Facile synthesis of silica-polymer hybrids via simultaneous RAFT process and hydroxyl-alkoxysilane coupling reaction

doi:10.1007/s11458-011-0253-6

Front Chem Chin

2011, Vol. 6

Issue (3) : 213-220 https://doi.org/10.1007/s11458-011-0253-6

RESEARCH ARTICLE

Facile synthesis of silica-polymer hybrids via simultaneous RAFT process and hydroxyl-alkoxysilane coupling reaction

Chunnuan YE, Weina QI, Xinhua YU, Peipei ZHANG, Tengteng HOU, Youliang ZHAO(

)

Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

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Abstract

This study aimed at the synthesis of silica particles grafted with better-defined homopolymers and block copolymers by tandem approach. Z-functionalized S-benzyl S’-(3-trimethoxysilyl)propyltrithiocarbonate (BTPT) was used as a couplable RAFT agent to synthesize the target inorganic-organic hybrids. Simultaneous coupling reaction and RAFT process using silica particles and BTPT as raw materials efficiently afforded homopolymers grafted silica, and RAFT-synthesized macro chain transfer agents with ω-terminal trimethoxysilane moiety were utilized to mediate graft reaction to prepare silica particles grafted with di-, tri- and tetrablock copolymers comprised of polymer segments such as polystyrene, polyacrylamides and polyacrylates. When the grafted chains had molecular weights ranging between 3920 and 24800 g/mol, the molar grafting ratios, which were dependent on reaction conditions and types and compositions of grafted chains, were estimated to be in the range of 15.2–101 μmol/g, and grafted polymers usually had polydispersity indices lower than 1.3, revealing that the grafting process was almost controllable. To the best of our knowledge, this versatile tandem approach is one of the most facile techniques to prepare silica particles grafted with polymeric chains with controlled molecular weight, low polydispersity and precise composition due to its minimal reaction steps, mild conditions, straightforward synthesis and satisfactory controllability.

Keywords hybrid material reversible addition fragmentation chain transfer (RAFT) coupling reaction block copolymer surface modification

Corresponding Author(s): ZHAO Youliang,Email:ylzhao@suda.edu.cn

Issue Date: 05 September 2011

Cite this article:

Chunnuan YE,Weina QI,Xinhua YU, et al. Facile synthesis of silica-polymer hybrids via simultaneous RAFT process and hydroxyl-alkoxysilane coupling reaction[J]. Front Chem Chin, 2011, 6(3): 213-220.

URL:

https://academic.hep.com.cn/fcc/EN/10.1007/s11458-011-0253-6
https://academic.hep.com.cn/fcc/EN/Y2011/V6/I3/213

Fig.1 Synthesis of homopolymers and block copolymers grafted silica via tandem coupling reaction and RAFT polymerization mediated by Z-alkoxysilane-functionalized RAFT agent

Fig.2 Pseudo-first-order kinetic curves for one-pot RAFT graft polymerization of MA mediated by BTPT. Reaction conditions: [MA]∶[BTPT]∶[AIBN] = 200∶1∶0.1, [MA] = 3.0 mol/L, / = 0.50 mmol/g, in toluene at 60°C.

Fig.3 Dependence of and PDI of free (circle) and grafted (triangle) PMAs on conversion. See Fig. 1 for polymerization conditions.

Fig.4 Effects of conversion on weight and molar grafting ratios of PMA grafted silica. See Fig. 1 for polymerization conditions.

Fig.5 Dependence of molar grafting ratio and (g)/(f) on molecular weight of grafted chains during tandem reaction to synthesize PMA grafted silica. See runs 1–5 of Table 1 for reaction conditions.

Tab.1 Synthesis of homopolymers grafted silica by tandem approach using BTPT mediator

Tab.2 RAFT polymerization of various monomers mediated by BTPT and macro CTAs

Tab.3 Synthesis of silica particles grafted with block copolymers by RAFT polymerization of MA mediated by various macro CTAs via one-pot method

Fig.6 TGA curves of silica particles and typical silica-polymer hybrids. The hybrid samples were synthesized by run 2 of Table 1 and runs 1, 4 and 6 of Table 3.

Fig.7 GPC traces of macro CTAs (solid line), free (dotted line) and grafted (dashed line) block copolymers obtained by tandem reaction. Free and grafted copolymers were PSt--PMA (a), PSt--PNIPAM--PMA (b) and PSt--PNIPAM--PBA--PMA (c), respectively. See runs 1, 4 and 6 in Table 3 for detailed reaction conditions.

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