Batch and semicontinuous emulsion copolymerization of vinylidene chloride and butyl methacrylate. II. Physical and mechanical properties of copolymer latex films

Lee, K. C.; El‐Aasser, M. S.; Vanderhoff, J. W.

doi:10.1002/app.1992.070451218

Cited by 8 publications

(5 citation statements)

References 14 publications

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“…It is well-known that the level of homogeneity of the copolymer is an important factor determining the physical properties of the material , and the experimental − points of view. Yet, remarkably little quantitative information is available on heterogeneity on the colloidal scale, determining the morphology of a latex particle.…”

Section: Introductionmentioning

confidence: 99%

“…It is well-known that the level of homogeneity of the copolymer is an important factor determining the physical properties of the material. 1 Heterogeneity on the molecular level, arising both from the statistical nature of the copolymerization process and from the composition drift occurring along the reaction course, have been extensively studied both from the theoretical 2,3 and the experimental [4][5][6][7] points of view. Yet, remarkably little quantitative information is available on heterogeneity on the colloidal scale, determining the morphology of a latex particle.…”

Section: Introductionmentioning

confidence: 99%

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Inner Structure of Inhomogeneous Copolymer Latex Particles

1997

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A small-angle X-ray scattering (SAXS) study of a model copolymer latex, composed of styrene and pentabromobenzyl acrylate (PBBA, 40 wt %), is presented. The contrast variation method employed in this study was shown to be a sensitive probe for inhomogeneity in the particles. The separation of the homogeneous function allows direct calculation of the size distribution of the spherical particles (volume average diameter, 26.7 ± 1.3 nm). The SAXS analysis reveals a particle's inner structure described as a continuos copolymer phase, of composition being slightly richer in PBBA, within which domains of polystyrene are randomly distributed. The volume fraction of the polystyrene domains was estimated as 11 vol % and their characteristic length as 5.1 nm.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Inner Structure of Inhomogeneous Copolymer Latex Particles

1997

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“…31, No. 12,1999 fractional conversion due to its lower reactivity ratio. The trend observed in VA V triad is similar to that of VVV triad.…”

Section: Monte Carlo Simulation Studiesmentioning

confidence: 99%

“…Lee et a/. 12 have reported the physical and mechanical properties of vinylidene chloridejbutylmethacrylate copolymer. Solaro et a!.…”

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confidence: 99%

“…The central methine proton ofV A V shows a coupling with methylene proton of VA VV and VA VA (AA VV). Thus the cross peaks at !5 3.89/3.06 and 3.93/3.29 ppm are assigned to VAAVV (12) and VAAVA (13) and are assigned to VVV, AVV, and AVA triads, respectively on the basis of the variation in the copolymer composition. The concentration of various A-and V-centered triads were calculated from the relative areas of the resonance signals.…”

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trans-4-Acryloyloxyazobenzene/Vinylidene Chloride Copolymers. Nuclear Magnetic Resonance Characterization

Brar

Thiyagarajan

1999

Polym J

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ABSTRACT:trans-4-Acryloyloxyazobenzenelvinylidene chloride (A/V) copolymers of different monomer concentrations were prepared by solution polymerization using benzoyl peroxide as initiator. The copolymer composition was determined from the quantitative 13 C{'H} NMR spectrum. The carbonyl carbon of A-and the quaternary carbon of V-centered resonances were used for determining the sequences in terms of the distribution of A-and V-centered triads. The sequence distribution of A-and V-centered triads determined from 13 C{'H} NMR spectrum of the copolymer is in good agreement with triad concentration calculated from statistical model. The comonomer reactivity ratios, determined by both Kelen-Tiidos (KT) and nonlinear error in variables (EVM) method are rA =0.36±0.03, rv = 1.02±0.06; rA =0.37 and rv= 1.04, respectively. 13 C Distortionless enhancement by polarization transfer (DEPT) spectrum was used to differentiate the resonance signals of methine (A) and methylene carbon signals of A-and V-units. Assignments to the methinc and methylene resonance signals have been assigned up to the tetrad levels using 2D HSQC experiments. The geminal coupling in the methylene and methine proton region is shown in the 2D TOCSY spectrum.KEY WORDS 13 and trans-4-methacryloyloxyazobenzene/menthyl methacrylate copolymer. 14 The chiroptical properties and photochromic behavior of the copolymers were reported by AI tomare e t a!. 15 To the best of our knowledge, the detailed microstructure study of trans-4-acryloyloxyazobenzenejvinylidene chloride (A/V) copolymers have not been reported so far. In this work, we report the stereochemical structure and sequence distribution of (A/V) copolymers by one and two-dimensional NMR spectroscopy. The 1 H NMR spectrum of copolymer is complex and hasTo whom all correspondence should be addressed. 1224been interpreted with the help of 2D heteronuclear single quantum correlation (HSQC) NMR spectroscopy. The reactivity ratios of the comonomers have been calculated using Kelen-Tiidos (K T) 16 and the non-linear Error in Variable Model (EVM) 17 methods, using the compositional data. The A-and V-centered triad sequence distribution obtained from 13 C{ 1 H} NMR spectrum and are compared with those calculated from the first order Markov model using reactivity ratios determined from the EVM 18 method. EXPERIMENTALThe details of the copolymerization process and NMR measurements are explained in our earlier publications. 19 · 20 RESULTS AND DISCUSSION Reactivity Ratios DeterminationThe copolymer composition of the A/V copolymers were determined from the quantitative 13 CCH} NMR spectra using the inverse gated decoupling pulse program with 8 s as delay time. Table I shows the comonomers mole fractions in the feed and in the copolymer. The initial estimate of the reactivity ratios was done by the KT method. The values of the terminal model reactivity ratios obtained from the KT plot are r A= 0.36 ± 0.03 and rv = 1.02 ± 0.06. These values along with the copolymer data were used to calculate the reactivity rat...

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The effect of composition drift and copolymer microstructure on mechanical bulk properties of styrene‐methyl acrylate emulsion copolymers

Schoonbrood

Brouns

Thijssen

et al. 1995

Macromolecular Symposia

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. (1995). The effect of composition drift and copolymer microstructure on mechanical bulk properties of styrene-methyl acrylate emulsion copolymers. Macromolecular Symposia, 92, 133-156. DOI: 10.1002/masy.19950920113 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Macromol. Symp. 92, 133-156 (1995) Abstract: In order to determine thc inÍ'luencc of composition driÍt and copolymer microstructure on the mcchanical bulk propcrties of styrcnemethyl acrylate oopolymers, scveral copolymers were produced by emulsion copolymerizalion.'l'hree diÍíerent average compositions were used. By pcrlbrming 1he copolyn.rcrizations under batch and scmicontinuous conditions with two diÍferent monomor addition strategies (starvcd conditions and optimal addition) it was possible to control composition drilt and to produce copolymers with differcnt microstructures (chcmical composition distributions). All these oopolymers were processed in a way that ensured that the original particle structure was lost belbre the polymers wcre tested. It was Íbund that composition driÍ1 had an inÍluenos on the mcchanical properties (Young's modulus, maximum stress' clongation at break). This influencc could be undcrstood vcry well on the basis of prcscnt knowlcdge about structure-mechanical properties rclationships. In thc case of homogeneous copolymers maximum stress and elongation at break arc depcndent on thc moleoular weight, and only wcakly depcndent on the chemioal composition, and Young's modulus is indepcndent of chemical composition and molecular wcight irr the rangc of compositions investigated, as expected. ln the case of heterogeneous copolymers' thc inÍluence of copolymer microstructure on Young's modulus, maximum stress and elongation at break is very large. Depending on the extent of control of composition driÍï during the polymerizations, phase separation was observed in the processed polymers, and the presencc of a rubber phase affected the properties profoundlY.

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Batch and semicontinuous emulsion copolymerization of vinylidene chloride and butyl methacrylate. II. Physical and mechanical properties of copolymer latex films

Cited by 8 publications

References 14 publications

Inner Structure of Inhomogeneous Copolymer Latex Particles

Inner Structure of Inhomogeneous Copolymer Latex Particles

trans-4-Acryloyloxyazobenzene/Vinylidene Chloride Copolymers. Nuclear Magnetic Resonance Characterization

The effect of composition drift and copolymer microstructure on mechanical bulk properties of styrene‐methyl acrylate emulsion copolymers

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