RAFT Polymerization of Styrene Using Dithioester with Anthracene Z Group as Chain Transfer Agent

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Zhou Nianchen ◽  
Zhu Jian ◽  
Zhang Zhengbiao ◽  
Zhu Xiulin
Keyword(s):  
Raft Polymerization ◽  
Controlled Radical Polymerization ◽  
Polymer Chains ◽  
Chain Extension ◽  
Enhanced Fluorescence ◽  
H Nmr ◽  
Nmr Characterization ◽  
Raft Agent ◽  
Living Controlled Radical Polymerization

AbstractA novel dithioester, bearing anthracene as Z group, benzyl anthracene-10-carbodithioate (BAC) was successfully synthesized and used as the RAFT agent for the RAFT polymerizations of styrene (St). The results indicated that the polymerization presented the characteristics of “living”/controlled radical polymerization. 1H NMR characterization of obtained polystyrene confirmed that most of the polymer chains were end-capped by the anthracene moiety. The successful chain extension experiment further demonstrated the “living” character of the polymer. The fluorescence investigation of the polymers contained an anthrancene moiety of BAC in the chain end expressed enhanced fluorescence property than that of BAC in CHCl3 solution.

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Zhengbiao Zhang ◽  
Xiulin Zhu ◽  
Jian Zhu ◽  
Zhenping Cheng
Keyword(s):  
Methyl Methacrylate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Controlled Radical Polymerization ◽  
Polymer Chains ◽  
Poly Methyl Methacrylate ◽  
Molecular Weights ◽  
H Nmr ◽  
Reversible Addition ◽  
Living Controlled Radical Polymerization

AbstractPoly(methyl methacrylate) peroxide (PMMAP) was synthesized and used as the initiator in the reversible addition-fragmentation chain transfer (RAFT) polymerization. Methyl methacrylate (MMA) as the monomer and 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as the chain transfer agent was used in the polymerization system. The polymerization was successfully initiated by PMMAP while maintaining features of “living”/controlled radical polymerization such as the number-average molecular weights (Mn) increasing linearly with the monomer conversions and low polydispersity index (PDI) values. The results of 1H NMR and IR spectra confirmed that a small quantity of polymer chains were derived from the PMMAP moieties. The PMMAP can also initiate the RAFT polymerization of styrene (St) and methyl acrylate (MA), and the polymerization proceeded in a “living”/controlled fashion.

Synthesis of Well-defined Carbazole Group Labelled Polymer via RAFT Polymerization and Study on the Optical Properties

e-Polymers ◽  
2006 ◽  
Vol 6 (1) ◽  
Author(s):  
Di Zhou ◽  
Xiulin Zhu ◽  
Jian Zhu ◽  
Lihua Hu ◽  
Zhenping Cheng
Keyword(s):  
Optical Properties ◽  
Raft Polymerization ◽  
Chain Extension ◽  
Dimethyl Formamide ◽  
Coupling Scheme ◽  
H Nmr ◽  
Azo Polymer ◽  
Raft Agent ◽  
Carbazole Group ◽  
Polymerization Conditions

AbstractBenzyl 9H-carbazole-9-carbodithioate (BCC) was synthesized and characterized. The single-crystal structure of BCC was first reported. The RAFT polymerizations of styrene and acrylates using BCC as the RAFT agent under conventional polymerization conditions were investigated. The results showed that the BCC was an effective RAFT agent for the polymerizations of styrene and acrylates. The well-controlled polymers were labelled with carbazole group, which was confirmed by 1H NMR and the chain extension of the obtained polymer. Azo modified poly(methyl acrylate) (PMA) was synthesized through a postpolymerization azo-coupling scheme. The optical properties of obtained polymer were also characterized. The results showed that the carbazole group labelled polymer exhibited fluorescence and the azo polymer exhibited UV absorption behaviour in N,N-dimethyl formamide (DMF).

scholarly journals Copolymer chain formation of 2-oxazolines by in situ1H-NMR spectroscopy: dependence of sequential composition on substituent structure and monomer ratios

RSC Advances ◽  
2021 ◽  
Vol 11 (18) ◽  
pp. 10468-10478
Author(s):  
Sabina Abbrent ◽  
Andrii Mahun ◽  
Miroslava Dušková Smrčková ◽  
Libor Kobera ◽  
Rafał Konefał ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Polymer Chains ◽  
Chain Formation ◽  
Molar Ratios ◽  
H Nmr ◽  
Copolymer Chain ◽  
Nmr Characterization ◽  
Insight Into

In situ1H NMR characterization of copolymerization reactions of various 2-oxazoline monomers at different molar ratios offers detailed insight into the build-up and composition of the polymer chains.

Synthesis and characterization of a new (phthalocyani-nato)bis(carboxylate) silicon(IV) compound with increased solubility

2002 ◽  
Vol 06 (03) ◽  
pp. 198-202 ◽  
Author(s):  
José L. Sosa-Sánchez ◽  
Alberto Galindo ◽  
Dino Gnecco ◽  
Sylvain Bernès ◽  
George R. Fern ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Structure Determination ◽  
Spectroscopic Characterization ◽  
X Ray Diffraction ◽  
H Nmr ◽  
Axial Ligands ◽  
Nmr Characterization ◽  
Soluble Silicon ◽  
Soluble Material

The synthesis and spectroscopic characterization of a new soluble silicon(IV) phthalocyanine complex is presented. The compound shows an increased solubility compared to its SiPcCl 2 precursor and this allowed solution 1 H NMR characterization. The assignment of the 1 H NMR signals for the axial ligands is greatly facilitated due to the anisotropic high ring current effects from the macrocycle. In addition, good quality crystals were grown from this more soluble material for molecular structure determination by single-crystal X-ray diffraction analysis. The molecular structure determination shows that the complex crystallizes in a non-centrosymmetric space group due to the inherent chirality of the naproxene ligands. Bond lengths and angles fit well to other analogous compounds previously reported.

scholarly journals Synthesis and characterization of triphenylamine and Bbis(indolyl)methane center-functionalized polymer via reversible addition-fragmentation chain transfer polymerization

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Jie Xu ◽  
Wei Shang ◽  
Jian Zhu ◽  
Zhenping Cheng ◽  
Nianchen Zhou ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Chloroform Solution ◽  
Monomer Conversion ◽  
Benzyl Ester ◽  
Chain Extension ◽  
Reversible Addition ◽  
Raft Agent ◽  
Cyclic Voltammetry Method

AbstractA novel bis-functional reversible addition-fragmentation chain transfer (RAFT) agent bearing triphenylamine (TPA) and bis(indolyl)methane (BIM) groups, {4-[bis(1-carbodithioic acid benzyl ester-indol-3-yl)methyl]phenyl}diphenylamine (BCIMPDPA), was synthesized and successfully used as the RAFT agent to mediate the polymerization of styrene (St). The polymerization results showed that reversible addition-fragmentation chain transfer (RAFT) polymerization of St could be well controlled. The kinetic plot showed it was of first order and the numberaverage molecular weight (Mn(GPC)) of the polymer measured by GPC increased linearly with monomer conversion, simultaneously, the molecular weight distribution of the polymer was also relatively narrow. In addition, the existence of the TPA and BIM groups in the middle of polymer chain was confirmed by chain extension reaction and 1H NMR spectrum. The optical properties of the functionalized polystyrene (PS) in chloroform solution were also investigated. Furthermore, the redox process of the RAFT agent and the functionalized PS were studied by cyclic voltammetry method.

Nine-Vertex Polyhedral Monoazaborane Chemistry: Synthesis and NMR Characterization of exo-6-Ligand-arachno-4-azanonaboranes(11), 6-L-4-NB8H11

1994 ◽  
Vol 59 (10) ◽  
pp. 2244-2252 ◽  
Author(s):  
Tomáš Jelínek ◽  
Bohumil Štíbr ◽  
John D. Kennedy
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Lewis Bases ◽  
H Nmr ◽  
Nmr Characterization ◽  
Complete Assignment

Reactions between arachno-4-NB8H13 and Lewis bases L in dichloromethane or without solvent generate the previously unreported series of arachno compounds exo-6-L-arachno-4-NB8H11, where L = pyridine (py), quinoline (quin), isoquinoline (i-quin), urotropine (uro), and MeCN. These are characterized by mass spectrometry together with 11B and 1H NMR spectroscopy. The NMR results permit complete assignment of all resonances and thence permit comparison with the structurally similar compounds exo-6-L-arachno-4-EB8H10 (for E = CH2 or S).

Reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in fluid CO2

e-Polymers ◽  
2004 ◽  
Vol 4 (1) ◽  
Author(s):  
Toshihiko Arita ◽  
Sabine Beuermann ◽  
Michael Buback ◽  
Philipp Vana
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Molecular Weights ◽  
Reversible Addition ◽  
Significant Difference ◽  
Raft Agent ◽  
Successful Control ◽  
A Minor ◽  
Peak Widths

Abstract Reversible addition fragmentation chain transfer (RAFT) polymerizations of styrene in fluid CO2 have been carried out at 80°C and 300 bar using cumyl dithiobenzoate as the controlling agent in the concentration range of 3.5·10-3 to 2.1·10-2 mol/L. This is the first report on RAFT polymerization in fluid CO2. The polymerization rates were retarded depending on the employed RAFT agent concentration with no significant difference between the RAFT polymerization performed in fluid CO2 and in toluene. Full chain length distributions were analyzed with respect to peak molecular weights, indicating the successful control of radical polymerization in fluid CO2. A characterization of the peak widths may suggest a minor influence of fluid CO2 on the addition reaction of macroradicals on the dithiobenzoate group.

Living free radical polymerization of styrene with 2-cyanoprop-2-yl dithionaphthalate as RAFT agent

e-Polymers ◽  
2003 ◽  
Vol 3 (1) ◽  
Author(s):  
Zhu Jian ◽  
Zhu Xiulin ◽  
Zhou Di ◽  
Chen Jianying
Keyword(s):  
Molecular Weight ◽  
Reaction Temperature ◽  
Raft Polymerization ◽  
Monomer Concentration ◽  
Gel Permeation Chromatography ◽  
Monomer Conversion ◽  
Bulk Polymerization ◽  
Polymerization Rate ◽  
Chain Extension ◽  
Raft Agent

Abstract The reversible addition-fragmentation chain transfer (RAFT) bulk polymerization of styrene was studied using 2-cyanoprop-2-yl dithionaphthalate (CPDN) as RAFT agent in the presence or absence of 2,2’-azoisobutyronitrile (AIBN). The results of both thermally and AIBN-initiated styrene (St) polymerizations show that St can be polymerized in a controlled way using CPDN as RAFT agent; i.e., the polymerization rate is first order with respect to monomer concentration, and molecular weight increases linearly with monomer conversion. The molecular weights obtained from gel permeation chromatography are close to the theoretical values and molecular weight distributions are relatively narrow (Mw/Mn < 1.2). It is confirmed by chain extension reaction that the polymer prepared via RAFT polymerization can be used as a macroRAFT agent. The effects of reaction temperature and mole ratios [St]0/[CPDN]0/[AIBN]0 on the polymerization were investigated. The results indicate that the reaction temperature has a positive effect on the polymerization rate, but little effect on molecular weight and molecular weight distribution, and the optimum mole ratios were found to be [CPDN]0/[AIBN]0 > 4/3 and [St]0/[CPDN]0 < 800.

Synthesis of azobenzene-centered (co)polymers via reversible addition-fragmentation chain transfer (RAFT) polymerization

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Yu Liping ◽  
Zhu Jian ◽  
Cheng Zhenping ◽  
Zhang Zhengbiao ◽  
Zhang Wei ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Gel Permeation Chromatography ◽  
Polymer Chains ◽  
Dimethyl Formamide ◽  
Reversible Addition ◽  
Raft Agent ◽  
Pentablock Copolymers ◽  
Ft Ir

Abstract An azobenzene-based dithiocarbamate, 4,4'-bis[2-(carbazole-N-dithio formatyl)-2-methyl-propionatyl]-azobenzene (CDMPA), was synthesized and used as the chain transfer agent (CTA) for reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene in anisole solution. Well-defined azobenzene-centered and carbazole-ended polystyrene (PS) with well-controlled molecular weight (Mn) and narrow molecular weight distributions (Mw/Mn) was obtained. The good agreement between the theoretical molecular weight (Mn,th) and the 1H NMR determined molecular weight (Mn,NMR) indicated that most of the polymer chains contained an azo-functional center-group end-capped with the carbazole moieties, which were derived from the RAFT agent. The obtained polystyrene (PS) showed a strong ultraviolet absorption in tetrahydrofuran (THF) and emitted fluorescence after excited by UV-irradiation in N,N’-dimethyl formamide (DMF) solutions. The PS was used as the macro-RAFT agent to carry out the polymerization of methyl acrylate (MA) and N-isopropylacrylamide (NIPAAM). Triblock copolymers (PMA-b-PS-b-PMA), and pentablock copolymers (PNIPAAM-b-PMA-b-PS-b-PMA-b-PNIPAAM) were obtained, respectively. These copolymers were characterized by gel permeation chromatography (GPC), FT-IR spectroscopy and NMR spectroscopy.

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