Free Radical Copolymerization Reactivity Ratios

Greenley, Robert Z.

doi:10.1002/0471532053.bra007

Cited by 42 publications

(55 citation statements)

References 722 publications

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“…Figure 3 displays the results of our investigations of the AT-SCVP of St and VBC in T and A at various temperatures (50,70, and 110 °C). When considering the same solvent (Figure 3a,b for T; Figure 3c,d for A), VBC underwent both faster polymerization and higher conversion than did St at each temperature, consistent with that the reactivity of VBC being slightly higher than that of St (rVBC/rSt ≈ 2.0) [63,64]. When considering the same monomer (Figure 3a,c for St; Figure 3b,d for VBC), the polymerizations in A were faster and occurred with higher conversions at the various temperatures than did those in T, due to the higher-polarity solvent accelerating the reaction rate.…”

Section: Resultssupporting

confidence: 56%

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

2014

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Abstract:In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP) to atom transfer self-condensing vinyl polymerization (AT-SCVP) through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy)) in a mixture of styrene (St), 4-vinyl benzyl chloride (VBC), and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC) macroinitiator (name as: hbPSt MI) with either St or tBA (tert-butyl acrylate). The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98); hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid) segments. OPEN ACCESSPolymers 2014, 6 2553

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Section: Resultssupporting

confidence: 56%

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

2014

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“…The Polymer Handbook, 3rd Ed., quotes just one work on reactivity ratios of hydroxyethyl methacrylate (1) with acrylamide (2) (r 1 Hydroxyalkyl esters of acrylic acid and metha-Å 1.890; r 2 Å 0.050). 22 crylic acid make the basic substrates for the proWorth mentioning is the work of Babu and duction of polymers which, in turn, are the main Deshpande, 23,24 who determined reactivity ratios component of water-soluble or water-thinned lacof hydroxypropyl methacrylate with methyl methquers and varnishes. [1][2][3][4] Their reaction with isocyacrylate or butyl methacrylate and 2-ethylhexyl anates or diols give resins for the production of methacrylate.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of hydroxyalkyl methacrylates with acrylamide and methacrylamide I. Determination of reactivity ratios

Kucharski

Lubczak

1997

J. Appl. Polym. Sci.

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“…For the monomer pair styrene/NVP the values are r 1 ¼ 17.2 and r 2 ¼ 0.057. [16] This means that in a copolymer of these monomers the inclusion of styrene in the copolymer composition is strongly preferred and the inclusion of NVP would follow later. If this was the case for the BM and NVP pair, the crosslinked segments of polyBM would be formed first, and then homopolymer segments of polyNVP would be formed as dangling ends or not incorporated into the network structure.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of New Hydrogels by Copolymerization of Poly(2‐methyl‐2‐oxazoline) Bis(macromonomers) and N‐Vinylpyrrolidone

Rueda

Komber

Cedrón

et al. 2003

Macro Chemistry & Physics

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New non‐ionic hydrogels were synthesized by radical homopolymerization of vinyl end‐functionalized poly(2‐methyl‐2‐oxazoline) bis(macromonomers), or by radical copolymerization of these bis(macromonomers) with N‐vinyl‐2‐pyrrolidone (NVP). The poly(2‐methyl‐2‐oxazoline) bis(macromonomers) were synthesized through “living” cationic ring‐opening polymerization of 2‐methyl‐2‐oxazoline (MeOXA), using, simultaneously, the known “initiating” and “end‐capping” method for synthesis of macromonomers. Chloromethyl styrene was used as initiator and N‐(4‐vinylbenzyl)‐piperazine was used as the terminating agent. Well defined poly(2‐methyl‐2‐oxazoline) bis(macromonomers) were obtained with Pn = 4, 11, and 17. The hydrogel structures were characterized by high‐resolution magic angle spinning NMR technique and their solvent absorption capacity was tested by swelling experiments in different solvents. The bis(macromonomers) were characterized by NMR spectroscopy and gel permeation chromatography.Schematic of polymerizationmagnified imageSchematic of polymerization

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Free Radical Copolymerization Reactivity Ratios

Cited by 42 publications

References 722 publications

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

Copolymerization of hydroxyalkyl methacrylates with acrylamide and methacrylamide I. Determination of reactivity ratios

Synthesis of New Hydrogels by Copolymerization of Poly(2‐methyl‐2‐oxazoline) Bis(macromonomers) and N‐Vinylpyrrolidone

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