar 

  30. Zhang G, Wu C (2001) Reentrant coil-to-globule-to-coil transition of a single linear homopolymer chain in a water/methanol mixture. Phys Rev Lett 86:822

    Article  CAS  Google Scholar 

  31. Li Y, Huang Q, Shi T, et al. (2006) Effects of chain flexibility on polymer conformation in dilute solution studied by lattice Monte Carlo simulation. J Phys Chem B 110:23502–23506

    Article  CAS  Google Scholar 

  32. Xu Z, Hadjichristidis N, Fetters LJ et al (1995) Structure/chain-flexibility relationships of polymers. Physical Properties of Polymers, Springer Berlin Heidelberg, pp 1–50

  33. Choi J, Rubner MF (2005) Influence of the degree of ionization on weak polyelectrolyte multilayer assembly. Macromolecules 38:116–124

    Article  CAS  Google Scholar 

  34. Pohlmeier A, Haber-Pohlmeier S (2004) Ionization of short polymethacrylic acid: titration, DLS, and model calculations. J Colloid Interface Sci 273:369–380

    Article  CAS  Google Scholar 

  35. Bakshi MS, Sachar S (2004) Surfactant polymer interactions between strongly interacting cationic surfactants and anionic polyelectrolytes from conductivity and turbidity measurements. Colloid Polym Sci 282:993–999

    Article  CAS  Google Scholar 

  36. Cametti C, Truzzolillo D (2010) Many facets of the polyelectrolyte and oppositely charged colloidal particle complexation: counterion release and electrical conductivity behavior. J Phys Chem B 115:7248–7255

    Article  Google Scholar 

  37. Manning GS (1969) Limiting laws and counterion condensation in polyelectrolyte solutions I. Colligative properties. J Chem Phys 51:924–933

    Article  CAS  Google Scholar 

  38. Fixman M (2010) Electrostatic persistence length. J Phys Chem B 114:3185–3196

    Article  CAS  Google Scholar 

  39. Ran Q, Somasundaran P, Miao C, et al. (2009) Effect of the length of the side chains of comb-like copolymer dispersants on dispersion and rheological properties of concentrated cement suspensions. J Colloid Interface Sci 336:624–633

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (51408272, 51272100), the Natural Science Fund for Distinguished Youth Scholars (51225801), and the Natural Science Foundation of Jiangsu Province (BK20131013, BK20141012). We are grateful to the High Performance Computing Center of Nanjing University for doing the numerical calculations in this paper on its IBM blade cluster system.

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Authors and Affiliations

  1. State Key Laboratory of High Performance Civil Engineering Materials (HPCEM), Jiangsu Research Institute of Building Science, Nanjing, Jiangsu, 210008, China

    Qian Zhang, Qianping Ran, Hongxia Zhao, Xin Shu, Yong Yang & Huaxin Zhou

  2. Jiangsu Sobute New Materials Co. Ltd., Nanjing, Jiangsu, 211103, China

    Qian Zhang, Qianping Ran, Hongxia Zhao, Xin Shu, Yong Yang & Huaxin Zhou

  3. School of Material Science and Engineering, Southeast University, Nanjing, Jiangsu, 211189, China

    Jiaping Liu

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  1. Qian Zhang
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  2. Qianping Ran
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Correspondence to Qianping Ran.

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Zhang, Q., Ran, Q., Zhao, H. et al. pH-induced conformational changes of comb-like polycarboxylate investigated by experiment and simulation. Colloid Polym Sci 294, 1705–1715 (2016). https://doi.org/10.1007/s00396-016-3932-5

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  • DOI: https://doi.org/10.1007/s00396-016-3932-5

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