Kinetic approach to modeling the radical polymerization of styrene in the presence dibenzyl trithiocarbonate

A mathematical model of the kinetics of the radical polymerization of styrene in the presence of dibenzyl trithiocarbonate by the reversible addition-fragmentation chain transfer mechanism with cross-termination of radicals and intermediates and quadratic termination of intermediates is developed. The adequacy of the polymerization mechanism underlying the model and the related mathematical formalism are tested by comparing the calculated and measured values of the average molecular-weight characteristics of resulting polystyrene.     

Molecular weight properties of poly(butyl acrylate): Computational experiment based on a kinetic model of “living” radical polymerization with reversible addition-fragmentation chain transfer

Based on a kinetic model of “living” radical polymerization of butyl acrylate with reversible chain-transfer, the characteristics of altering the molecular weight properties of the polymer by varying the initial concentrations of the reactants and temperature are established.     

甲基丙烯酸甲酯—丙烯酸丁酯共聚物微观结构研究

用＾１３Ｃ ＮＭＲ研究了由基团转移共聚得的的甲基丙烯酸甲酯－丙烯酸酯共聚物的微观结构，共聚物中单体链节的三元组含量从季碳和羰基碳的共振信号测得，实验测得的三元组分数与通过竞聚率和单体组成比按末端基效应模式的计算值相符，丙烯酸丁酯由于具有大得多的竞聚率值而呈现较强的均聚倾向。     

Preparation of BA/ST/AM nano particles by ultrasonic emulsifier-free emulsion polymerization

A kind of nano particle of butyl acrylate (BA)/styrene (ST)/acrylamide (AM) was prepared through a new method that was ultrasonic emulsifier-free emulsion polymerization, which was a kind of environmental protection and economical method. And no any volatile organic solvent (VOC), emulsifier and initiator were used in this method. Only water was used as solvent. The effects of sonic intensity, sonic time, inorganic salt content, N2 flow velocity, etc. on monomer conversion were studied. TEM photographs showed that its particles size was about 80 nm, which was less than particles size (about 140 nm) through conventional emulsifier-free emulsion polymerization method. The FTIR spectrum showed that after extracted by water for 48 h, CHCl3 for 48 h and THF for 48 hr, respectively, the sample obtained by this way was a ternary copolymer of BA, ST and AM, but not a blend of poly(butyl acrylate), polystyrene and polyacrylamide.     

Complex nanostructured materials from segmented copolymers prepared by ATRP

The development of new controlled/living radical polymerization processes, such as Atom Transfer Radical Polymerization (ATRP) and other techniques such as nitroxide mediated polymerization and degenerative transfer processes, including RAFT, opened the way to the use of radical polymerization for the synthesis of well-defined, complex functional nanostructures. The development of such nanostructures is primarily dependent on self-assembly of well-defined segmented copolymers. This article describes the fundamentals of ATRP, relevant to the synthesis of such systems. The self-assembly of block copolymers prepared by ATRP is illustrated by three examples. In the first, block copolymers of poly(butyl acrylate) with polyacrylonitrile phase separate, leading to spherical, cylindrical or lamellar morphologies, depending on the block copolymer composition. At a higher temperature, polyacrylonitrile block converts to nanostructured carbon clusters, whereas poly(butyl acrylate) block serves as a sacrificial block, aiding the development of designed nanostructures. In the second example, conductive nanoribbons of poly(n-hexylthiophene) surrounded by a matrix of organic polymers are formed from block copolymers prepared by ATRP. The third example describes an inorganic-organic hybrid system consisting of hard nanocolloidal silica particles (20 nm) grafted by ATRP with well-defined polystyrene-poly(benzyl acrylate) block copolymer chains (1000 chains per particle). Silica cores in this system are surrounded by a rigid polystyrene inner shell and softer polyacrylate outer shell. Received 9 July 2002 Published online: 11 March 2003     

Preparation and Properties of Water-Soluble Sodium Polyacrylates

Butyl acrylate-acrylic acid copolymer and poly (butyl acrylate) were synthesized via suspension polymerization by using butyl acrylate as the main monomer and acrylic acid as a secondary monomer. Then these polymers were swollen in ethanol and hydrolyzed in an aqueous solution of sodium hydroxide. Finally, water-soluble sodium polyacrylates were obtained by washing and drying the hydrolyzed resultant. The influence of the mass fraction of acrylic acid in the monomer feed ratio, swelling time, and hydrolysis time on hydrophilicity, solubility, and absolute viscosity of the prepared sodium polyacrylates was researched. In addition, an Ubbelohde viscometer was used to determine the intrinsic viscosity of the aqueous solutions of the prepared sodium polyacrylates. The Mark–Houwink equation was applied to calculate their viscosity average molecular weight. Finally, their chemical structures and heat resistance properties were analyzed by using nuclear magnetic resonance spectroscopy and thermogravimetric analysis; additionally, the changes of the surface elements before and after hydrolysis were researched by using X-ray photoelectron spectroscopy.     

Numerical modeling of self-propagating polymerization fronts: The role of kinetics on front stability

Frontal propagation of a highly exothermic polymerization reaction in a liquid is studied with the goal of developing a mathematical model of the process. As a model case we consider monomers such as methacrylic acid and n-butyl acrylate with peroxide initiators, although the model is not limited to these reactants and can be applied to any system with the similar basic polymerization mechanism. A three-step reaction mechanism, including initiation, propagation and termination steps, as well as a more simple one-step mechanism, were considered. For the one-step mechanism the loss of stability of propagating front was observed as a sequence of period doubling bifurcations of the front velocity. It was shown that the one-step model cannot account for less than 100% conversion and product inhomogeneities as a result of front instability, therefore the three-step mechanism was exploited. The phenomenon of superadiabatic combustion temperature was observed beyond the Hopf bifurcation point for both kinetic schemes and supported by the experimental measurements. One- and two-dimensional numerical simulations were performed to observe various planar and nonplanar periodic modes, and the results for different kinetic schemes were compared. It was found that stability of the frontal mode for a one-step reaction mechanism does not differ for 1-D and 2-D cases. For the three-step reaction mechanism 2-D solutions turned out to be more stable with respect to the appearance of nonplanar periodic modes than corresponding 1-D solutions. Higher Zeldovich numbers (i.e., higher effective activation energies or lower initial temperatures) are necessary for the existence of planar and nonplanar periodic modes in the 2-D reactor with walls than in the 1-D case. (c) 1997 American Institute of Physics.     

IR-UV联合法测定固相微萃取涂层中单体含量

合成了作为固相微萃取涂层的苯乙烯-丙烯酸丁酯-乙烯基三乙氧基硅氧烷三元共聚物。采用红外光谱(IR)和紫外光谱(UV)相结合的方法测定了聚合物中苯乙烯和丙烯酸丁酯的含量。由IR法测得样品中二者的摩尔比。采用双波长紫外光谱法测得苯乙烯的含量。由苯乙烯与丙烯酸丁酯的摩尔比及苯乙烯的含量得出样品中丙烯酸丁酯含量,进而得出乙烯基三乙氧基硅氧烷的含量。苯乙烯与丙烯酸丁酯的摩尔比测定的外标曲线方程为A_r=0.114m_r+0.032,相关系数r2=0.999 3;苯乙烯含量测定的标准曲线方程为ΔA=0.078 6c+0.081 2,相关系数r2=0.998 9。苯乙烯含量测定的相对标准偏差(RSD)为0.41%,加标回收率为97.8%～104.0%;丙烯酸丁酯含量测定的相对标准偏差(RSD)为0.39%,加标回收率为97.1%～99.6%。     

红外光谱法测定固相微萃取新型吸附质中单体的摩尔比

以丙烯酸丁酯和苯乙烯为单体 ,过氧化苯甲酰为引发剂 (用量为wt 0 3% ) ,醋酸丁酯和甲苯作混合溶剂 ,溶剂用量与单体混合物的体积相同 ,采用溶液聚合的方法合成了一种新型固相微萃取吸附质 (苯乙烯 丙烯酸丁酯共聚物 )。以朗伯 比耳定律为依据 ,通过一系列的推导过程 ,得出了共聚物中两种官能团的吸收值比与共聚物中两种单体摩尔比的线性关系式A1 /A2 =kn1 /n2 。采用红外光谱法测定聚合物中两种官能团的吸收值比 ,再通过外标曲线法确定了共聚物中两种官能团的吸收值比 (y)与共聚物中两种单体的摩尔比 (x)的线性回归方程 y =0 136 2 0 0 84 1x。方法的精密度RSD(% ) =2 4 6 4 ,方法的回收率为 92 89%～10 3 94 %。红外光谱法测定作为固相微萃取新型吸附质的苯乙烯与丙烯酸丁酯共聚物中单体的摩尔比是一种快速准确的分析方法     

Synthesis and Characterization of Methylacrylic Acid and Butyl Acrylate Grafted onto Ethylene-Propylene-Diene Terpolymer

A multi-component polymer of methacrylic acid (MAA) and butyl acrylate (BA) grafted onto ethylene-propylene-diene (EPDM) terpolymer was synthesized in toluene using benzoyl peroxide (BPO) as initiator. The effect of EPDM/MAA-BA ratio and MAA/BA ratio on the grafting ratio of polymerization was investigated. The products were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), surface energy, inherent viscosity, and atomic force microscopy (AFM). The results showed that the MAA and BA monomers were successfully grafted onto EPDM. Furthermore, after being grafted, the polarity of the surface of the EPDM-g-MAA-BA increased with increasing grafting ratio, and the morphology of its surface became more smooth.     

Preparation of Al(OH)3/Acrylic Copolymer Latex by Emulsion Polymerization

The Al(OH)₃/acrylic copolymer latexes were synthesized through the emulsion polymerization of acrylic monomers, butyl acrylate and 2-ethylhexyl acrylate in the presence of surface-functionalized Al(OH)₃ filler particles. The polymerization was stabilized by polyoxyethylene (50) nonyl phenyl ether (NP-1050, nonionic surfactant) and ammonium (POE) alkyl aryl ether sulfate (EU-S133D, anionic surfactant) to produce stable composite latexes. The improved compatibility of Al(OH)₃ surface with acrylic monomers was achieved by the modification with 3-(trimethoxysilyl) propyl methacrylate (γ-MPS). Transmission electron microscopy showed that nano-sized Al(OH)₃ particles were slightly agglomerated in the copolymer latex. When pristine Al(OH)₃ was used as a filler or γ-MPS-modified Al(OH)₃ particles were added above 30 wt% with respect to monomers, unstable latexes were obtained, which were partially precipitated out on standing for prolonged time. The flame retardation effect was not apparent with the incorporation of Al(OH)₃ in the latexes by 30 wt% as shown by LOI test.     

The effect of convection on a propagating front with a liquid product: Comparison of theory and experiments

This work is devoted to the investigation of propagating polymerization fronts converting a liquid monomer into a liquid polymer. We consider a simplified mathematical model which consists of the heat equation and equation for the depth of conversion for one-step chemical reaction and of the Navier-Stokes equations under the Boussinesq approximation. We fulfill the linear stability analysis of the stationary propagating front and find conditions of convective and thermal instabilities. We show that convection can occur not only for ascending fronts but also for descending fronts. Though in the latter case the exothermic chemical reaction heats the cold monomer from above, the instability appears and can be explained by the interaction of chemical reaction with hydrodynamics. Hydrodynamics changes also conditions of the thermal instability. The front propagating upwards becomes less stable than without convection, the front propagating downwards more stable. The theoretical results are compared with experiments. The experimentally measured stability boundary for polymerization of benzyl acrylate in dimethyl formamide is well approximated by the theoretical stability boundary. (c) 1998 American Institute of Physics.     

Synthesis and Characterization of Multi-layered Core/Shell Particles by Sequential Emulsion Polymerization

A series of core/shell particles were prepared by sequential emulsion polymerization. The core/shell particles consisting of poly(methyl methacrylate) core grafted with using rubbery layer [poly(butyl acrylate)co-(styrene)] and then glassy layer [poly(methyl methacrylate)-co-(ethyl acrylate)] were prepared. The conditions which led to controlled particle size and morphology were discussed. A highly cross-linked structure was formed in both the cores and the shells by using a cross-linking agent, which could prevent the migration of hydrophobic shells to the inside of the particles. The core/shell particles were characterized by Fourier-transform infrared spectroscopy, solid state ¹³C-NMR. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were used to determine the thermal stability and glass transition temperature of the core/shell particles, respectively. Results of the particle size analysis indicate that particle sizes were decreased when there is a rubbery layer as outer layer (0.44 μm) whereas it increases when there is a glassy layer as outer layer (324 μm). Scanning electron microscopy (SEM) also confirms the multi-layers formation in the polymer.     

Silane-modified polymers as interphases in glass-fibre-reinforced composites: 1. Synthesis and characterisation of alkoxy-silane functionalized polymers

This paper presents techniques for the functionalization of polymer materials with alkoxy-silane groups. Alkoxy-silane groups are key intermediates in bonding organic materials onto glass-fibre surfaces. Two reaction routes are described: (1) Chain copolymerization of butyl acrylate (BuA) and γ-methacryloxypropyltrimethoxy-silane (MPS) and (2) grafting of MPS onto polyethylene (PE) and poly(styrene-block-ethylene-co-1-butene-block-styrene) (SEBS). It is concluded that chain copolymerization is the superior route since it gives almost unlimited possibilities of adjusting the degree of alkoxy-silane functionality. The paper also demonstrates the advantage of performing graft copolymerization in the melt instead of in solution. Solution grafting is of low efficiency and is probably directed to chains having reactive sites, e.g. branch points. It is proposed that the primary cause is the lower temperatures used in solution grafting in comparison to the melt reaction.     

Polymerization rate and mechanism of ultrasonically initiated emulsion polymerization of n-butyl acrylate

The factors affecting the induction period and polymerization rate in ultrasonically initiated emulsion polymerization of n-butyl acrylate (BA) were investigated. The induction period takes only an instant in ultrasonically initiated emulsion polymerization of BA without any added initiator by enhancing the N2 flow rate. Increasing temperature, power output and SDS concentration, decreasing the monomer concentration results in further decreasing induction period and enhanced polymerization rate. Under optimized reaction conditions the conversion of BA reaches 92% in 11 min. The polymerization rate can be controlled by varying reaction parameters. The apparatus of ultrasonically initiated semi-continuous and continuous emulsion polymerization were set up and the feasibility was first studied. Based on the experimental results, a free radical polymerization mechanism for ultrasonically initiated emulsion polymerization was proposed, including the sources of the radicals, the process of radical formation, the locus of polymerization and the polymerization process. Compared with conventional emulsion polymerization, where the radicals come from thermal decomposition of a chemical initiator, ultrasonically initiated emulsion polymerization has attractive features such as no need for a chemical initiator, lower reaction temperature, faster polymerization rate, and higher molecular weight of the polymer prepared.     

Liquid–Liquid Transition and Detrapping of Trapped Carriers of P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly (methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M _η～2×10⁵) with different mass percentages of PMMA (100/0, 90/10, 81/19, and 75/25), were synthesized by the method of solution polymerization. In addition to the normal α and ρ peak, a third τ peak is observed in thermally stimulated depolarization current (TSDC) spectra of the copolymers in the high temperature region. The α peak‐corresponds to the glass transition, the ρ peak originates from the detrapping of trapped carriers in the bulk amorphous structure related with flexible side groups, and the τ peak can be attributed to the charge detrapping related to the liquid–liquid transition of the copolymers. The three peaks all move to lower temperature with an increase of the BA component, indicating that the flexible side groups of butyl acrylate not only have an effect of plasticization on the glass transition and liquid–liquid transition, but also make the trap depth shallower and the detrapping process easier for the ρ and τ peaks. The experimental results confirm that TSDC analysis is very sensitive for investigating the liquid–liquid transition of polymers. The liquid–liquid transition temperature (T _LL) of the copolymers follows a type of the Fox equation. Fitting the results gives a T _LL of 102°C for polybutyl acrylate.     

Improvement of polyacrylate coating by filling modified nano-TiO2

Nano-TiO₂ is modified by a method, by which nano-TiO₂ first reacts with silane coupling agent WD-70 with double bond group which subsequently copolymerizes with methyl methacrylate and butyl acrylate to produce a thin polymer shell on the nanoparticles. The modified nanoparticles have stable organophilicity. They are applied to polyacrylate coating and performances of the coating are measured by different methods. The modification of nano-TiO₂ particles can improve their dispersibility in coating, enhance hardness of coating and reduce water absorption and permeability of polyacrylate coating. The mechanism has been analyzed in this paper.     

Formation and decomposition of N‐alkylnaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8‐N‐butyl‐naphthalimide (1,8‐NBN) to 1,8‐N‐butyl‐naphthalamide (1,8‐NBAmide) and of 2,3‐N‐butyl‐naphthalimide (2,3‐NBN) to 2,3‐N‐butyl‐naphthalamide (2,3‐NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8‐NBN equilibrates with 1,8‐NBAmide in mild alkali. Under the same conditions 2,3‐NBN quantitatively yields 2,3‐NBAmide. Over a wide range of acidities the reactions of the 1,8‐ and 2,3‐N‐butyl‐naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH's. Anhydride formation in acid was demonstrated for 1,8‐NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8‐ and 2,3‐N‐butyl‐naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six‐membered ring intermediates. The rate of carboxylic acid assisted 1,8‐N‐Butyl‐naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation of Fe3O4/poly(styrene-butyl acrylate-[2-(methacryloxy)ethyl]trimethylammonium chloride) by emulsifier-free emulsion polymerization and its interaction with DNA

Cationic magnetic polymer particles Fe₃O₄/poly(styrene-butyl acrylate-[2-(methacryloxy)ethyl]trimethylammonium chloride), a type of potential gene carrier, were prepared by emulsifier-free emulsion polymerization with oleic acid modified magnetite Fe₃O₄, styrene, butyl acrylate and [2-(methacryloxy)ethyl]trimethylammonium chloride) (METAC). The morphology of the particles was characterized by transmission electron microscopy and the composites of particles were characterized by FT-IR spectroscopy, X-ray diffraction. These results showed that magnetic particles were well dispersed in polymers with the content of about 15%(wt/wt). The composites exhibited superparamagnetism and possessed a certain level of magnetic response. The interactions between the particles with calf-thymus DNA (ct DNA) were confirmed by zeta potential measurement, UV-vis spectroscopy and fluorescence spectroscopy. The DNA-binding capacity determined by the agarose gel electrophoresis showed good binding capacity of the emulsion to DNA. These results suggested the potential of the cationic magnetic polymer emulsion as gene target delivery carrier.     

Effect of Surfactant Type and Concentration on Surfactant Migration,Surface Tension,and Adhesion of Latex Films

The effect of surfactant type and concentration on the migration behavior of surfactant in a latex film was investigated. Two types of surfactant, including an anionic (sodium lauryl sulfate, SLS) and a non-ionic (nonylphenol ethoxylate, average number of ethylene oxide units = 40, NP-40) surfactant, were used in an emulsion polymerization of methyl methacrylate butyl acrylate copolymer (MMA–BA). The total amount of surfactant was varied in three levels, i.e., 1.5, 3, and 4.5 wt%, and the surfactants were used both pure and in a mixture state. The surfactant migration to the film–air (F–A) and film–substrate (F–S) interfaces of the latex films was determined by using an attenuated total reflection-Fourier transform infrared (ATR-FTIR) method. In addition, the adhesion of the latex films to glass substrates was measured by a pull-off test. The results showed that the migration of anionic surfactant to the interfaces was greater than the non-ionic one. It was also found that the use of non-ionic surfactant along with anionic surfactant could decrease the migration of the anionic surfactant to the interfaces.