Study on the Structural Characteristics and Copolymerization Activity of Polyether Macromonomers for Polycarboxylate Superplasticizer

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Title: Study on the Structural Characteristics and Copolymerization Activity of Polyether Macromonomers for Polycarboxylate Superplasticizer

Author(s): Zhao Meili, Zhang Lin, Liu Xiao, Wang Ziming

Publication: Symposium Paper

Volume: 354

Issue:

Appears on pages(s): 113-124

Keywords: copolymerization activity; free radical activity; monomer activity; polyether macromonomer; structural characteristics

DOI: 10.14359/51736066

Date: 7/1/2022

Abstract:
Polyether macromonomers, used for synthesizing polycarboxylate superplastizers (PCE), have been continuously innovated and developed into a series of products possessing different structures and molecular weights with the continuous application expansion of PCE. In this paper, the development process of polyether macromonomers was briefly reviewed, then in order to understand the copolymerization reactivity of commonly used polyether macromonomers (APEG, MAPEG, IPEG, and EVPEG), the structural characteristics, and the electron effect of polyether macromonomers were analyzed. The copolymerization activity of polyether macromonomers was further confirmed by monitoring the conversion rate and composition in copolymers in the copolymerization process. The results show that the electron cloud distribution of polymerizable double bonds in polyether macromonomers is evidently affected by their different end groups. In free-radical copolymerization, the free radical activity of polyether macromonomer, instead of its reactivity ratio, determines the chain growth rate and monomer copolymerization activity. In addition, EVPEG-3000 manifested the highest conversion rate and the highest content in the copolymer, compared with APEG-1200, MAPEG-2400, and IPEG-2400 when copolymerized with acrylic acid (AA) via aqueous free radical copolymerization (acid/ether ratio was 3.75). From high to low, the copolymerization activity of polyether macromonomers is in the order of EVPEG (VPEG), IPEG, MAPEG, and APEG.

Related References:

1. Wang, Z. M., “Polycarboxylates High Performance Water-reducing Admixture : preparation, performance and application,” China Building Industry Press, Beijing, 2009.

2. Li, X. F. et al., “Research Progress and Prospects of Polycarboxylate Superlasticizers Polyether Monomer,” Daily Chemical Science, V. 36, No. 11, 2013, pp. 21-23.

3. Wang, Z. M., and Li, H. Q., “New Progress in Research and Application of Polycarboxylate Superlasticizer,” World of Concrete, No. 8, 2013, pp. 52-58.

4. Chen, N. et al., “Application Progress of the Ethylene Oxide and Propylene Oxide Copolymer,” Daily Chemical Science, V. 33, No. 9, 2010, pp. 18-19.

5. Liu, X. J. et al, “Research on Low-air-entraining Polycarboxylate Superlasticizer,” Proceedings of Academic Exchange Conference on New Progress in Production Technology and Application of Concrete Admixtures, 2012.

6. Li, N., “Development and Application Performance Evaluation of Low-air-entraining Polycarboxylate Superlasticizer,” China Building Materials Federation Concrete Admixture Branch. China Building Materials Federation Concrete Admixture Branch 14th Member Representative Conference-"Cologne Cup" Collection of Essays on Concrete Admixtures (Volume 1). Concrete Admixture Branch of China Building Materials Federation: China Ceramic Society, 2014, PP. 139-145.

7. Liu, X. J. et al., “Study on the Performance of Early-strength Polycarboxylate Superlasticizer Polyether,” Guangdong Chemical Industry, V. 42, No. 2, 2015, pp. 56-57.

8. Liu, X. et al., “Preparation Method of Polycarboxylate Superlasticizer Synthesized by One-step Amidation Reaction, ” China, 102181062AP.. 2011, pp. 09-14.

9. Liu, X. et al., “Preparation and Characterization of a Novel Polycarboxylate Superlasticizer with Amide Structure,” Journal of The Chinese Ceramic Society, V. 41, No. 8, 2013, pp. 1079-1086.

10. Yu, L. L. and Zhou, L. M., “Research on Polycarboxylate Superlasticizer Containing Phosphoric Acid Functional Group,” The 13th Member Congress of the Concrete Admixture Branch of China Building Materials Federation, 2012, pp. 108-113.

11. Akimoto, S. et al., “Additives for Cement”: US, 4946904P.. 1990, pp. 08-07.

12. Hamada, D. et al., “Additive Mixture for Cement-based Concrete or Mortar Contains a Copolymer of Polyalkoxylated Unsaturated Acid and a Mixture of Alkoxylated Carboxylic Acid with a Corresponding Ester and/or an Alkoxylated Alcohol”: DE, 000010048139P.. 2001, pp. 04-12.

13. Yamamoto, M. et al. “Copolymer for Cement Admixtures and its Production Process and Use”: US, 6727315B2P.. 2004, pp. 04-27.

14. Zhou, P. Y., “Preparation of a New Polyether EVPEG at Room Temperature and its Performance of Polycarboxylate Superlasticizer,” New Building Materials, V. 46, No. 4, 2019, pp. 113-116.

15. Albrecht, G. et al., “Copolymers Based on Oxyalkyleneglycol Alkenyl Ethers and Derivatives of Unsaturated Dicarboxylic Acids”: EP, 0736553P.. 1996, pp. 10-09.

16. Pei, J. K. et al., “A Polycarboxylate Superlasticizer and its Preparation Method”: China, 106277899AP.. 2017, pp. 01-04.

17. Lai, H. Z. et al., “Preparation and Performance Evaluation of Low-sensitivity Polycarboxylate Superlasticizer,” New Building Materials, V. 44, No. 8, 2017, pp. 34-36, 57.

18. Liu, G. J. et al., “Research Progress in the Application of Polycarboxylate Superlasticizer Polyether Macromonomers,” Daily Chemical Science, V. 41, No. 10, 2018, pp. 13-16, 28.

19. Pang, J. J. et al., “Evolution of Macromonomers of Polycarboxylate Superlasticizer and Analysis of Causes of Deterioration,” The 14th Member Representative Conference of Concrete Admixture Branch of China Building Materials Federation, 2014, pp. 42- 47.

20. Ying, S. K., “Principle of Copolymerization,” Chemical Industry Press, Beijing: 1984.

21. Pan, Z. R., “Polymer Chemistry (Fifth Edition),” Chemical Industry Press, Beijing: 2011.

22. Wang, Z. M., “Eactivity Ratio and Copolymer Segment Distribution of Isobutenol Polyoxyethylene ether and Acrylic Acid,” Polymer Materials Science & Engineering, V. 34, No. 2, 2018, pp. 19-23.

23. Peng, J. Y., “Study on the Polymerization Activity of Isobutenyl Polyoxyethylene Ether and Different Monomers,” Beijing University of Technology, 2018.

24. Ye, C. J., “Study on the Preparation of Polycarboxylate Superlasticizer with Allyl Polyoxyethylene ether and Acrylic Acid as Main Monomers,” Hebei University of Science and Technology, 2014.

25. Zhang, Z. S. et al., “Determination of Monomer Reactivity Ratio of Acrylic Comb Copolymer AA-TPEG,” Journal of Shanxi University (Natural Science Edition), V. 38, No. 2, 2015, pp. 332-334.

26. Wang, S. F., “Study on the Molecular Structure and Polymerization Mechanism of Polymethacrylic acid High-performance Water Reducing Agent,” Wuhan University of Technology, 2011.

27. Wang, F. et al., “Free Radical Polymerization Reactivity Ratio of Microwave-synthesized Polycarboxylate Superlasticizer,” Journal of The Chinese Ceramic Society, V. 46, No. 8, 2015, pp.1103-1110.

28. Gao, W., “Study on the Preparation of Polycarboxylate Superplasticizer by AAMPEG1500/AA Copolymerization,” Hebei University of Science and Technology, 2010.

29. Abdollahi, H. et al., “Radical Copolymerization of Acrylic Acid and OEGMA475: Monomer Reactivity Ratios and Structural Parameters of the Copolymer,” Macromolecular Research, V. 22, No. 12, 2014, pp.1330-1336.

30. Li, J. L., “Mechanism Analysis of Polycarboxylate Superplasticizer and Determination of Reactivity Ratio,” North University of China, 2014.

31. QIN, X., “Measurement and Analysis of the Reactivity Ratio of two Polyether Macromonomers and Acrylic Acid,” Shanxi University, 2019.

32. YIN, D. J., “Study on theActivity of Comonomers of Polycarboxylate Superplasticizer,” Beijing University of Technology, 2016.

33. Pan, Z. R., “Polymer Chemistry: Enhanced Edition,” Chemical Industry Press, Beijing, 2007.

34. Xu, S. C., “Organic Chemistry (Second Edition),” Higher Education Press, Beijing, 1993.

35. Jiang, M. Q., “Homologous Linear Lw of Organic Compounds,” Science Press, Beijing, 1980.

36. Liu G. J. et al., “Study on the Activity Difference of Macromonomers for Preparing Polycarboxylic Superplasticizers,” Journal of Applied Polymer Science, V. 137, No. 26, 2020, pp.1-10.

37. Fineman, M. and Ross, S. D., “Linear Method for Determining Monomer Reactivity Ratios in Copolymerization,” Journal of Polymer Science, V. 5, No. 2, 1950, pp.259-262.

38. Kelen, T. and Tüds, F. , “Analysis of the Linear Methods for Determining Copolymerization Reactivity Ratios. I. A New Improved Linear Graphic Method,” Journal of Macromolecular Science Part A Chemistry, V. 9, No. 1, 1975, pp.1-27.

39. Lei, L. and Plank, J., “Synthesis and Properties of a Vinyl Ether-Based Polycarboxylate Superplasticizer for Concrete Possessing Clay Tolerance,” Industrial & Engineering Chemistry Research, V. 53, No. 3, 2014, pp.1048-1055.

40. Wang, Z. M. et al., “Analysis of Co-monomer Activity and Copolymer Structure Composition of Polycarboxylate Superplasticizer,” Polymer Material and Engineering, V. 36, No. 10, 2020, pp.29-35.

41. Li, J. N. et al., “Organic Chemistry (Volume One). 5th edition,” Higher Education Press, Beijing, 2011.

42. Francis, A. C. and Richard, J. S., “Advanced Organic Chemistry: Part A: Structure and Mechanisms,” Science Press, Beijing, 2007.

43. Sun, F. et al., “Synthesis and Application of Polyoxyethylene Macromers (Ⅰ)——Synthesis and Characterization of Polyoxyethylene Macromers with Allyl End Groups,” Chemical Journal of Chinese Universities, No. 2, 1987, pp.89-94.

44. Ding, J. C., “A Method for Judging the Relative Stability of Carbon Free Radicals,” Journal of Wenzhou Normal University, No. 54, 1992, pp.64-68.

45. Carpenter, B. K. et al., “Research Method of Organic Reaction Mechanism Determination,” Peking University Press, Beijing, 1991.

46. Evans, M. G., “Polymerisations. Introductory paper,” Discussions of the Faraday Society, No. 2, 1947, pp.271-279.