Determination of Homopolymerization Kinetics of 10‐(N‐Methylacrylamido)‐decylphosphonic acid, Its Diethyl ester, and 10‐(Methacryloyloxy)‐decylphosphonic acid, and Their Copolymerization with Methyl methacrylate

Abstract

Two polymerizable phosphonic acids destined to be constituents of self-etch adhesives as well as a diethyl phosphonate bearing an N -methylacrylamide group are examined for their polymeriza tion and copolymerization activity in methanol between 45 and 65 °C. Polymerization proceeds readily through a thermal free radical initiator. The intensity exponents for the monomer and initiator are only slightly over 1 and ≈0.5, respectively, in accordance with the results typically observed for an ideal free radical polymerization with bimolecular termination. The specifi c feature of this process is the absence of auto-acceleration during the phosphonic acid monomer polymerization and polymer network formation in case of the phosphonate monomer. The kinetics of copolymerization with methyl methacrylate (MMA) are monitored by online 1 H NMR spectroscopy. Two copolymerization reactions for each pair of comonomers are suffi cient to evaluate the kinetic data using the Jaacks method, the Fineman-Ross method, and the nonlinear least squares method. All three methods give similar results for particular monomer/MMA couples.

Synthesis and homopolymerization kinetics of 7-(methacroyloxy)-2-oxo-heptylphosphonic acid and its copolymerization with methyl methacrylate

“…The calculation of the copolymerization parameters was performed using the Jaacks method [9], the Fineman-Ross method [10] and the nonlinear least-squares method [11]. Copolymerization parameters for similar monomers as studied in this work were determined in our previous articles [12,13]. The reactivity ratios for the couple 10-(N-methylacrylamido)decylphosphonic acid (MADPA) and MMA were r MADPA = 0.48 and r MMA = 2.32.…”

Automatic Control of Polymer Molecular Weight during Synthesis

“…Small scale research oriented studies maximize accuracy of the information about the system using advanced online monitoring techniques. ,− The kinetic information gained from online characterization has been left for future model predictive control (MPC) and process optimization in most cases. Spectroscopic techniques such as online GPC, UV, and NMR can be used for direct measurement of process variables, while Raman, ATR FTIR, NIRS, and low-resolution Raman can be used in combination with other techniques to obtain calibration curves related to conversion, molecular weight, copolymer composition, and other process characteristics. , The limitations of all the above-mentioned methods are detailed in the literature . Incorporation of control and online optimization with online active process characterization were presented by Skilton et al, using NMR, and Sans et al, using ATR FT-IR.…”

“…6,8−10 The kinetic information gained from online characterization has been left for future model predictive control (MPC) and process optimization in most cases. Spectroscopic techniques such as online GPC, 11 UV, and NMR 12 can be used for direct measurement of process variables, while Raman, 13 ATR FTIR, 14 NIRS, 15 and lowresolution Raman 16 can be used in combination with other techniques to obtain calibration curves related to conversion, molecular weight, copolymer composition, and other process characteristics. 6,11 The limitations of all the above-mentioned methods are detailed in the literature.…”