Emulsion Polymerization of Styrene Mediated by TEMPO at Low Temperature

NMRP is a controlled polymerization technique with the ability to produce polymers with a highly controlled microstructure. The properties of the thus obtained polymers make it desirable to scale this technique to an industrial level, but there are still some challenges to be faced, e.g., to develop emulsion NMRP at low temperatures (lower than about 100 °C) with inexpensive, commercially available nitroxides such as TEMPO. Here, the emulsion NMRP of styrene using TEMPO at temperatures lower than 100 °C is described. An optimal control of molecular weights and polydispersities and a fast polymerization rate are obtained.

     

Kinetics of Stable Free Radical Mediated Polymerization inside Submicron Particles

Controlled/living radical polymerization systems in which the active period is extremely small, ϕ_A ≪ 1, such as the cases of stable free radical mediated polymerization (or nitroxide mediated polymerization) and atom transfer radical polymerization, are considered theoretically. The polymerization rate, R_p, for such systems increases by lowering the trapping agent concentration [X]. When the polymerization is conducted inside small particles, R_p decreases with D below the diameter D_p,SMC at which a single molecule concentration (SMC) is equal to [X]_bulk. On the other hand, when the average number of trapping agents in a particle is smaller than about 10, the fluctuation of n_X among particles is significant, which leads to a larger R_p than in the cases where all particles contain the same n_X. Because of the effects of SMC and fluctuation, R_p may show an acceleration window, D_p,SMC < D_p < D_p,Fluct where R_p is slightly larger than that in bulk.

     

On the Nitroxide Quasi‐Equilibrium in the Alkoxyamine‐Mediated Radical Polymerization of Styrene

Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, k_c[P][N] = k_d[P N], where P, N and P N are living, nitroxide radicals and dormant species respectively, with kinetic constants k_c and k_d, is found valid only for small values of the equilibrium constant K (10⁻¹¹–10⁻¹² mol · L⁻¹) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, k_c[P][N] = k_d[P N]₀ was found to be remarkably good up to values of K around 10⁻⁸ mol · L⁻¹. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.

Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.     

Copolymerization of 2-Hydroxy.(2,3-epoxypropoxy)benzophenone with Phthalanhydride Catalyzed by Tertiary Amine

The copolymerization of an epoxide, 2-hydroxy-4-(2,3-epoxy-propoxy)benzophenone, with cyclic anhydride catalyzed by tertiary amine in different solvents was studied. The copolymerization curves are sigmoidal in character with an induction period. In the region following the induction period, the loss in epoxide or anhydride may be correlated with the kinetic equation of the first order reaction provided the monomers are present in equimolar ratio or anhydride is in excess with respect to epoxide. The rate constant found experimentally after the induction period depends on the first power of the concentrations of amine, epoxide, and anhydride. The activation energy of copolymerization in o-xylene is 58.2 kJ/mole (13.9 kcal/mole) and log A = 3.6. The rate of copolymerization depends on polarity of the solvent and increases with dielectric constant. A reaction scheme has been proposed for the copolymerization of epoxides with cyclic anhydrides catalyzed by tertiary amines which involves the formation of a catalytic center of ionic character by isomerization of epoxide into a derivative of allyl alcohol and its subsequent interaction with tertiary amine and anhydride in equilibrium reactions, In this way, an active center of the carboxylic anion type is formed which reacts with epoxide to give alkoxide anion. This alkoxide anion reacts with anhydride to yield carboxylic anion. By interchange of these reactions, an alternating copolymer-polyester arises. The termination involves the decay of the active center into tertiary amine and carboxylic or hydroxylic endgroups. The kinetic solution of this scheme is in agreement with the experimental results of kinetic measurements and the rate of copolymerization is governed by the equation: -d[epoxide] /dt = k_p [amine] ₀ [epoxide]₀ [anhydride]₀ [epoxide].     

Nitroxide‐Mediated Controlled/Living Free Radical Copolymerization of Styrene and Divinylbenzene in Aqueous Miniemulsion

Summary: The nitroxide‐mediated controlled/living free radical copolymerization of styrene and divinylbenzene using a polystyrene‐TEMPO macroinitiator in aqueous miniemulsion and in bulk have been investigated. The crosslink densities were estimated based on the content of pendant vinyl groups as determined by ¹H NMR. Considerably lower crosslink densities were revealed in the miniemulsion than in the corresponding bulk system. The rate of polymerization in the miniemulsion increased with decreasing particle size, and was significantly higher than in bulk.

Crosslink density for the TEMPO‐mediated free radical copolymerization of S(1) and DVB(2) (f = 0.99, f = 0.01) at 125 °C in bulk (□) and in miniemulsions with d_n = 585 nm (○) and 53.3 nm (•).     

Semibatch Atom Transfer Radical Copolymerization of Styrene and Butyl Acrylate

Summary: Batch and semibatch butyl acrylate (BA) polymerizations are carried out using a heterogeneous atom transfer radical polymerization (ATRP) catalyst system, with excellent molecular weight (MW) control maintained at temperatures below 80 °C. A kinetic model, using rate coefficients from literature and catalyst solubility data from this study, provides a good representation of the experimental results, after modifying the model to account for the decrease in rate caused by intramolecular chain transfer. It is also demonstrated experimentally that well-defined random, gradient, and block styrene/BA copolymers can be synthesized by manipulating monomer feed profiles in the ATRP semibatch process.     

Thioketone‐Mediated Polymerization of Butyl Acrylate: Controlling Free‐Radical Polymerization via a Dormant Radical Species

It is demonstrated by experiment and simulation that the commercially available thioketone 4,4‐bis(dimethylamino)thiobenzophenone is capable of controlling AIBN‐initiated bulk butyl acrylate polymerization at 80 °C. On the basis of molecular weight data and from monomer conversion versus time curves, the associated rate parameters are estimated. The addition rate coefficient, k_ad, for the reaction of a propagating chain with the thioketone is close to 10⁶ L · mol⁻¹ · s⁻¹ and the fragmentation rate coefficient, k_frag, is around 10⁻² s⁻¹ giving rise to large equilibrium constants in the order of 10⁸ L · mol⁻¹. Furthermore, cross‐ and self‐termination of the dormant radical species are identified to be operational.

     

Trends in Kinetic Behavior during Ester-Ester Exchange Reactions in Polyesters by Mass Spectrometry. I

The kinetics of the ester-ester exchange reaction between polyesters from adipic acid and various linear and branched glycols were investigated by mass spectometry using the dimer analysis method (DAM). Rate constants, activation energies, and frequency factors are given for reactions studied in the temperature range of 572–585 K. Correlation of glycol methylene ratios with activation energies and frequency factors shows an alternating trend in kinetic behavior. Reaction systems containing even numbers of methylene groups in the glycol moiety of the reactants exhibited slower reaction rates than systems with odd numbers of methylene groups, while branched reaction systems followed very similar trends when the influence of pendant groups is ignored.     

Simulation of Styrene Polymerization by Monomolecular and Bimolecular Nitroxide‐Mediated Radical Processes over a Range of Reaction Conditions

Simulations of polymerization rate, molecular weight development and evolution of the concentrations of species participating in the reaction mechanism over a range of operating conditions, and a parameter sensitivity analysis showing the effects of temperature, activation/deactivation equilibrium constant and initial concentrations of controller and initiator (if present) on these variables are presented for the nitroxide‐mediated radical polymerization of styrene. The simulations were performed with a computer program based on a detailed reaction mechanism. The simulated profiles of conversion, number average molecular weight ( ), and polydispersity agree well with experimental data. Previously unknown activation energies for reactions involved in the mechanism are estimated. The temperature dependence of the kinetic rate constants obtained in this study will be useful for future modeling and optimization studies.

     

Kinetics of Nitroxide Mediated Radical Polymerization of Styrene with Unimolecular Initiators

Summary: This study examined the kinetics of nitroxide-mediated radical polymerization of styrene with unimolecular (alkoxyamine) initiators. Control of polymerization rate and polymer molecular weight in unimolecular nitroxide-mediated radical polymerization was studied by looking at the effects of the three main factors: initiator concentration, temperature, and initiator molecular weight on polymerization rate, molecular weight and polydispersity. In addition, the behavior of the unimolecular initiating systems was compared to that of the corresponding bimolecular system. The effective TEMPO concentration and degree of self-initiation of styrene were proved to be significant in dictating magnitudes of molecular weight averages and widths of molecular weight distribution.     

Towards a Living Radical Polymerization of Styrene by Using Dithiolactone as a New Type of Mediating Agent

In this communication, γ‐phenyl‐γ‐butyrodithiolactone (DTL1) is presented as the first example of a new type of control agent. The styrene polymerization carried out at 60 °C in the presence of DTL1 exhibits living characteristics, without consuming DTL1 during the process. This unprecedented behavior was explained by a mechanism based on the reversible formation of a persistent radical adduct between the DTL1 and the polystyrene macroradicals.

     

Rapid additive‐free TEMPO‐mediated stable free radical polymerizations of styrene

The stable free radical polymerization (SFRP) of styrene, initiated with benzoyl peroxide in the presence of TEMPO, under bulk conditions, is demonstrated to proceed rapidly without the need for any rate enhancing additives such as camphorsulfonic acid, 2‐fluoro‐1‐methyl pyridinium p‐toluenesulfonate, or acetic anhydride. Monomer conversions as high as 70% can be achieved in 5 h or less while maintaining polydispersity indexes of 1.15. These results stand in stark contrast to earlier reactions that required 70 h to achieve similar conversions. This study demonstrates that the single largest factor governing the rates of polymerization is the molar concentration of excess TEMPO remaining in solution after initiation. A reduction in the TEMPO to BPO ratio is required when large amounts of BPO are used to target low molecular weight polystyrenes. However, when a lower molar amount of BPO is used to obtain high molecular weight polystyrenes, a higher TEMPO to BPO ratio is required. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5487–5493, 2007     

不饱和环缩醛与苯乙烯的原子转移自由基共聚合反应

不饱和环状单体与烯类单体共聚所得的共聚物 ,已经或正在开发成一系列新的产品 .例如 ,水解后得到末端带有—OH,— SH,—COOH等官能团的聚苯乙烯、聚乙烯、聚甲基丙烯酸甲酯等的低聚物[1] ,用于制备新型聚酯和聚氨酯 ;与乙烯的共聚物可在细菌作用下彻底分解成脂肪酸或醇 ,可赋予聚合物生物降解活性 ;与双甲基丙烯酸酯等的共混物 ,可用于制作高强度补牙材料[2 ] 等 .以前报道的不饱和环状单体与烯类单体的共聚反应 ,均为无规共聚 ,而且是普通自由基引发聚合 ,不能控制分子量 ,分子量分布很宽 .原子转移自由基聚合是近几年发展起来的实现…     

水分散体系中丙烯酸四氟丙酯与苯乙烯的原子转移自由基共聚合

以2－溴代异丁酸乙酯（EBiB）为引发剂、CuBr/CuBr_2/1, 10-邻二氮菲（ phen）配合物为催化剂,在水分散体系中进行了丙烯酸四氟丙酯（TFPA）与苯乙烯 (St)的原子转移自由基共聚合,所得共聚物的分子量（M_n）随着单体总转化率的 增加而增大,分子量分布（M_w/M_n）较窄（1.26～1.65）,表现出“活性”聚合 的特征。用拓展的Kelen-Tudos法和Fineman-Ross法估算了共单体的表观竞聚率, 发现St的相对反应活性高于TFPA,因此当St和TFPA起始组成为1:1（摩尔比）时, 反应自发生成了含氟的准梯度或“渐变”共聚物。实验分别考察了三种乳化剂体系 ,即十二烷基磺酸钠（SLS）、全氟辛酸钠（SPFS）／SLS和全氟壬烯氧基苯磺酸钠 （OBS）／SLS对共聚合反应的影响,发现它们对共聚合的可控制性影响不大,且反 应过程中均无破乳现象发生;然而,以OBS/SLS复合乳化剂体系制备的共聚物乳液 的贮存稳定性明显优于以SLS或SPFS／SLS为乳化剂体系制备的共聚物乳液的稳定性 。     

稳定自由基存在下苯乙烯聚合的加速剂

研究了稳定自由基存在下苯乙烯的活性聚合,发现在β－酮酸酯－乙酰乙酸乙酯,乙二酸二乙酯,1,3－二酮－乙酰丙酮的少量存在下,苯乙烯聚合速率显著增加,分子量可控,分子量在布较窄。而乙酰丙酮较大量存在下,聚苯乙烯分散性稍微变宽。     

Particle Size Effects in TEMPO‐Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion

Summary: 2,2,6,6‐Tetramethylpiperidinyl‐1‐oxy (TEMPO)‐mediated radical polymerization of styrene in aqueous miniemulsion at 125 °C using sodium dodecylbenzenesulfonate and poly(vinyl alcohol), respectively, as colloidal stabilizers has been investigated. The particle size had a dramatic effect on the polymerization process. Decreasing particle size led to a markedly higher polymerization rate, but less control and a lower degree of livingness. For particles with diameters greater than approximately 170 nm, the polymerization behavior was essentially the same as in the corresponding bulk system. By varying the particle size within an appropriate range, it is possible to tune the polymerization such that the polymerization rate is increased while still maintaining reasonable control and livingness.

     

Microwave‐assisted nitroxide‐mediated radical polymerization of acrylamide in aqueous solution

The present work describes a combination of microwave irradiation as a heating source and water as a solvent for carrying out a living/controlled polymerization of acrylamide. Reasonable results were obtained for a nitroxide‐mediated radical polymerization (NMP) with a combination of a conventional hydrosoluble radical initiator and a β‐phosphonylated nitroxide. The microwave enhancement of the polymerization was found to depend on the mode of irradiation, i.e., either a dynamic (DYN) mode or an pulse (SPS) mode. The former mode corresponded to a dynamic control of the temperature by way of a high initial microwave power, and in this case, no specific microwave effect was observed. On the other hand, in the SPS mode, which is a pulsed power mode, the result showed a strong acceleration of the polymerization process (>50 times) without the loss of the living/controlled polymerization characteristics, which is relevant with a reinitiation of the polyacrylamide macroinitiator even after 100% of conversion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

活性自由基聚合法制备以C60封端的聚苯乙烯

通过活性自由基聚合的方法制备了以２,２,６,６－四甲基－４－羟基呱啶氮氧自由基（ＴＥＭＰＯＬ）封端的聚苯乙烯大分子,实验结果证明该反应体系是一个典型的活性自由基聚合体系,同时研究了ＴＥＭＰＯＬ／ＡＩＢＮ的比例及ＡＩＢＮ的含量对聚合反应的影响。用以ＴＥＭＰＯＬ封端的聚苯乙烯和Ｃ６０反应,制得了Ｃ６０的聚苯乙烯高分子衍生物,紫外和ＧＰＣ结果均证明Ｃ６０已连接到聚苯乙烯的长链上,ＧＰＣ的结果还证明,Ｃ６     

Modeling of Nitroxide‐Mediated Semibatch Radical Polymerization

A mechanistic model is developed for high‐temperature (138 °C) styrene semibatch thermally and conventionally initiated FRP, as well as NMP with a two‐component initiating system (tert‐butyl peroxyacetate, 4‐hydroxy‐TEMPO). The model, using kinetic coefficients from literature, provides a good representation of the FRP experimental results. Implementation of a gel effect correlation to represent the change in the diffusion‐controlled termination rate coefficient with conversion improves the fit to the thermally initiated system, but is not required to represent the production of low molecular weight material ( Dalton) by conventionally initiated FRP or NMP. The low initiator efficiency found in NMP is well explained by a reaction network involving combination of free nitroxide with methyl radicals formed from initiator decomposition.