Bimolecular Termination Research Articles

Studies on the Termination Behavior of Styrenic Free‐Radicals

AbstractIn order to provide more evidence to understand the termination mechanism in styrene free‐radical polymerization, (1‐bromoethyl) benzene and polystyrene with bromide end group (PSt‐Br) synthesized by atom transfer radical polymerization (ATRP) were used as the model compound and model polymer to study the termination behavior of styrenic radical by atom transfer radical coupling (ATRC), and then the NMR chemical shifts of the head‐to‐head enchainment from coupling termination were obtained. SEC and different NMR measurement methods were used to analyze and characterize the products. It is confirmed that there is no bimolecular disproportionation termination between styrenic free radicals, but only coupling termination to form the head‐to‐head enchainment. The proton and carbon chemical shifts of the head‐to‐head enchainment from coupling termination for (1‐bromoethyl) benzene are 2.7–2.86 ppm and ~47.3 ppm. As for the polystyrene through ATRC from PSt‐Br, the corresponding chemical shifts are 2.61–3.29 ppm and ~46.4 ppm, respectively, they are almost the same as the data in our previous paper (~3.05 ppm, ~46.6 ppm) for polystyrene initiated by BPO, proving that the chain termination in free‐radical polymerization of styrene initiated by BPO occurs through primary termination between chain radical and primary radical rather than bimolecular termination between chain radicals.

Correlation between Critical Energy, Penetration Depth, and Photopolymerization Kinetics in Aluminum–Phosphate–Silicate Hybrid Materials for Vat Photopolymerization

The photopolymerization of aluminum–phosphate–silicate resins obtained from the hybrid sol–gel route for Vat photopolymerization (VPP) process was investigated. The printing parameters derived from Jacob’s work curve model, critical energy (Ec) and penetration depth (Dp), were determined as a function of laser power and MPTMS (silicate) concentration for materials with stoichiometry Si(x)-(Al + P)(1–x), 0 ≤ x ≤ 0.7. The kinetics of photopolymerization was further explored using steady- and unsteady-state photo-DSC experiments. The oxygen inhibition and primary termination had similar contributions to the polymerization process for all compositions, while the propagation and bimolecular termination constants increased with MPTMS concentration. These experimental results were used to test the validity of the Ec ∝ kt1/2/kp and Dp ∝ ϵ relationship derived from a photochemical model for VPP assuming steady-state kinetics. Both Ec ∝ (kt1/2/kp) and Dp ∝ ϵ may be used to predict critical energy and penetration values for an arbitrary resin without calculating its work curve function, according to our study.

Analysis of Dynamic Efficacy Profile of Corneal Cross-Linking: Role of Oxygen and Rate Constants in Type-I and II Processes

Purpose: To explore (theoretically) the key parameters and their influence on the time profiles of photosensitizer (riboflavin), free radicals, singlet oxygen, oxygen and the efficacy of corneal collagen crosslinking (CXL) in both type-I and oxygen-mediated type-II mechanisms, specially the role of oxygen and the initiator regeneration.
 Study Design: Numerical solutions of the rate equation of CXL.
 Place and Duration of Study: New Taipei City, Taiwan, between October, 2021 and November, 2021.
 Methodology: Coupled kinetic equations are derived and numerically solved under the quasi-steady state condition for the 2-pathway mechanisms of CXL. The key parameters explored include (bI, V, Q', K, K',Q,P) and their influence on the time profiles of photosensitizer (riboflavin, C), radicals (R), singlet oxygen(S), oxygen (X) and efficacy (E), parameters of (K,K',Q) define the relative strength of type-I and type-II process. The oxygen depletion profile, X(t), and the associated singlet oxygen, S(t), depend on the parameters of V, Q' and the initial value of oxygen. The coupling strength given by (bI) governs almost all profiles, where b is an effective absorption parameter and I is the UV light intensity.
 Results: Our numerical method for CXL dynamic profiles demonstrated the following important features: (i) Type-I and type-II co exit in CXL, in the presence of oxygen. However, there is no type-II when oxygen is depleted or in a condition without oxygen. (ii) Type-I with bimolecular termination, the radical R(t) is a function of [K'(bIgC)]0.5, leading to the steady-state efficacy given by a scaling law of 1/(bI)0.5, in contract to that of type-II which is almost independent to the light intensity. (iii) The depletion rate (2 to 5 minutes) of X(t) is much faster than that of C(t) (10 to 20 minutes), (iv) The pure type-II profile, has a transition point from straight line to saturating curve and matches the depletion point of singlet oxygen S(t). (v) Improved CXL efficacy of type-I and type-II may be achieved by external supply of photoinitiator (riboflavin) and oxygen, respectively.

Ultraviolet cure kinetics of a low Tg polyurethane acrylate network under varying light intensity and exposure time

We investigated the photopolymerization kinetics of a low glass transition temperature (Tg) urethane acrylate network as a model soft coating system. We used real-time Fourier transform infrared (RT-FTir) spectroscopy to measure the acrylate conversion and fast sampling photorheology to measure the developing mechanical properties during cure. Experiments were conducted using a 395 nm LED ultraviolet (UV) source at different incident intensities ranging from 5 to 200 mW/cm2 at 25 °C. We found that the maximum rate of conversion and rate of complex shear modulus development scaled with incident UV intensity (I0) to an exponent (β) ≈ 0.53. This finding is consistent with the classical prediction of free radical photopolymerization that cure speed should increase to the ½ power of intensity when a bimolecular termination mechanism takes place during the reaction. A consequence of this is that the degree of conversion and complex shear modulus were not constant at a fixed energy dose (I0t) when intensity was varied illustrating that this system does not obey the exposure reciprocity rule. Instead we observed that the degree of cure and rheological properties were a universal function of I0βt. We also found that β increased only slightly throughout the reaction reaching a value of 0.65 at 95% conversion. This result indicates that bimolecular termination was predominant throughout nearly the entire reaction due to a high degree of molecular mobility in this flexible network.

One-pot strategy for obtaining magnetic PMMA particles through ATRP using Fe(CO)5 as co-initiator

The first aim of this study was to develop an ATRP process for methyl methacrylate (MMA) polymerization using Fe(CO)5 as co-initiator. The kinetics analysis of the reaction in solution confirmed the controlled characteristic of the polymerization process. The process displays a slow initiation step and presents bimolecular termination reactions at higher molecular weights, confirmed by NMR analysis. Also, these observations are sustained by GPC, FT-IR, and XPS analyses, explaining the rather unusual dispersity values (1.4) for an ATRP reaction. The use of formic acid, which shifts the equilibrium towards Fe2+ species affording a quasi-controlled controlled polymerization process, is a key element in achieving control over the reaction. The Fe2+/Fe3+ ratio at the end of the reaction, determined by XPS analysis, suggests the possibility to generate magnetic iron oxide particles. Therefore, the synthesis strategy was adapted for use in the suspension polymerization process of MMA which permitted the production of magnetic PMMA particles through a facile one-pot approach, using only an ammonia treatment stage. The obtained PMMA particles, characterized by SEM, XPS, TEM, TGA, and XRD analyses, have porous characteristics and magnetic properties which makes them good candidates as catalyst supports, separation processes, or biomedical applications.

Mathematical Modeling of 1, 3-Butadiene Polymerization Initiated by Hydrogen Peroxide

In this study, the modeling of polymerization of 1, 3-butadiene in the presence of hydrogen peroxide has been reported for the first time. For this purpose, the Method of double moments was applied. The modeling has been performed to investigate the effect of reaction condition on the properties of synthesized Polybutadiene, and the role of kinetic coefficients on the output of model i.e. sensitivity analysis. A comprehensive kinetic model was developed based on previous experimental studies. Then, the moment and population balance of the reactants were obtained. Modeling results were used to study the role of initiator concentration and the type of solvent in polymerization kinetics and final polymer properties. In addition, the sensitivity of modeling results in a transfer to the initiator, radical coupling, and finally transfer to polymer reactions was investigated. This study opens a way for the engineering of manufacturing the Hydroxyl-Terminated PolyButadiene (HTPB) process to obtain the desired products with optimized reaction conditions. Results show that initiator concentration and type of solvent are important in polymerization kinetics and properties of HTPBs. A higher amount of initiator increases radical concentration and consequently rates of bimolecular termination and at the lower level, rate of propagation, and polymer double bonds reactions.

Study of polymerization kinetics and copolymerization behavior ofN‐[3‐(dimethylamino)propyl]methacryamide and cationic surfmers

AbstractGas flotation is one of the important technologies for oily wastewater treatment and the surface‐active polymer is an important kind of developing flotation agents. In this article, the flotation performance, polymerization kinetics, and copolymerization behavior of surface‐active copolymer ofN‐[3‐(dimethylamino) propyl] methacrylamide (DMAPMA) and dodecyl dimethyl propenyl ammonium chloride (C12DM) and copolymer of DMAPMA and decyl dimethyl vinylbenzyl ammonium chloride(C10MVBA) were investigated. The flotation experiment showed that both copolymers had an oil removal of 97% at the concentration of 30 mg/L. The result of polymerization kinetics showed that the polymerization initiation rate was influenced by the monomer concentration and the polymerization termination was dominated by bimolecular termination and accompanied by unimolecular termination. The activation energy of DMAPMA‐C12DM copolymerization (89.64 kJ/mol) was smaller than that of DMAPMA‐C10MVBA (91.65 kJ/mol) copolymerization. The reactivity ratios of DMAPMA and C12DM were 0.46 and 15.52, respectively, as well as the reactivity ratios of DMAPMA and C10MVBA were 1.19 and 35.77, respectively. These results are meaningful for the oily wastewater flotation and the copolymerization mechanism of DMAPMA‐based copolymer.

Reversible inhibition in the formation of copolymers based on alkyl (meth)acrylates with vinyl butyl ethers under compensation of the active monomer depending on their nature when initiated by the triethylborane–oxygen system

Compensatory (or compensation) copolymerization of alkyl (meth)acrylates (AMA) with boiling vinyl butyl ether (VBE), initiated by the system of triethylborane (TEB)–oxygen, has been studied. The obtained data indicate a partial formation of copolymer macromolecules with close to an alternating structure, according to the reversible inhibition mechanism, along with a copolymer formation on the scheme of conventional bimolecular termination. Specific features of used acrylic monomers have been revealed. Copolymers of methyl methacrylate (MMA) and VBE were applied as macroinitiators for block-copolymer syntheses when adding new portions of butyl acrylate (BA).

Effect of UV-curing conditions on the polymer structures: a comparison between coating and adhesive

Radical photopolymerization of acrylate was carried out without a degassing process under conditions suitable for UV-curable coatings and UV-curable adhesives. We examined the differences in the resulting polymer structures obtained from the coating and adhesive by employing the same formulation. 2,2-Dimethoxy-2-phenylacetophenone was employed as a photoinitiator. The UV-curable coating yielded polymers terminated by either a hydroxyl group or a terminal carbonyl group as the main products. On the other hand, the UV-curable adhesive yielded a multitude of polymers that were terminated by disproportionation. In the latter case, some polymers underwent hydrogen abstraction from the polymer backbone, resulting in β-scission of the midchain radical to generate polymers with an α-substituted acryloyl group as the terminal group. We examined the differences between the resulting polymer structures in the cases of a coating and an adhesive employing the same formulation. The UV-curable coating yielded polymers terminated by either a hydroxyl group or a terminal carbonyl group as the main products, suggesting that bimolecular termination was strongly inhibited by oxygen. On the other hand, the UV-curable adhesive yielded a multitude of disproportionation products, whereas some polymers underwent hydrogen abstraction from the polymer backbone, resulting in β-scission of the midchain radical to generate polymers with an α-substituted acryloyl group.

Enhanced municipal sludge dewaterability using an amphiphilic microblocked cationic polyacrylamide synthesized through ultrasonic-initiation: Copolymerization and flocculation mechanisms

Flocculation is an important pretreatment technique for sludge dewatering, the performance of employed flocculants is the key factor determine the flocculation efficiency. Herein, an amphiphilic cationic polyacrylamide (CPAM) with microblock structure was synthesized through template copolymerization initiated by ultrasonic. The chemical components and cationic microblock structure of copolymers were confirmed through comparative characterization by Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (1H NMR) spectrum. The copolymerization mechanism was investigated through kinetics study and association coefficient (KM) determination. The results indicated that the reaction followed free radical copolymerization and terminated mainly through bimolecular termination. The pre-adsorption between acryloyloxyethyltrimethylammonium chloride (DAC) and sodium polyacrylate (NaPAA) before reaction confirmed the template polymerization met the type I (ZIP) mechanism. Cationic microblocks and hydrophobic association together contributed to the optimal dewaterability (FCMC=67.2 %, SRF=3.84×1012 m·kg−1) using TP(AM-DAC-LA). Hydrophobic association enhanced bridging and sweeping effect to promote the floc size growth. Cationic microblocks produced compacter flocs with stronger mechanical strength through enhanced charge neutralization and patching effects, which acted as skeletons to make filter cakes less compressible and more permeable in mechanical dewatering. This work developed a highly effective flocculant for sludge dewatering, the synthesis and working mechanism of which were also given.

Does bimolecular termination dominate in benzoyl peroxide initiated styrene free-radical polymerization?

It is believed that polymer chains mainly terminate through bimolecular termination in free-radical polymerization, however, there is few convincing evidence to support it. In benzoyl peroxide (BPO) initiated styrene free-radical polymerization, our studies demonstrate that polymer chain terminates dominantly through primary radical termination rather than by bimolecular termination as described in polymer textbooks. Even at very high primary radical concentration or at very low monomer concentration, primary radical termination still dominates (FPRT&CTI>70%) besides the occurrence of some bimolecular coupling terminations. Two kinds of model polymers were prepared, one for bimolecular coupling termination, and the other for primary radical termination. The 1H-, 13C-, DEPT135-, and 2D HSQC NMR spectra of the polystyrene initiated by BPO are almost the same as those of the model polystyrene for primary radical termination, but they are quite different from those of the model polystyrene for bimolecular coupling termination, demonstrating directly that primary radical termination rather than bimolecular coupling termination dominates in BPO-initiated styrene free-radical polymerization.

Modeling the Kinetics, Curing Depth, and Efficacy of Radical-Mediated Photopolymerization: The Role of Oxygen Inhibition, Viscosity, and Dynamic Light Intensity.

Kinetic equations for a modeling system with type-I radical-mediated and type-II oxygen-mediated pathways are derived and numerically solved for the photopolymerization efficacy and curing depth, under the quasi-steady state assumption, and bimolecular termination. We show that photopolymerization efficacy is an increasing function of photosensitizer (PS) concentration (C0) and the light dose at transient state, but it is a decreasing function of the light intensity, scaled by [C0/I0]0.5 at steady state. The curing (or cross-link) depth is an increasing function of C0 and light dose (time × intensity), but it is a decreasing function of the oxygen concentration, viscosity effect, and oxygen external supply rate. Higher intensity results in a faster depletion of PS and oxygen. For optically thick polymers (>100 um), light intensity is an increasing function of time due to PS depletion, which cannot be neglected. With oxygen inhibition effect, the efficacy temporal profile has an induction time defined by the oxygen depletion rate. Efficacy is also an increasing function of the effective rate constant, K = k′/, defined by the radical producing rate (k′) and the bimolecular termination rate (kT). In conclusion, the curing depth has a non-linear dependence on the PS concentration, light intensity, and dose and a decreasing function of the oxygen inhibition effect. Efficacy is scaled by [C0/I0]0.5 at steady state. Analytic formulas for the efficacy and curing depth are derived, for the first time, and utilized to analyze the measured pillar height in microfabrication. Finally, various strategies for improved efficacy and curing depth are discussed.

Thiol–Ene Photopolymerization: Scaling Law and Analytical Formulas for Conversion Based on Kinetic Rate and Thiol–Ene Molar Ratio

Kinetics and analytical formulas for radical-mediated thiol–ene photopolymerization were developed in this paper. The conversion efficacy of thiol–ene systems was studied for various propagation to chain transfer kinetic rate-ratio (RK), and thiol–ene concentration molar-ratio (RC). Numerical data were analyzed using analytical formulas and compared with the experimental data. We demonstrated that our model for a thiol–acrylate system with homopolymerization effects, and for a thiol–norbornene system with viscosity effects, fit much better with the measured data than a previous model excluding these effects. The general features for the roles of RK and RC on the conversion efficacy of thiol (CT) and ene (CV) are: (i) for RK = 1, CV and CT have the same temporal profiles, but have a reversed dependence on RC; (ii) for RK >> 1, CT are almost independent of RC; (iii) for RK << 1, CV and CT have the same profiles and both are decreasing functions of the homopolymerization effects defined by kCV; (iv) viscosity does not affect the efficacy in the case of RK >> 1, but reduces the efficacy of CV for other values of RK. For a fixed light dose, higher light intensity has a higher transient efficacy but a lower steady-state conversion, resulting from a bimolecular termination. In contrast, in type II unimolecular termination, the conversion is mainly governed by the light dose rather than its intensity. For optically thick polymers, the light intensity increases with time due to photoinitiator depletion, and thus the assumption of constant photoinitiator concentration (as in most previous models) suffers an error of 5% to 20% (underestimated) of the crosslink depth and the efficacy. Scaling law for the overall reaction order, defined by [A]m[B]n and governed by the types of ene and the rate ratio is discussed herein. The dual ratio (RK and RC) for various binary functional groups (thiol–vinyl, thiol–acrylate, and thiol–norbornene) may be tailored to minimize side effects for maximal monomer conversion or tunable degree of crosslinking.

Kinetics of Enhancement for Corneal Cross-linking: Proposed Model for a Two-initiator System

Aims: To derive kinetic equations and analytic formulas for efficacy enhancement of corneal collagen crosslinking (CXL) in a 2-initiator system.&#x0D; Study Design: Modeling the kinetics of CXL.&#x0D; Place and Duration of Study: Taipei, Taiwan, between between January 2019 to June, 2019.&#x0D; Methodology: Coupled rate equations are derived for two initiators system for a type-II process, consisting of a primary initiator (PA), and a co-initiator (PB) as an enhancer, having 3 cross linking pathways: Two radical-mediated (or electron transfer) pathways, and one oxygen-mediated (or energy transfer) pathway. For a type-II process, the triplet state T* interacts with the co-initiator, PB, to form the primary radicals R’, and an active intermediates radical, R, which could interact with the substrate [M] for crosslink, or be inhibited by oxygen [O2], or bimolecular termination. Rate equations, based on lifetime of triplet-state and oxygen singlet-state, are used to analyze the measured results in a rose-Bengal system with an enhanced initiator.&#x0D; Results: Additive enhancer-monomer of arginine added to a rose Bengal photosensitizer may enhance the production of free radicals under a green-light CXL. D2O may extends the lifetime of oxygen singlet state and thus improve the efficacy. Our formulas predicted features are consistent with the measured results.&#x0D; Conclusion: Efficacy may be improved by enhancer-monomer or extended lifetime of photosensitizer triplet-state or oxygen singlet state.

Effect of temperature on the formation of highly oxygenated organic molecules (HOMs) from alpha-pinene ozonolysis

Abstract. Highly oxygenated organic molecules (HOMs) are important contributors to secondary organic aerosol (SOA) and new-particle formation (NPF) in the boreal atmosphere. This newly discovered class of molecules is efficiently formed from atmospheric oxidation of biogenic volatile organic compounds (VOCs), such as monoterpenes, through a process called autoxidation. This process, in which peroxy-radical intermediates isomerize to allow addition of molecular oxygen, is expected to be highly temperature-dependent. Here, we studied the dynamics of HOM formation during α-pinene ozonolysis experiments performed at three different temperatures, 20, 0 and −15 ∘C, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50 ppb α-pinene and 100 ppb ozone), decreased considerably at lower temperature, with molar yields dropping by around a factor of 50 when experiments were performed at 0 ∘C, compared to 20 ∘C. At −15 ∘C, the HOM signals were already close to the detection limit of the nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer used for measuring gas-phase HOMs. Surprisingly, comparing spectra measured at 0 and 20 ∘C, ratios between HOMs of different oxidation levels, e.g., the typical HOM products C10H14O7, C10H14O9, and C10H14O11, changed considerably less than the total HOM yields. More oxidized species have undergone more isomerization steps; yet, at lower temperature, they did not decrease more than the less oxidized species. One possible explanation is that the primary rate-limiting steps forming these HOMs occur before the products become oxygenated enough to be detected by our CI-APi-TOF (i.e., typically seven or more oxygen atoms). The strong temperature dependence of HOM formation was observed under temperatures highly relevant to the boreal forest, but the exact magnitude of this effect in the atmosphere will be much more complex: the fate of peroxy radicals is a competition between autoxidation (influenced by temperature and VOC type) and bimolecular termination pathways (influenced mainly by concentration of reaction partners). While the temperature influence is likely smaller in the boreal atmosphere than in our chamber, both the magnitude and complexity of this effect clearly deserve more consideration in future studies in order to estimate the ultimate role of HOMs on SOA and NPF under different atmospheric conditions.

Exploitation of Compartmentalization in RAFT Miniemulsion Polymerization to Increase the Degree of Livingness

ABSTRACTIt is demonstrated that the degree of livingness (chain‐end fidelity) in RAFT polymerization for a given degree of polymerization can be markedly increased in miniemulsion polymerization relative to the corresponding homogeneous bulk system. Polymerization of styrene was conducted using a poly(methyl methacrylate) benzodithioate as macroRAFT agent in both miniemulsion and bulk. The substantially higher polymerization rate in miniemulsion, which is attributed to the segregation effect (compartmentalization) causing a reduction in the rate of bimolecular termination, makes it possible to reach a given degree of polymerization in a significantly shorter time than in the corresponding bulk system. As a consequence, fewer initiating radicals are required throughout the polymerization, leading to higher livingness in the more rapid miniemulsion system. It is demonstrated how this approach facilitates synthesis of high‐molecular‐weight block copolymers comprising slowly propagating monomers such as styrene and methacrylates. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1938–1946

Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring.

Polymer brush coatings are frequently prepared by radical polymerization, a notoriously oxygen sensitive process. Glucose oxidase (GOx) can inexpensively enable radical polymerization in solution by enzymatically consuming oxygen as it oxidizes glucose. Here, we report the growth of polymeric brushes using GOx-assisted atom transfer radical polymerization (ATRP) from a surface while open to air. Specifically, we grew a set of biomedically relevant polymer brushes, including poly(oligo(ethylene glycol) methacrylate) (POEGMA), poly(2-dimethylaminoethyl methacrylate) (PDMAEMA), poly(sulfobetaine methacrylate) (PSBMA), and poly(2-(methylsulfinyl)ethyl acrylate (PMSEA). For each of these polymers, we monitored GOx-assisted and GOx-free ATRP reaction kinetics in real time using quartz crystal microbalance (QCM) and verified findings with localized surface plasmon resonance (LSPR). We modeled brush growth kinetics considering bimolecular termination. This model fit our data well ( r2 > 0.987 for all samples) and shows the addition of GOx increased effective kinetic chain lengths, propagation rates, and reproducibility. We tested the antifouling properties of the polymer brush coatings against human blood plasma and were surprised to find that coatings prepared with GOx repelled more plasma proteins in all cases than their GOx-free counterparts.

Experimental and theoretical investigations of free radical photopolymerization: Inhibition and termination reactions

In this work, the inhibition and termination reactions occurring throughout a free radical photopolymerization initiated by a type-I photoinitiator are studied by kinetic modeling. The role of the macroradicals as the main oxygen trapping agents during the inhibition time is identified, and the absence of primary radical consumption by oxygen can be related to a high initiation efficiency at early times. The ratio of the termination reactions reveals that bimolecular termination remains the principal pathway for the cessation of macromolecule growth, even at high polymer conversion. Moreover, the evolution of the termination ratio during the polymerization can be correlated to both the diffusional control of the polymerization reactions as the polymer network grows and the photoinitiator consumption. Finally, the effect of the incident light intensity and the initial photoinitiator concentration on the termination reactions is assessed, and the validity of the steady-state assumption applied to the macroradical concentration discussed.

Determination of homopolymerization kinetics and copolymerization with methyl methacrylate of diethyl 9-(methacryloyloxy)-2-oxo-nonylphosphonate, 9-(methacryloyloxy)-2-oxo-nonylphosphonic acid and diethyl 9-(methacryloyloxy)-nonylphosphonate

AbstractThe three polymerizable monomers diethyl 9-(methacryloyloxy)-2-oxo-nonylphosphonate M1, 9-(methacryloyloxy)-2-oxo-nonylphosphonic acid M2 and diethyl 9-(methacryloyloxy)-nonylphosphonate M3 are examined for their free radical polymerization and copolymerization activity in methanol between 40 and 65°C. Polymerization proceeds readily through a thermal free radical initiation. The intensity exponents for the monomer and initiator are only slightly over 1 and approximately 0.5, respectively. This is in accordance with the results typically observed for an ideal free radical polymerization with bimolecular termination. The kinetics of copolymerization with methyl methacrylate (MMA) are monitored by online 1H nuclear magnetic resonance (NMR) spectroscopy. Two copolymerization reactions for each pair of co-monomers are sufficient 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.

Disproportionation or Combination? The Termination of Acrylate Radicals in ATRP

The termination of acrylate radicals in atom transfer radical polymerization (ATRP) can involve either conventional bimolecular radical termination (RT) or catalytic radical termination (CRT). These processes were investigated using a poly(methyl acrylate)–Br macroinitiator under different initial conditions tuned to change the RT/CRT ratio. The polymers, obtained from alkyl halide chain-end activation by [CuI(L)]+ (L = tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA), or tris(3,5-dimethyl-4-methoxy-2-pyridylmethyl)amine (TPMA*3)) in the absence of monomer, were analyzed by size exclusion chromatography (SEC). RT-promoting conditions resulted in the increase of a shoulder with double molecular weight (MW) relative to the macroinitiator distribution, indicating that RT occurred predominantly via radical combination. Conversely, when CRT was promoted, the macroinitiator distribution did not shift, indicating a disproportionation-like pathway. The termination reactions for the T...