scholarly journals The influence of hydrogen bonding on radical chain-growth parameters for butyl methacrylate/2-hydroxyethyl acrylate solution copolymerization

2016 ◽  
Vol 7 (27) ◽  
pp. 4567-4574 ◽  
Author(s):  
Jan E. S. Schier ◽  
Robin A. Hutchinson
Keyword(s):  
Growth Parameters ◽  
Propagation Rate ◽  
Size Exclusion ◽  
Rate Coefficients ◽  
Butyl Methacrylate ◽  
Chain Growth ◽  
Copolymer Composition ◽  
Radical Chain ◽  
Effect Of Solvent ◽  
Exclusion Chromatography

Pulsed laser polymerizations coupled with size exclusion chromatography (PLP-SEC) and NMR analyses were performed to determine radical kinetic parameters for BMA/HEA, with a focus on the effect of solvent choice and H-bonding on both copolymer composition and copolymer-averaged propagation rate coefficients.

scholarly journals Solvent Effects on Radical Copolymerization Kinetics of 2-Hydroxyethyl Methacrylate and Butyl Methacrylate

Polymers ◽  
2019 ◽  
Vol 11 (3) ◽  
pp. 487 ◽  
Author(s):  
Loretta Idowu ◽  
Robin Hutchinson
Keyword(s):  
Monomer Concentration ◽  
Propagation Rate ◽  
Radical Copolymerization ◽  
Size Exclusion ◽  
Butyl Methacrylate ◽  
Copolymer Composition ◽  
Solvent Mixtures ◽  
Hydroxyethyl Methacrylate ◽  
Kinetic Coefficients ◽  
Exclusion Chromatography

2-Hydroxyethyl methacrylate (HEMA) is an important component of many acrylic resins used in coatings formulations, as the functionality ensures that the chains participate in the cross-linking reactions required to form the final product. Hence, the knowledge of their radical copolymerization kinetic coefficients is vital for both process and recipe improvements. The pulsed laser polymerization (PLP) technique is paired with size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) to provide kinetic coefficients for the copolymerization of HEMA with butyl methacrylate (BMA) in various solvents. The choice of solvent has a significant impact on both copolymer composition and on the composition-averaged propagation rate coefficient (kp,cop). Compared to the bulk system, both n-butanol and dimethylformamide reduce the relative reactivity of HEMA during copolymerization, while xylene as a solvent enhances HEMA reactivity. The magnitude of the solvent effect varies with monomer concentration, as shown by a systematic study of monomer/solvent mixtures containing 50 vol%, 20 vol%, and 10 vol% monomer. The observed behavior is related to the influence of hydrogen bonding on monomer reactivity, with the experimental results fit using the terminal model of radical copolymerization to provide estimates of reactivity ratios and kp,HEMA.

scholarly journals Critically evaluated propagation rate coefficients for radical polymerizations: acrylates and vinyl acetate in bulk (IUPAC Technical Report)

2019 ◽  
Vol 91 (11) ◽  
pp. 1883-1888
Author(s):  
Robin A. Hutchinson ◽  
Sabine Beuermann
Keyword(s):  
Vinyl Acetate ◽  
Propagation Rate ◽  
Size Exclusion ◽  
Rate Coefficients ◽  
Data Sets ◽  
Chromatography Method ◽  
Benchmark Data ◽  
Technical Report ◽  
Exclusion Chromatography ◽  
Secondary Radical

Abstract Arrhenius parameters capturing the temperature dependence of radical polymerization propagation rate coefficients, kp, for methyl acrylate, butyl acrylate, and vinyl acetate in bulk are reported, based on the fitting of benchmark data sets compiled from independent laboratories using the pulsed-laser polymerization/size exclusion chromatography method. The reported kp values for acrylates hold for secondary-radical propagation and are needed to calculate effective propagation rate coefficients in situations where there is a significant population of mid-chain acrylate radicals resulting from backbiting, as will be the case at technically relevant temperatures. The results are compared to those previously reported for styrene and methacrylates to highlight the large differences in kp values seen between the major monomer families.

Critically evaluated propagation rate coefficients in free-radical polymerizations: Part III. Methacrylates with cyclic ester groups (IUPAC Technical Report)

2003 ◽  
Vol 75 (8) ◽  
pp. 1091-1096 ◽  
Author(s):  
Sabine Beuermann
Keyword(s):  
Free Radical ◽  
Size Exclusion Chromatography ◽  
Ambient Pressure ◽  
Pulsed Laser ◽  
Propagation Rate ◽  
Size Exclusion ◽  
Rate Coefficients ◽  
Arrhenius Relation ◽  
Technical Report ◽  
Exclusion Chromatography

Propagation rate coefficients, kp, as a function of temperature, are reported for bulk free-radical homopolymerizations of oxiranylmethyl, cyclohexyl, and benzyl methacrylate at ambient pressure and low conversion. The data were obtained from experiments combining pulsed-laser initiated polymerization and size-exclusion chromatography. The data determined from experiments carried out in independent laboratories obey the consistency criteria established for this technique. The rate coefficients for the three monomers are well represented by a single Arrhenius relation.

Determination of vinyl acetate propagation rate coefficients via high frequency pulsed laser polymerization

e-Polymers ◽  
2009 ◽  
Vol 9 (1) ◽  
Author(s):  
Thomas Junkers ◽  
Dominik Voll ◽  
Christopher Barner-Kowollik
Keyword(s):  
Vinyl Acetate ◽  
Pulsed Laser ◽  
Propagation Rate ◽  
Size Exclusion ◽  
Rate Coefficients ◽  
Exclusion Chromatography ◽  
Propagation Rate Coefficient ◽  
Good Agreement ◽  
Pulsed Laser Polymerization

AbstractNew data on the propagation rate coefficient, kp, of vinyl acetate (VAc) are obtained via the IUPAC recommended method of pulsed laser polymerization - size exclusion chromatography (PLP-SEC) operated at 500 Hz laser repetition rate. An apparent dependency of the experiment’s outcome on the laser pulsing rate is identified with kp being about 25 % larger at 500 Hz compared to 100 Hz. The temperature dependence of kp was determined to fit ln kp = 17.12 - 2621 K/T; data is in generally good agreement with literature values when the previous underestimation of kp by 100 Hz laser pulsing experiments is taken into account.

Investigating the propagation kinetics of a novel class of nitrogen-containing methacrylates via PLP-SEC

2016 ◽  
Vol 7 (26) ◽  
pp. 4342-4351 ◽  
Author(s):  
Katrin B. Kockler ◽  
Friederike Fleischhaker ◽  
Christopher Barner-Kowollik
Keyword(s):  
Size Exclusion Chromatography ◽  
Rate Coefficient ◽  
Pulsed Laser ◽  
Propagation Rate ◽  
Size Exclusion ◽  
Arrhenius Parameters ◽  
Exclusion Chromatography ◽  
Kinetics Of ◽  
Propagation Rate Coefficient ◽  
Pulsed Laser Polymerization

The Mark–Houwink–Kuhn–Sakurada parameters as well as Arrhenius parameters of the propagation rate coefficient for a new group of nitrogen-containing methacrylates were determined via triple detector SEC and pulsed laser polymerization–size exclusion chromatography, respectively.

scholarly journals Towards Novel Fluorinated Methacrylic Coatings for Cultural Heritage: A Combined Polymers and Surfaces Chemistry Study

Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1190 ◽  
Author(s):  
Valentina Sabatini ◽  
Eleonora Pargoletti ◽  
Valeria Comite ◽  
Marco Aldo Ortenzi ◽  
Paola Fermo ◽  
...  
Keyword(s):  
Prolonged Exposure ◽  
Accelerated Aging ◽  
Water Repellency ◽  
Size Exclusion ◽  
Butyl Methacrylate ◽  
Capillary Absorption ◽  
Scanning Calorimetry ◽  
Water Contact ◽  
Coated Materials ◽  
Exclusion Chromatography

In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), and N-butyl methacrylate (nBuMA), containing just 1% mol × mol−1 of a fluorinated co-monomer, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl methacrylate (POMA), were synthesized. After an UV accelerated aging test, the photo-chemical stability of the polymers prepared was determined by 1H NMR and FT-IR spectroscopy, size exclusion chromatography, differential scanning calorimetry and wettability measurements. The polymers were applied to Botticino tiles to achieve better performances in terms of water repellency and consequently deterioration resistance. One-year prolonged exposure to a real environment was conducted and the properties of the coated materials and their performances were studied using different surface techniques such as water contact angle (WCA) and colorimetric measurements (CIELaB), capillary absorption, permeability (RVP) tests and soluble salts determination. The effectiveness of the fluorinated methacrylic coatings was clearly demonstrated; among all the resins, the co-polymer MMA_POMA seems to be the most performing one. Furthermore, both the UV photo-chemical resistance and the easiness of removal was successfully studied.

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