Investigation of the photoinitiation of methyl methacrylate polymerization by 2-morpholino acetonaphthone

2-Morpholino acetonaphthone (MPM) was synthesized as a cleavable photoinitiator and the structure of the photoinitiator was confirmed by spectral and elemental analysis. The photoinitiation capability of MPM was demonstrated by using methyl methacrylate and a formulation containing multifunctional monomers.     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Poly(methyl methacrylate)/POSS hybrid networks by type II photoinitiated free radical polymerization

A new strategy for organic–inorganic hybrid networks is presented through in‐situ Type II photoinitiated polymerization of methyl methacrylate with diethanolamino‐functionalized polyhedral oligomeric silsesquioxanes (POSS‐DEA). The diethanolamino groups are simply incorporated onto POSS nanoparticles by nucleophilic ring‐opening reaction of commercially available epoxycyclohexyl POSS and diethanol amine. The photoinitiated polymerization of methyl methacrylate in the presence of benzophenone as photosensitizer and POSS‐DEA as hydrogen donor leads to poly(methyl methacrylate) (PMMA)/POSS hybrid networks under UV light irradiation. The morphology and thermal properties of hybrid networks are investigated by using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy. The morphology results confirm that POSS cages are homogeneously distributed in PMMA matrix at the molecular levels, whereas the thermal analyses shows that the obtained hybrid networks have higher glass transition temperatures and better thermal stabilities compared to parent PMMA homopolymer. POLYM. COMPOS., 35:1614–1620, 2014. © 2013 Society of Plastics Engineers     

The mixing effect on the free radical MMA solution polymerization

Mathematical models of reactors for the polymerization of methylmethacrylate (MMA) have been developed and analyzed to elucidate reactor dynamics and to determine conditions for improved operation. The effects of mixing and heat transfer in an MMA polymerization reactor system have been explored by the development of an imperfect mixing model. To model imperfect mixing in polymerization, a reactor configuration using two tanks in parallel was used. Bifurcation diagrams developed using numerical analysis of the model have been drawn with two variable parameters, an exchange ratio, σ, and a volume ratio, κ. We use feed and coolant temperatures as bifurcation parameters. If variable parameters are small, the lower solution branch of the steady state solutions is quite different from that of a simple model that assumes perfect macro-mixing as bifurcation parameters change. If σ increases (κ=0.1, σ=1.0), the shape of a steady state solution curve differs significantly from that of a simple model as the feed temperature decreases.     

Modelling of free radical polymerization of styrene and methyl methacrylate by a tetrafunctional initiator

A mathematical model for free radical polymerizations initiated by tetrafunctional initiators is described in detail with comparisons to experimental results. Reactions involving the fate/efficiency of functional groups are properly accounted for, while in the past, kinetic models for difunctional initiators found in the literature have ignored this. Free volume theory is used to describe the diffusion-controlled regime. Based on model predictions, multi-radical concentrations were estimated to be several orders of magnitude smaller than mono-radical concentrations. Through various case studies, the model was able to demonstrate that the concentration and chain length of various polymer structures (i.e., linear, star or coupled stars) depend upon monomer type and reaction conditions. The model was found to be useful in explaining experimentally observed differences in the behaviour of a tetrafunctional initiator with styrene compared to methyl methacrylate (MMA). In both cases, higher reaction rates could be obtained when switching from a mono- to a tetrafunctional initiator; however, the influence on molecular weight was found to vary between the two systems. Work with styrene showed similar trends as with difunctional initiators, where the tetrafunctional initiator maintained similar molecular weights compared to a monofunctional initiator. Yet, for MMA, replacing the monofunctional initiator with its tetrafunctional counterpart decreased the molecular weight.     

Photoinitiated free radical polymerization of methylmethacrylate by using of quinoxalines in the presence of aldehydes

A series of quinoxalines at different concentrations were used in the presence of benzaldehyde (BA) and phthaldialdehyde (PDA) to initiate the polymerization of methylmethacrylate (MMA) formulation containing 2-ethyl-2-(hydroxymethyl)-1,3-propanediol-trimethylmethacrylate (TMPTMA) as a multifunctional acrylate. Highest conversion percentage of polymerization of MMA were obtained in the presence of benzaldehyde when diphenylquinoxaline, phenanthroquinoxaline and acenaphthoquinoxaline were used as an initiator. In the case of benzaldehyde, benzoyl radical were possibly responsible for the initiation of polymerization where quinoxalines do not initiate polymerization of acrylates in the presence of oxygen.     

Modeling methyl methacrylate free radical polymerization in nanoporous confinement

Nanoconfinement of methyl methacrylate free radical polymerization is known to impact the molecular weight and molecular weight distribution of the polymer produced, with results in the literature generally indicating an increase in molecular weight and a concomitant decrease in polydispersity index. In the present work, the mathematical model described by Verros et al. (2005) for free radical bulk polymerization of methyl methacrylate is extended to account for polymerization in nanopores. The model of Verros et al. (2005) incorporates diffusion effects and is capable of describing the conversion and the number- and weight-average molecular weights of the resulting poly(methyl methacrylate) as a function of polymerization time and process conditions. The model is extended by incorporating the effect of nanoconfinement on diffusivity using the scaling reported in the literature. The calculations indicate that nanoconfinement will lead to higher molecular weights and lower polydispersity, and the gel effect will occur earlier. The results are compared to experimental work and implications discussed.     

Visible light induced photopolymerization: speeding up the rate of polymerization by using co-initiators in dye/amine photoinitiating systems

The activity of six newly designed three-component systems (containing a dye, an amine and a triazine derivative) for the initiation of the photopolymerization of multifunctional acrylates under visible light has been evaluated. The selection of the dyes was based on thermodynamic considerations. A discussion of the photochemical reactivity of these systems reveals the role played by thermodynamics and outlines different aspects concerned with kinetics.     

Modeling the free radical solution and bulk polymerization of methyl methacrylate

This paper reviews our current understanding of the kinetics and mechanisms of free-radical chain polymerization of methyl methacrylate. A mathematical model previously proposed to describe the bulk polymerization of MMA is here extended to cover solution polymerization. This extended model is validated by comparing its predictions with experimental data over a range of conversions and product molecular weights.     

Photochemically masked benzophenone: Photoinitiated free radical polymerization by using benzodioxinone

A new photoinitiating system for free radical polymerization of methyl methacrylate (MMA) is reported. This system consists of benzodioxinone and hydrogen donors such as triethylamine (TEA), N,N-dimethyl ethanol amine (DMEA) and tetrahydrofuran (THF). A feasible mechanism involves photoinduced formation of benzophenone from benzodioxinone and subsequent hydrogen abstraction of photoexcited benzophenone from hydrogen donors to yield radicals capable of initiating polymerization of MMA.     

Modeling methyl methacrylate free radical polymerization: Reaction in hydrophobic nanopores

Free radical polymerization of methyl methacrylate in nanopores has been shown to result in a decrease in the time for the onset of autoacceleration. In this work, we simplify our previous kinetic model of nanoconfined methyl methacrylate polymerization, which was based on the work of Verros and coworkers, and incorporate diffusion effects into the model using the Doolittle free volume theory. The simplified model well describes the experimental calorimetric conversion versus time data for isothermal bulk methyl methacrylate polymerization, capturing autoacceleration and the dependence of the limiting conversion on temperature. In order to model the reaction in nanopores, we assume that the diffusion coefficient scales with molecular size to the ?3 power and with nanopore diameter to the 1.3 power. Experimental calorimetric conversion versus time data for polymerization in hydrophobic nanopores are well captured by the model, including the decrease in the time to reach autoacceleration with decreasing pore size. The scaling assumed is consistent with that predicted using molecular simulations for good solvent conditions by Avramova and Milchev and by Cui, Ding, and Chen. According to the fit of the experimental data, chain diffusivity is 20–50% of the bulk value in 13 nm-diameter pores.     

The influence of oxide nanoparticles on the kinetics of free radical methyl methacrylate polymerization in bulk

A series of poly(methyl methacrylate) (PMMA) nanocomposites were synthesized using free radical polymerization in bulk, by addition of 1 vol% of oxide nanoparticles (silica, alumina, and titania), differing in the nature and type. The influence of nanofiller presence on the kinetics of methyl methacrylate (MMA) free radical polymerization was investigated. For this purpose, the kinetic model that includes the contribution from the first‐order reaction and the autoacceleration was applied on data obtained following the isothermal polymerization at 70°C by differential scanning calorimetry (DSC). The effect of the size and the surface nature of nanofillers on the interfacial layer thickness (d), as well as the influence of d on the glass transition temperature (T_g) of PMMA hybrid materials was studied. It was found that hydrophilic particles accelerated the initiator decomposition and affected the monomer polymerization on the surface, which caused the formation of thicker interfacial layer compared to the one around hydrophobic fillers. The addition of smaller nanoparticles size decreased the glass transition temperature of pure poly(methyl metacrylate). The linear increase of PMMA T_g value with increasing the polymeric interfacial layer was determined. The T_g values of pure PMMA and PMMA nanocomposite with d of 1.4 nm were estimated to be the same. POLYM. COMPOS. 34:1342–1348, 2013. © 2013 Society of Plastics Engineers     

Addition-fragmentation of 5-bromopenta-1,3-diene in free radical polymerization of methyl methacrylate

5-Bromopenta-1,3-diene (BPD) was examined as an addition-fragmentation chain transfer agent (AFCTA) in the free radical polymerization of methyl methacrylate (MMA). Studies of the kinetics of polymerization in the presence of this compound showed it to be a very effective chain transfer agent and that retardation was not significant, implying efficient reinitiation by the expelled Br radical. Analysis of the resulting polymers showed that the intermediate radical formed by the addition of the propagating radical to the C₁ carbon of BPD underwent exclusive fragmentation. However, addition on the C₄ carbon, with a relative probability of 0·6, led to its copolymerization with MMA. Kinetic studies showed BPD to be a better chain-end functionalization agent than its 5-t-butyl thio derivative for deriving pentadiene-functional macromonomer. © 1998 SCI.     

The effect of amines on the polymerization of methyl methacrylate

Different amines, namely N-isopropylmorpholine, N-isopropylpyrrolidine, N-isopropylpiperidine, and 1,3-dimorpholinopropane were synthesised and they were used with type I and type II photoinitiators in the polymerization of methyl methacrylate. Their efficiency was compared with that of N-methyldiethanolamine (NMDEA), which is a well known synergist, and it was found that 1,3-dimorpholinopropane worked as well as NMDEA. High concentrations of N-isopropylpyrrolidine and 1,3-dimorpholinopropane lead to an increase in the rate of polymerization of methyl methacrylate.     

Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)

Living free radical polymerization technology (macromolecular design via the interchange of xanthates (MADIX)) was applied to give accesses to chain length and conversion dependent termination rate coefficients of vinyl acetate (VAc) at 80 °C using the MADIX agent 2-ethoxythiocarbonylsulfanyl-propionic acid methyl ester (EPAME). The kinetic data were verified and probed by simulations using the PREDICI^® modelling package. The reversible addition-fragmentation transfer (RAFT) chain length dependent termination (CLD-T) methodology can be applied using a monomer reaction order of unity, since VAc displays significantly lower monomer reaction orders than those observed in acrylate systems (ω(VAc, 80 °C)=1.17±0.05). The observed monomer reaction order for VAc is assigned to chain length dependent termination and a low presence of transfer reactions. The α value for the chain length regime of log(i)=1.25−3.25 (in the often employed expression ) reads 0.09±0.05 at low monomer to polymer conversion (10%) and increases significantly towards larger conversions (α=0.55±0.05 at 80%). Concomitantly with a lesser amount of midchain radicals, the chain length dependence of k_t is significantly less pronounced in the VAc system than in the corresponding acrylate systems under identical reaction conditions. The RAFT(MADIX)-CLD-T technique also allows for mapping of k_t as a function of conversion at constant chain lengths. Similar to observations made earlier with methyl acrylate, the decrease of k_t with conversion is more pronounced at increased chain lengths, with a strong decrease in k_t exceeding two logarithmic units from 10 to 80% conversion at chain lengths exceeding 1800.     

Development of a comprehensive mathematical model for free radical suspension polymerization of methyl methacrylate

In this work a detailed mathematical model for free radical suspension polymerization of methyl methacrylate (MMA) in water is developed. This model is based on sound principles such as the free volume theory to account for the diffusion limited reactions in suspension polymerization. Additionally, the complex polymerization kinetics process of the aqueous suspension polymerization of MMA is studied as a one‐dimensional numerical experiment. For this purpose, the polymerization process is modeled as a moving boundary mass transfer problem coupled with polymerization reactions. The Galerkin finite element method is used to simultaneously solve the nonlinear governing equations. The model predictions for conversion and average molecular weights vs. time were found to be in close agreement with laboratory data. It is believed that this work, as it provides fundamental understanding of the process, it might contribute to a more rational design of polymerization reactors. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Effect of LiClO4 on radical polymerization of methyl methacrylate

The effect of LiClO₄ on the polymerization of methyl methacrylate (MMA) with dimethyl 2,2′-azobisisobutyrate (MAIB) was investigated at 50°C in methyl ethyl ketone. The polymerization proceeded homogeneously even at [LiClO₄] as high as 3.00 mol/L. The polymerization rate (R_p) and the molecular weight of the resulting polymer profoundly increased with increasing [LiClO₄]. R_p at 3.00 mol/L [LiClO₄] was 12 times that in the absence of LiClO₄. The rate equation depended on the presence or absence of LiClO₄: R_p = k′[MAIB]^0.5 [MMA]^1.5 in the presence of 3.00 mol/L [LiClO₄] and R_p = k[MAIB]^0.5 [MMA]^1.0 in the absence of LiClO₄. The overall activation energies of polymerization were 38.5 kJ/mol in the presence of 3.00 mol/L [LiClO₄] and 77.4 kJ/mol in the absence of LiClO₄, respectively. The tacticities of resulting poly(MMA) were insensitive to the presence of LiClO₄. In the copolymerization of MMA and styrene, Q and e values of MMA increased with increasing [LiClO₄], leading to enhanced alternating copolymerizability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1361–1368, 1997     

Pseudohalogens in atom transfer radical polymerization of methyl methacrylate

In recent advances in controlled radical polymerization, atom transfer radical polymerization (ATRP) has achieved increasing interest. This investigation reports the ATRP of methyl methacrylate (MMA) using pseudohalogens as initiator as well as an anion for copper catalyst. The results were compared with the conventional halide system. Different pseudohalides were used as the initiator for the ATRP of MMA in combination with CuX (X = pseudohalide or halide) as the catalyst. Pseudohalide initiator in combination with Cu(halide) catalyst leads to inefficient ATRP due to slow initiation. Pseudohalide initiator in combination with Cu(pseudohalide) catalyst leads to uncontrolled or no polymerization. The polymers were characterized by using GPC, IR, MALDI‐TOF‐MS, and TGA analysis. IR and MALDI analysis showed that the resultant polymer had pseudohalide as the end group. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3857–3864, 2007     

甲基丙烯酸甲酯-甲基丙烯酸三氟乙酯共聚物细乳液的合成及其表征

以甲基丙烯酸甲酯(MMA)和甲基丙烯酸三氟乙酯(TFEMA)为反应单体进行细乳液聚合,制得了MMA-co-TFEMA共聚物乳液。利用FTIR和GPC表征了共聚物的结构和分子量,采用激光光散射法及透射电镜对乳胶粒子的粒径大小及形貌进行了表征,并通过接触角法对共聚物膜的表面性能进行了研究。结果表明,与常规乳液相比,以细乳液方法制得的MMA-co-TFEMA共聚物乳液稳定性好,粒径分布窄,聚合物的分子量分布窄,并且共聚物膜随着氟含量的增加疏水疏油性增强,表面能降低。     

Free radical polymerization of methyl methacrylate at high temperatures

Free-radical polymerization of methyl methacrylate in a tubular reactor has been conducted at above-Tg temperatures. A salient feature of these experiments is the very efficient control of reactor temperature by vapor-liquid equilibrium of the polymerizing mixture via monomer evaporation. The system pressure thus provides a powerful control variable, restricting the temperature in the entire reactor by changing the monomer evaporation rate. In the range of our experimental conditions, the temperature and pressure in the reactor follow the Antoine equation closely. High temperature runs also reduce the length requirement of the reactor. However, molecular weight averages of the products are not impressive, unless slow-burning initiators are used. Modeling of above-Tg reactions has been attempted at two-levels of sophistication. A plug-flow model gives predictions in good agreement with our experimental temperatures and conversion data. The predicted molecular weights are also consistent with the experimentally observed values. However, the more elaborate rheokinctic model suggests that the superficial agreement between model and experiment is due to initiator burn-out, which limits the final conversion to within 40 percent. The liquid layer next to the reactor wall can never be so viscous as to form a stagnant deposit, due to this conversion limitation. The velocity profiles are thus not very much distorted, and a plug-flow model is adequate. With a slow-burning initiator and a sufficiently long reactor, skewing of velocity profile and reactor channeling will eventually emerge. Hence, the rheokinetic model must be evoked to model the system under such conditions.