Copolymerization of acrylonitrile and methacrylic acid. An assessment of the copolymerization mechanism

Borbély, János; Hill, David J. T.; Lang, A.P.; O’Donnell, James H.

doi:10.1021/ma00009a012

Cited by 22 publications

(5 citation statements)

References 1 publication

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is in line with our own previous work7y8) and that of O'Donnell, Hill et al24,25). In addition, the applicability of the complex-dissociation model to this semi-alternating copolymerisation system suggests that it should be considered more often when studying the mechanism of the semi-alternating copolymerisation of comonomers that can form transitory contact 1 : 1 charge-transfer complexes between pairs of electron rich and electron deficient monomers in the comonomer feed.…”

Section: '411 + Aoll+liosupporting

confidence: 89%

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via ¹³C NMR spectroscopy

Brown

Fujimori

1994

Macro Chemistry & Physics

View full text Add to dashboard Cite

The composition and monomer unit sequence distribution of copolymers of p-chlorostyrene (p-CST) with citraconic (a-methylmaleic) anhydride (CA) prepared in methyl ethyl ketone (MEK) at 50,O i 0,l "C were determined over a range of comonomer feed mole fractions using 13C NMR spectroscopy. The monomeric units in these copolymers were found to display a mild tendency to alternate, which increased as the mole fraction of CA in the feed increased. The existence of a 1 : 1 charge-transfer complex formed between p-CST and C A in the feed was confirmed via UV spectroscopy and the equilibrium constant for complex formation determined to be 0,lO i 0,04 L/mol in MEK at ambient temperature. The terminal, penultimate, complexparticipation and complex-dissociation models were each tested for applicability to the mechanism of copolymerisation for this comonomer system. On the basis of copolymer composition data, the penultimate, complex-participation and complex-dissociation models were each found to provide an adequate description of the mechanism of copolymerisation in the comonomer system via non-linear least squares methods. An analysis of the comonomer unit sequence distributions for these semi-alternating copolymers and the application of reactivity ratio related test functions to this data allowed applicability of the four models under investigation to be separated more explicitly, with the complex-dissociation model providing the best fit to the data.

show abstract

Section: '411 + Aoll+liosupporting

confidence: 89%

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via ¹³C NMR spectroscopy

Brown

Fujimori

1994

Macro Chemistry & Physics

View full text Add to dashboard Cite

show abstract

“…The copolymerization of AN with vinyl monomers has been carried out by bulk,10 solution,11 and suspension12 methods by various authors. In bulk polymerization, viscosity builds up rapidly at a low conversion,13 which leads to a low‐molecular‐weight gelled polymer in which membrane preparation is impossible.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of highly selective copolymer membranes and their application for the dehydration of tetrahydrofuran by pervaporation

Ray

2006

J of Applied Polymer Sci

View full text Add to dashboard Cite

Acrylonitrile was copolymerized with 2-hydroxyethyl methacrylate (HEMA) at three different copolymer compositions by emulsion polymerization to produce polyacrylonitrile-2-hydroxyethyl methacrylate (PANHEMA) copolymer membranes containing increasing amounts of HEMA from PANHEMA-1 to PANHEMA-3. The dehydration of tetrahydrofuran (THF) over a concentration range of 0-14 wt % water in the feed was studied by pervaporation with these three copolymer membranes. The permeate water flux and separation factor for water was measured over the same concentration range at 30, 40, and 508C. Among the copolymer membranes, PANHEMA-1 exhibited a reasonable water flux (34.9 g m À2 h À1) with a very high water selectivity (264), whereas PANHEMA-3 showed a higher water flux (52 g m À2 h À1 ) but a lower water selectivity (176.5) for highly concentrated THF (0.56 wt % water in the feed) at 308C. The permeation factors of water for all of the membranes were much greater than unity, which signified a strong positive coupling effect of THF on water permeation.

show abstract

“…Many studies have been performed on the copolymerization of acrylonitrile with vinyl monomers, with 13 C NMR spectroscopy being used to analyze distribution of monomer sequences. Various researchers have used 13 C NMR spectroscopy to determine the microstructure of copolymers of acrylonitrile with alkyl acrylates [15][16][17] .…”

Section: Introductionmentioning

confidence: 99%

NMR spectroscopy based configurational and compositional analysis of isobornyl methacrylate—Acrylonitrile copolymers

Khandelwal

Misra

Sachdeva

et al. 2023

ACE

View full text Add to dashboard Cite

The authors conducted free radical polymerization using an initiator to synthesize a copolymer of isobornyl methacrylate—Acrylonitrile (I/A). The reactivity ratios of I (r1) and A (r2) monomers were determined as r1 = 1.63 ± 0.14, r2 = 0.61 ± 0.06 for linear KT (Kelen–Tudos) method and r1 = 1.58, r2 = 0.60 for the EVM (Error-in-Variable Method). We interpreted 1H and 13C{1H} NMR spectra of the I/A copolymers using DEPT-135 and 2D HSQC spectra. The α-CH3 carbon in the I-unit was identified and confirmed using a 2D HSQC NMR spectrum, up to the level of triad of compositional and configurational sequences. The CH (C14) and β-CH2 carbon peaks were also identified up to the triad level and higher, respectively. A 2D TOCSY spectrum revealed geminal and vicinal interactions within various CH and β-CH2 protons. A 2D HMBC NMR spectrum provided a complete assignment of the coupling between nitrile, carbonyl, and quaternary carbons with CH3 and CH2 protons.

show abstract

Copolymerization of acrylonitrile and methacrylic acid. An assessment of the copolymerization mechanism

Cited by 22 publications

References 1 publication

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via ¹³C NMR spectroscopy

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via ¹³C NMR spectroscopy

Synthesis of highly selective copolymer membranes and their application for the dehydration of tetrahydrofuran by pervaporation

NMR spectroscopy based configurational and compositional analysis of isobornyl methacrylate—Acrylonitrile copolymers

Contact Info

Product

Resources

About

Copolymerization of acrylonitrile and methacrylic acid. An assessment of the copolymerization mechanism

Cited by 22 publications

References 1 publication

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via 13C NMR spectroscopy

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via 13C NMR spectroscopy

Synthesis of highly selective copolymer membranes and their application for the dehydration of tetrahydrofuran by pervaporation

NMR spectroscopy based configurational and compositional analysis of isobornyl methacrylate—Acrylonitrile copolymers

Contact Info

Product

Resources

About

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via ¹³C NMR spectroscopy

A mechanistic study of the radical copolymerisation of p‐chlorostyrene with citraconic anhydride via ¹³C NMR spectroscopy