In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

doi:10.1016/j.cjche.2014.06.030

›› 2014, Vol. 22 ›› Issue (9): 1046-1054.DOI: 10.1016/j.cjche.2014.06.030

In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

Wenjing Lin¹, Youqiang Yang¹, Ruihao Chen¹, Xiufang Wen¹, Yu Qian¹, Chengzhi Cai², Lijuan Zhang¹

1 School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China;
2 Department of Chemistry & Center for Materials Chemistry, University of Houston, Houston, TX 77204-5003, USA

收稿日期:2013-07-03 修回日期:2013-11-01 出版日期:2014-09-28 发布日期:2014-11-04
通讯作者: Lijuan Zhang
基金资助:
Supported by the National Natural Science Foundation of China (21176090, 21136003), Team Project of Natural Science Foundation of Guangdong Province (S2011030001366), Science and Technology Foundation of Guangdong Province (2012B050600010), and Fundamental Research Funds for the Central Universities (2013ZP0010).

In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

Wenjing Lin¹, Youqiang Yang¹, Ruihao Chen¹, Xiufang Wen¹, Yu Qian¹, Chengzhi Cai², Lijuan Zhang¹

1 School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China;
2 Department of Chemistry & Center for Materials Chemistry, University of Houston, Houston, TX 77204-5003, USA

Received:2013-07-03 Revised:2013-11-01 Online:2014-09-28 Published:2014-11-04
Supported by:
Supported by the National Natural Science Foundation of China (21176090, 21136003), Team Project of Natural Science Foundation of Guangdong Province (S2011030001366), Science and Technology Foundation of Guangdong Province (2012B050600010), and Fundamental Research Funds for the Central Universities (2013ZP0010).

摘要/Abstract

摘要： The amphiphilic copolymer poly(hydroxyethyl methacrylate-co-tert-butyl methacrylate) [P(HEMA-co-tBMA)] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP), with the synthesis process monitored by in-situ infrared spectroscopy (IR). The molecular weight, chemical structure and characteristics of the copolymer were determined by 1H NMR, gas chromatography and gel permeation chromatography. The influences of various parameters on the living polymerization were explored. The molecularweight of the copolymer with narrowmolecularweight distribution (M_w/M_n b 1.50) increases approximately linearly with the monomer conversion, indicating a good control of polymerization. In the reaction temperature range from 50℃ to 90℃, the monomer conversion is higher at 60℃. The tBMA conversion rate decreases gradually with the increase of tBMA content, while the HEMA conversion is hardly affected by HEMA content. Weak polar solvent is more favorable to the polymerization compared to polar solvent. The molar ratio of reducing agent to catalyst has significant effect on the polymerization and increasing the amount of reducing agent will accelerate the reaction rate but causes wider molecular weight distribution. It is indicated that in-situ IR monitoring contributes to a more in-depth understanding of the mechanism of methacrylate monomer copolymerization.

关键词: In-situ IR monitoring, Amphiphilic copolymer, ARGET ATRP, Conversion rate

Abstract: The amphiphilic copolymer poly(hydroxyethyl methacrylate-co-tert-butyl methacrylate) [P(HEMA-co-tBMA)] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP), with the synthesis process monitored by in-situ infrared spectroscopy (IR). The molecular weight, chemical structure and characteristics of the copolymer were determined by 1H NMR, gas chromatography and gel permeation chromatography. The influences of various parameters on the living polymerization were explored. The molecularweight of the copolymer with narrowmolecularweight distribution (M_w/M_n b 1.50) increases approximately linearly with the monomer conversion, indicating a good control of polymerization. In the reaction temperature range from 50℃ to 90℃, the monomer conversion is higher at 60℃. The tBMA conversion rate decreases gradually with the increase of tBMA content, while the HEMA conversion is hardly affected by HEMA content. Weak polar solvent is more favorable to the polymerization compared to polar solvent. The molar ratio of reducing agent to catalyst has significant effect on the polymerization and increasing the amount of reducing agent will accelerate the reaction rate but causes wider molecular weight distribution. It is indicated that in-situ IR monitoring contributes to a more in-depth understanding of the mechanism of methacrylate monomer copolymerization.

Key words: In-situ IR monitoring, Amphiphilic copolymer, ARGET ATRP, Conversion rate

Wenjing Lin, Youqiang Yang, Ruihao Chen, Xiufang Wen, Yu Qian, Chengzhi Cai, Lijuan Zhang. In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP[J]. , 2014, 22(9): 1046-1054.

参考文献

[1] X.D. Guo, L.J. Zhang, Y. Chen, Y. Qian, Core/shell pH-sensitivemicelles self-assembled from cholesterol conjugated oligopeptides for anticancer drug delivery, AICHE J. 56 (2010) 1922-1931.
[2] X.J. Li, M.H. Yin, G.L. Zhang, F.B. Zhang, Study and characterization of novel temperature and pH responsive hydroxylpropyl cellulose-based graft copolymers, Chin. J. Chem. Eng. 17 (2009) 145-149.
[3] Y.N. Xue, Z.Z. Huang, J.T. Zhang, M. Liu, M. Zhang, S.W. Huang, R.X. Zhuo, Synthesis and self-assembly of amphiphilic poly(acrylic acid-b-DL-lactide) to form micelles for pH-responsive drug delivery, Polymer 50 (2009) 3706-3713.
[4] K.S. Soppimath, T.M. Aminabhavi, A.R. Kulkarni,W.E. Rudzinski, Biodegradable polymeric nanoparticles as drug delivery devices, J. Control. Release 70 (2001) 1-20.
[5] P.V.Mendonca, A.C. Serra, J.F.J. Coelho, A.V. Popov, T. Guliashvili, Ambient temperature rapid ATRP ofmethyl acrylate,methylmethacrylate and styrene in polar solventswith mixed transition metal catalyst system, Eur. Polym. J. 47 (2011) 1460-1466.
[6] W. Jakubowski, K. Matyjaszewski, Activator generated by electron transfer for atom transfer radical polymerization, Macromolecules 38 (2005) 4139-4146.
[7] J. Magnus, N. Daniel, N. Ove, M. Eva, Surface modification of thermally expandable microspheres by grafting poly(glycidyl methacrylate) using ARGET ATRP, Eur. Polym. J. 45 (2009) 2374-2382.
[8] D.J. Siegwart, J.K. Oh, K. Matyjaszewski, ATRP in the design of functional materials for biomedical applications, Prog. Polym. Sci. 37 (2012) 18-37.
[9] K. Matyjaszewski, W. Jakubowski, K. Min, W. Tang, J. Huang, W.A. Braunecker, N.V. Tsarevsky, Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents, Proc. Natl. Acad. Sci. U. S. A. 103 (2006) 15309-15314.
[10] W. Jakubowski, B. Kirci-Denizli, R.R. Gil, K. Matyjaszewski, Polystyrene with improved chain-end functionality and higher molecular weight by ARGET ATRP, Macromol. Chem. Phys. 209 (2008) 32-39.
[11] W. Jakubowski, K.Min, K.Matyjaszewski, Activators regenerated by electron transfer for atom transfer radical polymerization of styrene, Macromolecules 39 (2006) 39-45.
[12] T. Pintauer, K. Matyjaszewski, Atom transfer radical addition and polymerization reactions catalyzed by ppm amounts of copper complexes, Chem. Soc. Rev. 37 (2008) 1087-1097.
[13] S.M. Paterson, D.H. Brown, T.V. Chirila, I. Keen, A.K. Whittaker, M.V. Baker, The synthesis of water-soluble PHEMA via ARGET ATRP in protic media, J. Polym. Sci. A Polym. Chem. 48 (2010) 4084-4092.
[14] Y.Q. Xiang, D.J. Chen, Preparation of a novel pH-responsive silver nanoparticle/ poly(HEMA-PEGMA-MAA) composite hydrogel, Eur. Polym. J. 43 (2007) 4178-4187.
[15] X.M. Li, Y.D. Cui, Study on synthesis and chloramphenicol release of poly(2-hydroxyethylmethacrylate-co-acrylamide) hydrogels, Chin. J. Chem. Eng. 16 (2008) 640-645.
[16] M.D.P.Wilcox, N. Harmis, B.A. Cowell, T.Williams, B.A. Holden, Bacterial interactions with contact lenses:effects of lens material, lens wear and microbial physiology, Biomaterials 22 (2001) 3235-3247.

[17] P.V.D.Wetering, E.E. Moret, N.M.E. Schuurmans-Nieuwenbroek, M.J.V. Steenbergen, W.E. Hennink, Structure-activity relationships of water-soluble cationic methacrylate/ methacrylamide polymers for nonviral gene delivery, Bioconjug. Chem. 10 (1999) 589-597.
[18] P. MacLaurin, N.C. Crabb, I.Wells, P.J.Worsfold, Quantitative in situ monitoring of an elevated temperature reaction using a water-cooled mid-infrared fiber-optic probe, Anal. Chem. 68 (1996) 1116-1123.
[19] L.K. Breland, F.S. Robson, Polyisobutylene-based miktoarm star polymers via a combination of carbocationic and atom transfer radical polymerizations, Polymer 49 (2008) 1154-1163.
[20] Y.S. Zhao, H.B. Wang, X.H. Hou, Y.H. Hu, A.W. Lei, H. Zhang, L.Z. Zhu, Oxidative cross-coupling through double transmetallation: surprisingly high selectivity for palladium-catalyzed cross-coupling of alkylzinc and alkynylstannanes, J. Am. Chem. Soc. 128 (2006) 15048-15049.
[21] A.E. Enriquez, J.L. Templeton, Monomeric and dinuclear tungsten carbyne complexes containing benzyl, allyl, and alkenyl carbyne substituents, Organometallics 21 (2002) 852-863.
[22] H. Hong, A.D. Marc, In-line monitoring of emulsion homo-and copolymerizations using ATR-FTIR spectrometry, Polym. React. Eng. 10 (2002) 21-39.
[23] A. Matsumoto, T. Otaka, H. Aota, In-situ kinetic pursuit of emulsion crosslinking copolymerizations of monomethacrylate and dimethacrylate by means of reactIR, Macromol. Rapid Commun. 22 (2001) 607-610.
[24] M. Krajnc, I. Poljansek, Characterization of phenol-formaldehyde prepolymer resins by in line FT-IR spectroscopy, Acta Chim. Slov. 52 (2005) 238-244.
[25] J. Scherble, B. Ivan, R. Mulhaupt, Onlinemonitoring of silicone network formation by means of in-situ mid-infrared spectroscopy, Macromol. Chem. Phys. 203 (2002) 1866-1871.
[26] K. Tanaka, K. Matyjaszewski, Copolymerization of (meth) acrylates with olefins using activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP), Macromol. Symp. 261 (2008) 1-9.
[27] W. Jakubowski, K. Matyjaszewski, Activators regenerated by electron transfer for atom-transfer radical polymerization of (meth)acrylates and related block copolymers, Angew. Chem. Int. Ed. 45 (2006) 4482-4486.

In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 1

编辑推荐

Metrics

本文评价