A New Analytical Solution of the Binary Copolymer Composition Equation and Suggested Procedure for Deriving the Monomer Reactivity Ratios

Joshi, R. Malatesha; Joshi, S. G.

doi:10.1080/00222337108061112

Cited by 94 publications

(5 citation statements)

References 8 publications

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“…But it can also be seen that a large discrepancy may occur between r A and r B values for a given couple using different methods of analyses and determination. This is why we have chosen the Tidwell and Mortimer 31 method which is considered as one of the most suitable among others. − …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Polymerization of Fluorinated Monomers Bearing a Reactive Lateral Group. 9. Bulk Copolymerization of Vinylidene Fluoride with 4,5,5-Trifluoro-4-ene Pentyl Acetate

et al. 1999

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Bulk copolymerization of vinylidene fluoride (or 1,1-difluoroethylene (VDF)) with 4,5,5-trifluoro-4-ene pentyl acetate (FAc) initiated by di-tert-butyl peroxide is presented. A series of nine copolymerization reactions was investigated from initial [VDF] 0/[FAc]0 molar ratios ranging from 32/68 to 95/5. Both these comonomers copolymerized in this range of copolymerization. Moreover, these comonomers homopolymerized separately in these conditions. The copolymer compositions of these randomtype copolymers were calculated by means of 1 H and 19 F NMR spectroscopies and allowed one to quantify the respective amount of each monomeric unit in the copolymer. From the Tidwell and Mortimer method, the reactivity ratios, ri, of both comonomers were determined showing a higher incorporation of FAc in the copolymer (rFAc ) 3.26 ( 1.49 and rVDF ) 0.17 ( 0.10 at 120°C). Alfrey-Price's Q and e values of trifluorovinyl acetoxy monomer FAc were calculated to be 0.060 (from QVDF ) 0.008) or 0.040 (from QVDF ) 0.015) and +1.14 (vs eVDF ) 0.40) or +1.23 (vs eVDF ) 0.50), respectively, indicating that FAc is an electron-accepting monomer. The normalized monomer-diad and -triad fractions as a function of the polymer composition were obtained from the comonomer sequence distribution theory and this was evidenced by 19 F NMR analysis.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Polymerization of Fluorinated Monomers Bearing a Reactive Lateral Group. 9. Bulk Copolymerization of Vinylidene Fluoride with 4,5,5-Trifluoro-4-ene Pentyl Acetate

et al. 1999

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“…A variety of methods have been developed to determine the reactivity ratios, all with their own advantages and disadvantages. In this study, the linear-least-square (LLS), Joshi–Joshi (J–J) [ 30 ], Fineman–Ross (F–R) [ 31 ], inverted Fineman–Ross (Inv. F–R, in which the definition of monomer 1 and monomer 2 is inverted compared to the normal F–R method), Kelen–Tüdös (K–T) [ 32 ], extended Kelen–Tüdös (ext.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Functionalization of Periodic Copolymers

2017

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For the copolymerization of non-conjugated olefins and maleimides, it is known that under certain conditions periodic ABA monomer sequences are formed. In this work, such a copolymerization is used to create polymers which have defined (periodic) monomer sequences and can be functionalized after polymerization. The copolymerization of pentafluorophenol (PFP) active esters of 4-pentenoic acid and perillic acid with N-phenyl maleimide (PhMI) was studied in 1,2-dichloroethane (DCE) and 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol (HFPP). In DCE and for the copolymerization of the PFP ester of 4-pentenoic acid and PhMI in HFPP, polymers were formed where the active esters were separated by at least one PhMI unit. The average number of separating PhMI units can be controlled by varying the feed ratio of the monomers. For the copolymerization of the PFP ester of perillic acid in HFPP, a preference for the formation of periodic copolymers was observed, where active esters were preferably separated from each other by a maximum of two PhMI moieties. Therefore, the copolymerization of said active ester containing monomers with PhMI provides a platform to create polymers in which reactive moieties are distributed along the polymer chain in different fashions. The active esters in the non-conjugated vinyl monomers could be used in a post-polymerization functionalization step to create functionalized polymers with defined monomer sequences in a modular way.

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“…The solution copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was studied by online proton nuclear magnetic resonance spectroscopy ( 1 HNMR), and the monomer reactivity ratios were computed in a non-linear integrated form of the copolymerization equation which is described by Mayo and Lewis terminal model. A controlled/living photopolymerization of styrene (St) and acrylic acid (AA) was performed at room temperature under UV irradiation, and the monomer reactivity ratios were calculated by the methods of Mayo-Lewis [15], Kelen-Tüdös [11], and YBR [16]. In addition to the above-mentioned methods and means, the methods of Joshi-Joshi [17], extended Kelen-Tüdös [18], Tidwell-Mortimer [19], and error-in-variable [13] and the means of UV-vis [20], 13 C NMR [21], 1 H NMR [22][23][24], 19 F NMR [25], FTIR [26,27], elementary analysis [28], and elemental microanalysis [29] are appropriate for the determination of the monomer reactivity ratios at low conversions.…”

Section: Introductionmentioning

confidence: 99%

Polycarboxylate superplasticizers of acrylic acid–isobutylene polyethylene glycol copolymers: monomer reactivity ratios, copolymerization behavior and performance

et al. 2016

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A New Analytical Solution of the Binary Copolymer Composition Equation and Suggested Procedure for Deriving the Monomer Reactivity Ratios

Cited by 94 publications

References 8 publications

Synthesis and Polymerization of Fluorinated Monomers Bearing a Reactive Lateral Group. 9. Bulk Copolymerization of Vinylidene Fluoride with 4,5,5-Trifluoro-4-ene Pentyl Acetate

Synthesis and Polymerization of Fluorinated Monomers Bearing a Reactive Lateral Group. 9. Bulk Copolymerization of Vinylidene Fluoride with 4,5,5-Trifluoro-4-ene Pentyl Acetate

Synthesis and Functionalization of Periodic Copolymers

Polycarboxylate superplasticizers of acrylic acid–isobutylene polyethylene glycol copolymers: monomer reactivity ratios, copolymerization behavior and performance

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