Simulation of Molecular Weight Distributions Obtained by Pulsed Laser Polymerization (PLP): New Analytical Expressions Including Intramolecular Chain Transfer to the Polymer

A new approach for the simulation of PLP (pulsed laser polymerization) is presented. This approach allows one to obtain new analytical solutions for different polymerization schemes, including either chain transfer to the monomer or intramolecular chain transfer to the polymer. The first results of the simulation of PLP experiments on n‐butyl acrylate at 20 °C and ambient pressure are presented.

MWDs simulated for PLP of n‐butyl acrylate, in bulk at 20 °C and ambient pressure using three models: the model with intramolecular chain transfer to the polymer (solid line), the model with chain transfer to monomer (dashed line), and the classical model (dotted line).     

Initiation of radical polymerization by peroxyacetates: Polymer end-group analysis by electrospray ionization mass spectrometry

End-groups of poly(methyl methacrylate) from radical solution polymerization of MMA using tert-butyl peroxyacetate (TBPA), tert-amyl peroxyacetate (TAPA), 1,1,2,2- tetramethylpropyl peroxyacetate (TMPPA), and 1,1,3,3-tetramethylbutyl peroxyacetate (TMBPA) as the initiators were analyzed via electrospray ionization mass spectrometry (ESI-MS). The type and the relative concentration of the radical species, which actually initiate macromolecular growth, are determined. In the majority of cases, these species differ from the primary radicals from thermal decomposition of the peroxyacetates. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was applied for unambiguous peak assignment. The methylcarbonyloxyl radical, which is formed by the decomposition of all peroxyacetates, was found to undergo decarboxylation yielding an initiating methyl radical. TAPA- and TMPPA-derived alkoxyl radicals mainly show β-scission, TMBPA-derived alkoxyl radicals additionally undergo a 1,5-hydrogen-shift reaction. The tert-butoxyl radicals produced from TBPA undergo pronounced chain-transfer reaction prior to their decomposition into methyl radicals and acetone. In the case of using benzene as a relatively inert solvent, the tert-butoxyl radicals exhibit transfer to monomer yielding polymer molecules, which do not carry any initiator-derived end-groups. By using mesitylene as a cosolvent, small amounts of star polymer were generated via multiple hydrogen abstraction by tert-butoxyl radicals from the three individual methyl groups of mesitylene. This uncomplicated procedure of modification of end-group and polymer topology may be attractive for facile adjustment of polymer viscosity in technical processes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2453–2467, 2007     

Elementary Steps of Initiation and Termination Processes in Radical Polymerization

Investigations into the kinetics of primary radicals produced in photochemically and thermally induced decomposition of peroxides of type R₁C(O)O-OR₂ are presented. The correlation of peroxide structure with decomposition rate and with initiator efficiency in radical polymerizations is discussed. Termination rate coefficients, k_t, as a function of temperature, pressure, polymer content, and of chain length may be deduced from two types of time-resolved experiments in which, after applying an excimer laser pulse, either monomer conversion is measured via near-infrared spectroscopy or the decay in radical concentration is monitored via electron spin resonance.     

Determination of Propagation Rate Coefficient of Acrylates by Pulsed‐Laser Polymerization in the Presence of Intramolecular Chain Transfer to Polymer

Unusual difficulties are faced in the determination of propagation rate coefficients (k_p) of alkyl acrylates by pulsed‐laser polymerization (PLP). When the backbiting is the predominant chain transfer event, the apparent k_p of acrylates determined in PLP experiments for different frequencies should range between k_p (propagation rate coefficient of the secondary radicals) at high frequency and k at low frequency. The k value could be expressed from kinetic parameters: , where k_fp is the backbiting rate coefficient, k_p2 is the propagation rate coefficient of mid‐chain radicals, and [M] is the monomer concentration.

Apparent propagation rate coefficients determined for different frequencies by simulating the PLP of n‐butyl acrylate at 20 °C. Horizontal full lines show the values of k_p and k.     

Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

The propagation kinetics of isoprene radical polymerizations in bulk and in solution are investigated via pulsed laser initiated polymerizations and subsequent polymer analyses via size‐exclusion chromatography, the PLP‐SEC method. Because of low polymerization rate and high volatility of isoprene, the polymerizations are carried out at elevated pressure ranging from 134 to 1320 bar. The temperatures are varied between 55 and 105 °C. PLP‐SEC yields activation parameters of k_p (Arrhenius parameters and activation volume) over a wide temperature and pressure range that allow for the calculation of k_p at technically relevant ambient pressure conditions. The k_p values determined are very low, e.g., 99 L mol^?1 s^?1 at 50 °C, which is even lower than the corresponding value for styrene polymerizations. The presence of a polar solvent results in a slight increase of k_p compared to the bulk system. The k_p values reported are important for determining rate coefficients of other elemental reactions from coupled parameters as well as for modeling isoprene free‐radical polymerizations and reversible deactivation radical polymerization with respect to tailored polymer properties and optimizing the polymerization processes.     

Solvent Influence on Propagation Kinetics in Radical Polymerizations Studied by Pulsed Laser Initiated Polymerizations

The influence of the reaction medium (organic solvents, water, ionic liquids, supercritical CO₂) on the propagation rate in radical polymerizations has very different causes, e.g., hindered rotational modes, hydrogen bonding or electron pair donor/acceptor interactions. Depending on the origin of the solvent influence propagation rate coefficients, k_p, may be enhanced by up to an order of magnitude associated with changes in the pre‐exponential or the activation energy of k_p. In contrast, non‐specific interactions, size and steric effects lead to rather small changes in the vicinity of the radical chain end and are reflected by modest variations in k_p.

     

Pulsed Laser Polymerization at Low Conversions: Broadening and Chain Transfer Effects

Pulsed laser polymerization (PLP) is widely employed to measure propagation rate coefficients k_p in free radical polymerization. Various properties of PLP have been established in previous works, mainly using numerical methods. The objective of this paper is to obtain analytical results. We obtain the most general analytical solution for the dead chain molecular weight distribution (MWD) under low conversion conditions which has been hitherto obtained. Simultaneous disproportionation and combination termination processes are treated. The hallmarks of PLP are the dead MWD discontinuities located at integer multiples of n₀ = k_pt₀C_M, where t₀ is the laser period and C_M is the monomer concentration. We show that chain transfer reduces their amplitude by factors , consistent with numerical results obtained by other workers. Here c_tr is the chain transfer coefficient and Ln₀ (L = integer) are the discontinuity locations. Additionally, transfer generates a small amplitude continuous contribution to the MWD. These results generalize earlier analytical results which were obtained for the case of disproportionation only. We also considered two classes of broadening: (i) Poisson broadening of growing living chains and (ii) intrinsic broadening by the MWD measuring equipment (typically gel permeation chromatography, GPC). Broadening smoothes the MWD discontinuities. Under typical PLP experimental conditions, the associated inflection points are very close to the discontinuities of the unbroadened MWD. Previous numerical works have indicated that the optimal procedure is to use the inflection point to infer k_p. We prove that this is a correct procedure provided the GPC resolution σ is better than nequation/tex2gif-stack-1.gif. Otherwise this underestimates Ln₀ by an amount of order σ²/n₀.

Schematic of a chain transfer reaction with monomer as the transfer agent.     

Free‐Radical Termination Kinetics Studied Using a Novel SP‐PLP‐ESR Technique

Summary: A novel method for measuring termination rate coefficients, k_t, in free‐radical polymerization is presented. A single laser pulse is used to instantaneously produce photoinitiator‐derived radicals. During subsequent polymerization, radical concentration is monitored by time‐resolved electron spin resonance (ESR) spectroscopy. The size of the free radicals, which exhibits a narrow distribution increases linearly with time t, which allows the chain‐length dependence of k_t to be deduced. The method will be illustrated using dodecyl methacrylate polymerization as an example.

Two straight lines provide a very satisfactory representation of the chain‐length dependence of k_t over the entire chain‐length region (c_R = radical concentration).     

Electrospray ionization mass spectrometric study of end‐groups in peroxydicarbonate‐initiated radical polymerization

Initiation by diethyl peroxydicarbonate (E‐PDC), di‐n‐tetradecyl peroxydicarbonate (nTD‐PDC), di‐n‐hexadecyl peroxydicarbonate (nHD‐PDC), and di‐2‐ethylhexyl peroxydicarbonate (2EH‐PDC) of free‐radical polymerizations of methyl methacrylate in benzene solution was studied by end‐group analysis via electrospray ionization mass spectrometry (ESI‐MS). Unambiguous assignment of ESI‐MS peaks allows for identification of the type of radical that starts chain growth. In case of initiation by dialkyl peroxydicarbonates with linear alkyl groups, almost exclusively alkoxy carbonyloxyl species, which are the primary fragments from initiator decomposition, occur as end‐groups. With 2EH‐PDC, however, both the primary 2‐ethylhexoxy carbonyloxyl fragment and a second moiety, which is formed by decarboxylation of the 2‐ethylhexoxy carbonyloxyl radical, are clearly observed as end‐groups. The decarboxylation process is described by a concerted mechanism which involves a 1,5‐hydrogen shift reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6071–6081, 2008     

Laser Desorption Ionization Versus Electrospray Ionization Mass Spectrometry: Applications in the Analysis of Cluster Anions

Mass spectra of transition metal carbonyl cluster anions were recorded using laser desorption ionization time-of-flight (LDI-TOF) and electrospray ionization (ESI) techniques. The LDI spectra generally contain peaks corresponding the intact cluster together with extensive CO loss fragments ions whereas the ESI spectra exhibit peaks corresponding the intact cluster together with few (if any) CO loss fragment ions. The parameters of both techniques can be modified to vary the extent of fragmentation. In all cases no fragmentation of the metal core is observed. Overall, ESI is a more informative method for the analysis of these types of cluster anions.     

Studying the Fundamentals of Radical Polymerization Using ESR in Combination with Controlled Radical Polymerization Methods

Electron spin resonance (ESR) spectroscopy can contribute to understanding both the kinetics and mechanism of radical polymerizations. A series of oligo/poly(meth)acrylates were prepared by atom transfer radical polymerization (ATRP) and purified to provide well defined radical precursors. Model radicals, with given chain lengths, were generated by reaction of the terminal halogens with an organotin compound and the radicals were observed by ESR spectroscopy. This combination of ESR with ATRPs ability to prepare well defined radical precursors provided significant new information on the properties of radicals in radical polymerizations. ESR spectra of the model radicals generated from tert-butyl methacrylate precursors, with various chain lengths, showed clear chain length dependent changes and a possibility of differentiating between the chain lengths of observed propagating radicals by ESR. The ESR spectrum of each dimeric, trimeric, tetrameric, and pentameric tert-butyl acrylate model radicals, observed at various temperatures, provided clear experimental evidence of a 1,5-hydrogen shift.     

Determination of the Mode of Free Radical Termination from Pulsed Laser Polymerization Experiments

The molecular‐weight distribution (MWD), obtained by pulsed laser polymerization (PLP) at the high termination rate limit has been considered for investigating termination kinetics. The proposed methodology takes into account both the composite model for termination and the chain‐length dependencies of propagation for short‐chain and long‐chain radicals. Power‐law expressions are used to represent propagation and termination of long‐chain radicals (where k and k represent the maximum “virtual” rate coefficients for monomeric radicals, and α and β capture the chain‐length dependencies for propagation and termination), with the combined value of (β − α) evaluated from the MWD, after correcting for the influence of the kinetics of short‐chain radicals. A novel method is also developed for determining the mode of termination, δ, from MWDs produced by PLP at the high termination rate limit. Simulations for methyl methacrylate (MMA) polymerization at 25 °C confirm that the method can be applied robustly in the presence of complicating factors such as chain transfer to monomer and SEC broadening. The analysis of an experimental MWD obtained for MMA polymerization at 25 °C results in estimates of 0.14 ± 0.03 for (β − α) and 0.75 ± 0.04 for δ.

     

Free‐Radical Propagation Rate Coefficients via n‐Pulse Periodic Polymerization

Aspects of applying n‐pulse periodic initiation in pulsed laser polymerization/size‐exclusion chromatography (PLP/SEC) experiments are studied via simulation of molecular weight distributions (MWDs). In n‐pulse periodic PLP/SEC, sequences of n laser pulses at successive time intervals Δt₁ up to Δt_n are periodically applied. With the dark time intervals being suitably chosen, n‐modal MWDs with n well separated peaks occur. The n‐pulse periodic PLP/SEC method has the potential for providing accurate propagation rate coefficients, k_p. Among several measures for k_p, the differences in molecular weights at the MWD peak positions yield the best estimate of k_p under conditions of medium and high pulse laser‐induced free‐radical concentration. Deducing k_p from n dark time intervals (corresponding to n regions of free‐radical chain length) within one experiment at otherwise identical PLP/SEC conditions allows addressing in more detail a potential chain‐length dependence of k_p. Simulations are compared with experimental data for 2‐pulse periodic polymerization of methyl methacrylate.

Measured MWD (solid line) and associated first derivative curve (dotted line) for a 2‐pulse periodic bulk polymerization experiment of MMA at 20 °C.     

Laser Single Pulse Initiated RAFT Polymerization for Assessing Chain‐Length Dependent Radical Termination Kinetics

Summary: A novel method combining RAFT polymerization with pulsed‐laser initiation for determining chain‐length dependent termination rate coefficients, k_t, is presented. Degenerative chain‐transfer in RAFT enables single‐pulse pulsed‐laser polymerization (SP‐PLP) traces to be measured on systems with a narrow radical distribution that remains essentially unchanged during the experiment. SP‐PLP‐RAFT experiments at different polymerization times allow for determining k_t as a function of chain length via classical kinetics assuming chain‐length independent k_t.

Single‐pulse pulsed‐laser polymerization trace for BMPT‐mediated RAFT polymerization of butyl acrylate.     

Quantifying Photoinitiation Efficiencies in a Multiphotoinitiated Free‐Radical Polymerization

Online size exclusion chromatography–electrospray ionization–mass spectrometry (SEC/ESI–MS) is employed for quantifying the overall initiation efficiencies of photolytically generated radical fragments. In a unique experiment, we present the first quantitative and systematic study of methyl‐substituted acetophenone‐type photoinitiators being employed in a single cocktail to initiate the free‐radical polymerization of methyl methacrylate (MMA) in bulk. The photoinitiators are constituted of a set of two known and four new molecules, which represent an increasing number of methyl substituents on their benzoyl fragment, that is, benzoin, 4‐methylbenzoin, 2,4‐dimethylbenzoin, 2,4,6‐trimethylbenzoin, 2,3,5,6‐tetramethylbenzoin, and 2,3,4,5,6‐pentamethylbenzoin. The absolute quantitative evaluation of the mass spectra shows a clear difference in the initiation ability of the differently substituted benzoyl‐type radical fragments: Increasing the number of methyl substituents leads to a decrease in incorporation of the radical fragments.     

Radical polymerization of vinyl thiocyanatoacetate: Participation of group‐transfer mechanism

Vinyl thiocyanatoacetate (VTCA) was synthesized, and its radical polymerization behavior was studied in acetone with dimethyl 2,2′‐azobisisobutyrate (MAIB) as an initiator. The initial polymerization rate (R_p) at 60 °C was expressed by R_p = k[MAIB]^0.6±0.1 [VTCA]^1.0±0.1 where k is a rate constant. The overall activation energy of the polymerization was 112 kJ/mol. The number‐average molecular weights of the resulting poly (VTCA)s (1.4–1.6 × 10⁴) were almost independent of the concentrations of the initiator and monomer, indicating chain transfer to the monomer. The chain‐transfer constant to the monomer was estimated to be 9.6 × 10^?3 at 60 °C. According to the ¹H and ¹³C NMR spectra of poly (VTCA), the radical polymerization of VTCA proceeded through normal vinyl addition and intramolecular transfer of the cyano group. The cyano group transfer became progressively more important with decreasing monomer concentration. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 573–582, 2002; DOI 10.1002/pola.10137