Guolin Lu

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Organization: Shanghai Institute of Organic Chemistry

Department: 1 Key Laboratory of Organofluorine Chemistry and Laboratory of Polymer Materials

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TOPICS

Polymer

RAFT Atom Transfer Radical Polymerization

Chemicals
References

Constructing semi-fluorinated PDEAEMA-b-PBTFVBP-b-PDEAEMA amphiphilic triblock copolymer via successive thermal step-growth cycloaddition polymerization and ATRP

Co-reporter:Chun Feng, Chao Zhu, Wenqiang Yao, Guolin Lu, Yongjun Li, Xuliang Lv, Mingchun Jia and Xiaoyu Huang

Polymer Chemistry 2015 vol. 6(Issue 45) pp:7881-7892

Publication Date(Web):22 Sep 2015

DOI:10.1039/C5PY01404B

A series of amphiphilic perfluorocyclobutyl-containing ABA triblock copolymers, PDEAEMA-b-PBTFVBP-b-PDEAEMA (DEAEMA: 2-(diethylamino)ethyl methacrylate; BTFVBP: 4,4′-bis(1,2,2-trifluorovinyloxy)biphenyl), was synthesized through the site transformation strategy, combining thermal step-growth cycloaddition polymerization of BTFVBP and atom transfer radical polymerization (ATRP) of DEAEMA. A BTFVBP trifluorovinyl aryl ether monomer was first thermally polymerized to form a semi-fluorinated perfluorocyclobutyl aryl ether-based segment, followed by end functionalization for preparing a Br-PBTFVBP-Br macroinitiator bearing one ATRP initiating group at each end. ATRP of DEAEMA was initiated by Br-PBTFVBP-Br to afford four PDEAEMA-b-PBTFVBP-b-PDEAEMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.42) via varying the feeding ratio of DEAEMA to the macroinitiator. The critical micelle concentration (cmc) of the obtained amphiphilic triblock copolymers was determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as a probe. Micellar morphologies were investigated by transmission electron microscopy. It was shown that such triblock copolymers could self-assemble into large compound micelles, vesicles, and bowl-shaped micelles in aqueous solution with different initial water contents and compositions.

Main-chain PPEGMEMA-b-PBTFVPP-b-PPEGMEMA perfluorocyclobutyl aryl ether-based amphiphilic ABA triblock copolymer: synthesis and self-assembly

Co-reporter:Chun Feng, Wenqiang Yao, Guolin Lu, Yongjun Li and Xiaoyu Huang

RSC Advances 2015 vol. 5(Issue 94) pp:77388-77398

Publication Date(Web):07 Sep 2015

DOI:10.1039/C5RA14246F

A series of perfluorocyclobutyl aryl ether-based amphiphilic ABA triblock copolymers consisting of hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMEMA) and hydrophobic poly(2,2′-bis(4-trifluorovinyl-oxyphenyl)propane) (PBTFVPP) blocks were synthesized via the site transformation strategy. A semi-fluorinated PBTFVPP segment was first prepared via thermal step-growth cycloaddition polymerization of BTFVPP trifluorovinyl aryl ether monomer followed by end functionalization to be transformed into Br–PBTFVBP–Br macroinitiator bearing one ATRP initiating group at each end. The target PPEGMEMA-b-PBTFVPP-b-PPEGMEMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.32) were synthesized via ATRP of PEGMEMA macromonomer initiated by Br–PBTFVBP–Br macroinitiator. A fluorescent probe technique was used to determine the critical micelle concentrations (cmc) of the obtained amphiphilic copolymers in aqueous solution. The morphologies of the micelles formed by the copolymers were investigated by transmission electron microscopy. It was shown that such triblock copolymers could self-assemble into ovals, well-defined cylinders, and spheres in aqueous solution with different initial water contents and compositions.

The first amphiphilic graft copolymer bearing a hydrophilic poly(2-hydroxylethyl acrylate) backbone synthesized by successive RAFT and ATRP

Co-reporter:Xiuyu Jiang, Xue Jiang, Guolin Lu, Chun Feng and Xiaoyu Huang

Polymer Chemistry 2014 vol. 5(Issue 17) pp:4915-4925

Publication Date(Web):20 May 2014

DOI:10.1039/C4PY00415A

A series of well-defined amphiphilic graft copolymers consisting of a hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) backbone and hydrophobic polystyrene side chains were synthesized by the combination of reversible addition–fragmentation chain transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP), and the grafting-from strategy. A new acrylate monomer containing an ATRP initiating group, 2-hydroxyethyl 2-[(2-chloropropanoyloxy)methyl]acrylate, was first prepared via a four-step procedure using 2-hydroxyethyl acrylate as a starting material. This monomer was then RAFT homopolymerized to give a PHEA-based homopolymer bearing a Cl-containing ATRP initiating group in every repeating unit with a narrow molecular weight distribution (Mw/Mn = 1.08). This homopolymer directly initiated the ATRP of styrene to afford the desired well-defined poly(2-hydroxyethyl acrylate)-graft-polystyrene graft copolymers (Mw/Mn ≤ 1.30) containing a hydroxyl in every repeating unit of the backbone without polymeric functionality transformation. The self-assembly behavior of the amphiphilic graft copolymers obtained was investigated by dynamic light scattering and transmission electron microscopy.

Synthesis of PAA-g-PNIPAM well-defined graft polymer by sequential RAFT and SET-LRP and its application in preparing size-controlled super-paramagnetic Fe3O4 nanoparticles as a stabilizer

Co-reporter:Xiuyu Jiang, Sujuan Zhai, Xue Jiang, Guolin Lu, Xiaoyu Huang

Polymer 2014 Volume 55(Issue 16) pp:3703-3712

Publication Date(Web):5 August 2014

DOI:10.1016/j.polymer.2014.05.050

A series of well-defined double hydrophilic graft copolymers, poly(acrylic acid)-g-poly(N-isopropylacrylamide) (PAA-g-PNIPAM), was employed as a novel water-soluble coating for constructing superparamagnetic iron oxide nanoparticles. The copolymer was synthesized via a three-step procedure: firstly, a well-defined hydrophobic PtBA-based backbone, poly(tert-butyl 2-((2-chloropropanoyloxy)-methyl)acrylate)-co-poly(tert-butyl acrylate), (PtBCPMA19-co-PtBA18), was prepared through RAFT copolymerization of a new trifunctional acrylic monomer, tert-butyl 2-((2-chloropropanoyloxy)methyl)acrylate and tert-butyl acrylate; secondly, taking this backbone as a macroinitiator to initiate SET-LRP of N-isopropylacrylamide resulted in well-defined (poly(tert-butyl 2-((2-chloropropanoyloxy)methyl)-acrylate)-co-poly(tert-butyl acrylate))-g-poly(N-isopropylacrylamide) ((PtBCPMA-co-PtBA)-g-PNIPAM) amphiphilic graft copolymers with relatively narrow polydispersities (Mw/Mn ≤ 1.31); thirdly, handling (PtBCPMA-co-PtBA)-g-PNIPAM in acidic conditions afforded PAA-g-PNIPAM graft copolymers. The resulting PAA-g-PNIPAM copolymers were directly utilized as a polymeric stabilizer in the preparation of superparamagnetic Fe3O4 nanoparticles. The particle size can be readily tuned in the range of 12.1–23.2 nm by varying the amount of PAA-g-PNIPAM copolymer or the length of PNIPAM side chain. Besides, the structure and properties of prepared Fe3O4/polymer nanocomposites were characterized by XRD, FT-IR, TGA, TEM, and magnetic measurement in detail.

Construction of PIB-b-PDEAEMA well-defined amphiphilic diblock copolymers via sequential living carbocationic and RAFT polymerization

Co-reporter:Chunhong Ren;Xue Jiang;Xiuyu Jiang;Xiaoyu Huang

Journal of Polymer Science Part A: Polymer Chemistry 2014 Volume 52( Issue 10) pp:1478-1486

Publication Date(Web):

DOI:10.1002/pola.27142

ABSTRACT

A series of well-defined amphiphilic diblock copolymers consisting of hydrophobic polyisobutylene (PIB) and hydrophilic poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) segments was synthesized via the combination of living carbocationic polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization. Living carbocationic polymerization of isobutylene followed by end-capping with 1,3-butadiene was first performed at −70 °C to give a well-defined allyl-Cl-terminated PIB with a low polydispersity (M_w/M_n =1.29). This end-functionalized PIB was further converted to a macromolecular chain transfer agent for mediating RAFT block copolymerization of 2-(diethylamino)ethyl methacrylate at 60 °C in tetrahydrofuran to afford the target well-defined PIB-b-PDEAEMA diblock copolymers with narrow molecular weight distributions (M_w/M_n ≤1.22). The self-assembly behavior of these amphiphilic diblock copolymers in aqueous media was investigated by fluorescence spectroscopy and transmission electron microscope, and furthermore, their pH-responsive behavior was studied by UV-vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1478–1486

tBHBMA: a novel trifunctional acrylic monomer for the convenient synthesis of PAA-g-PCL well-defined amphiphilic graft copolymer

Co-reporter:Xuemei Song, Wenqiang Yao, Guolin Lu, Yongjun Li and Xiaoyu Huang

Polymer Chemistry 2013 vol. 4(Issue 9) pp:2864-2875

Publication Date(Web):25 Feb 2013

DOI:10.1039/C3PY00046J

A series of well-defined amphiphilic graft copolymers, consisting of a hydrophilic poly(acrylic acid) (PAA) backbone and hydrophobic poly(ε-caprolactone) (PCL) side chains, was synthesized by the combination of reversible addition–fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP). A new acrylate monomer containing a ROP initiation group, tert-butyl(2-((4-hydroxybutanoyloxy)methyl)acrylate), was first prepared using tert-butyl acrylate as the starting material, and it was homopolymerized by RAFT in a controlled way to give a well-defined homopolymer bearing ROP initiation group in every repeating unit. This homopolymer directly initiated ROP of ε-caprolactone to provide well-defined poly(tert-butyl acrylate)-g-poly(ε-caprolactone) graft copolymers via the grafting-from strategy without post-polymerization functionality transformation. Finally, the hydrophobic poly(tert-butyl acrylate) backbone was selectively hydrolyzed in an acidic environment without affecting the PCL side chains to afford poly(acrylic acid)-g-poly(ε-caprolactone) amphiphilic graft copolymers possessing the hydrophilic PAA backbone and equally distributed hydrophobic PCL side chains. The self-assembly behavior of the obtained amphiphilic graft copolymers and pH-sensitivity of the resultant micelles were investigated by fluorescence spectroscopy, DLS, and TEM. DSC and XRD analysis showed the crystallization behavior of poly(acrylic acid)-g-poly(ε-caprolactone) graft copolymers.

Well-Defined Triblock Copolymer Containing Perfluorocyclobutyl Aryl Ether and Poly(acrylic acid) Segments

Co-reporter:Guolin Lu;Sen Zhang;Yongjun Li ;Xiaoyu Huang

Chinese Journal of Chemistry 2011 Volume 29( Issue 12) pp:2791-2797

Publication Date(Web):

DOI:10.1002/cjoc.201100448

Abstract

A novel well-defined triblock copolymer containing perfluorocyclobutyl group was prepared by the combination of mechanism transformation strategy, thermal cycloaddition [2Π+2π] polymerization and atom transfer radical polymerization (ATRP). Firstly, a macroinitiator with two ATRP initiating end groups was synthesized by thermal polymerization of 4,4′-bis-(trifluorovinyloxy)biphenyl (BTFVBP) and sequential end-capping with a difunctional compound containing trifluorovinyl and ATRP initiation group. Secondly, this macroinitiator initiated ATRP of t-butyl acrylate to synthesize PtBA-b-PBTFVBP-b-PtBA triblock copolymer. This copolymer was hydrolyzed to afford PAA-b-PBTFVBP-b-PAA amphiphilic triblock copolymer. This kind of fluorine-containing well-defined structure should benefit the study of self-assembly behaviors.