Effect of synthesis parameters on polymethacrylic acid xerogel structures and equilibrium swelling

Hydrogels based on crosslinked polymethacrylic acid were synthesized via free-radical polymerization in aqueous solution, using N,N′-methylene bisacrylamide as a crosslinking agent and 2,2′-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride as an initiator. The influence of the reaction parameters (the neutralization degree of methacrylic acid and the initial monomer concentration) on the equilibrium swelling degree, the swelling kinetic parameters and the basic structural properties of xerogels was investigated. The change of synthesis parameters leads to the change of the basic structural parameters of xerogel, as well as the equilibrium swelling degree and the initial swelling rate of the hydrogels. It is found that there are power form relationships between the equilibrium swelling degree, the initial swelling rate and the structural xerogel’s properties and the change of the neutralization degree of monomer, i.e. the monomer concentration. The examined correlations proved that the crosslinking density is the crucial parameter which determines all the other investigated structural and swelling parameters. The article is published in the original.     

Rate mechanisms of a novel thiol-ene photopolymerization reaction

A novel thiol-ene photopolymerization reaction involving copolymerization of tetrathiol monomer with vinyl silazane is experimentally characterized and is modeled successfully. The overall polymerization rate is found to be controlled by the ratio of the propagation to chain transfer kinetic parameters. The polymerization rate of this mixture, in the presence of added photoinitiator, is approximately first order in ene functionality and is independent of thiol functional group concentration. Initiation rates in this system, when cured utilizing a light centered around 365 nm light, and in the presence of no added photoinitiator, are shown to be proportional to the ene monomer concentration. When the mixture is polymerized utilizing light centered at 254 nm light, and without photoinitiator, the initiation rates are proportional to the thiol monomer concentrations. This novel reaction scheme is further utilized to form ultra rapidly polymerizable polymer derived ceramic structures with high aspect ratios.     

Synthesis of monodisperse polymer suspensions with a narrow particle size distribution in the presence of water-insoluble triple block copolymers of polypropylene oxide and polyethylene oxide (pluronics)

The colloidal chemical properties of triple block copolymers of polypropylene oxide and polyethylene oxide (pluronics of various structures) were studied in comparison. All of them are shown to be surfactants but differ in interfacial tension, surface activity, surface area occupied in the adsorption layer, and adsorption layer thickness. The kinetic regularities of polymerization of styrene and methyl methacrylate were studied. The particle diameters and their size distribution were determined. Distinctions in the kinetic regularities of polymerization are shown: the shape of the conversion—time curves (for the duration of the initial and stationary stages of polymerization) and the dependences of the diameter on the surfactant concentration and monomer to water volume ratio. In the presence of the water-insoluble pluronics, the mechanism of formation of polymer—monomer particles and interfacial layer on the surface differs from that when using water-soluble surfactants, which makes it possible to distinguish these processes into an independent type of heterophase polymerization.

     

二甲基二烯丙基氯化铵反相乳液聚合动力学及机理的研究

研究以异构烷烃混合物为连续相,以丁二酸二(2-乙基)己酯磺酸钠(Sodium-di-2-ethylhexylsulfosuccinate,CH~3CH~2CH~2CH~2CH(C~2H~5)CH~2OCOCH(SO~3Na)CH~2COOCH~2CH(C~2H~5)-CH~2CH~2CH~2CH~3,AOT)和山梨糖醇单油酸酯(SMO)为乳化剂,以偶氮二异庚腈(ADVN)为引发剂的二甲基二烯丙基氯化铵的反相乳液聚合,得到了R~P~,~0=kc^0^.^4~Ⅰ~,~0c^0^.^5~A~O~Tc^-^0^.^4~S~M~Oc^3^.^0~M~,~0的表观动力学表达式。首次提出并研究了反相乳液聚合中单体在单体液滴和胶束中的分配系数对聚合动力学的影响,成功地解释了初始聚合反应速度和单体浓度三次方成正比的原因。通过对胶粒(latex)直径、单体在油相中的溶解度、聚合反应速度与AOT浓度及搅拌速度间的关系的测定,证明聚合反应是通过胶束(micelle)成核机理而进行的。通过对不同单体浓度下的^1H NMR盐效应的研究,证明溶液聚合的速度和单体浓度二次方成正比不是由于生成双分子π配合物,而是由静电屏蔽效应和粘度的改变引起的。     

Copolymerization of divinyl monomers with maleic and fumaric acid derivatives

The process of formation of reticular copolymer molecular structures produced in free radical copolymerization of divinyl monomers (divinyl ethers of diethylene glycol and hydroquinone, divinyl sulfide, p-divinylbenzene, etc.) with maleic and fumaric acid derivatives is studied. The basic factor that determines the features of molecular and network structures of copolymers is reactivity of the divinyl monomer in copolymerization with monovinyl monomer. The network of copolymers of maleic anhydride with the divinyl ether of hydroquinone is formed out of oligomer microgels. Divinyl sulfide in copolymerization with maleic acid is disposed to cyclocopolymerization; also crosslinking reactions occur. Formation of a network structure of copolymers of divinylbenzene with maleic and fumaric acid derivatives is shown to proceed via an alternating copolymerization mechanism. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 371–378, 1998     

Cyclopolycondensations. VII. Preparation of aromatic poly(ureido acids) by the low-temperature solution polymerization and cyclodehydration to fully aromatic polyquinazolinediones

Fully aromatic polyquinazolinediones (IV) of high molecular weight were obtained by thermal cyclodehydration of aromatic poly(uredio acids) (III) prepared by the polyaddition reaction of 4,4′-diaminobiphenyl-3,3′-dicarboxylic acid (I) with aromatic diisocyanates (II). From the kinetic study of reactions of model systems (anthranilic acid with phenyl isocyanate) in the presence of a variety of basic catalysts, it was established that tertiary amines had the highest catalytic activity for the formation of ureido linkage. The optimum polymerization conditions were determined by the study of reaction variables such as monomer concentration, polymerization temperature, monomer ratio, and catalyst concentration. The effect of polarity and purity of organic solvents and reactants was also studied.     

Radiation-induced terpolymerization of methyl α,β,β-trifluoroacrylate with tetrafluoroethylene and α-olefin

Radiation-induced terpolymerizations of methyl α,β,β-trifluoroacrylate (MTFA) with tetrafluoroethylene (TFE) and α-olefins, such as ethylene, propylene, and isobutylene, were carried out in bulk at 25°C for the purpose of controlling the content of ester group in the MTFA-α-olefin alternating copolymers. These monomers polymerized to form alternating terpolymers which contained 50 mole % α-olefin in a wide range of monomer composition. The content of MTFA, namely, the ester group in polymer, can be varied without destruction of the alternating structures between fluoroolefins (MTFA, TFE) and α-olefin by changing the MTFA/TFE ratio in the monomer mixture. The relative reactivities of MTFA and TFE in the terpolymerization were discussed according to kinetic treatments by free propagating and complex mechanisms. The relation between the MTFA/TFE ratio in the monomer mixture and that in terpolymer was explained favourbly by the complex mechanism. It was also concluded that the relative reactivity of MTFA is larger than that of TFE in the terpolymerizations.     

Step‐Growth Copolymerization Between an Immobilized Monomer and a Mobile Monomer in Metal–Organic Frameworks

The A–A/B–B step‐growth copolymerization between a monomer immobilized in the crystalline state and a monomer mobile in the solution state is demonstrated. One of the two monomers was immobilized as organic ligands of the metal–organic framework (MOF) and polymerized with the mobile guest monomer, resulting in the formation of linear polymers. The polymerization behavior was completely different from that of the solution polymerizations. In particular, the degrees of polymerization (DP) converged to a specific value depending on the MOF structures. The inevitable termination is caused not by imperfectness of the polymerization reaction, but by the selection of the two polymerization partners among the several adjacent immobilized monomers. This is fully supported by the Monte Carlo simulation on the basis of the polymerization mechanism. Precise immobilization of monomers in the supramolecular assemblies is a promising way for the controlled A–A/B–B step‐growth polymerization.     

Kinetics and mechanisms of emulsion polymerization initiated by oil-soluble initiators. IV. Kinetic modeling of unseeded emulsion polymerization of styrene initiated by 2,2′-azobisisobutyronitrile

To explain the kinetic features of particle formation and growth in unseeded emulsion polymerization initiated by oil-soluble initiators, a mathematical kinetic model is proposed, based on the assumption that when initiator radicals or monomer radicals in the water phase enter monomer-solubilized emulsifier micelles, initiate polymerization, and propagate to a chain length which is long enough not to desorb from the micelles, the micelles are regarded to be transformed into polymer particles. It is demonstrated by comparing the experimental results obtained in the emulsion polymerization of styrene initiated by the oil-soluble initiator, 2,2'-azobisisobutyronitrile, with sodium lauryl sulfate as emulsifier that the proposed kinetic model satisfactorily explains the kinetic features such as the effects of initial emulsifier, initiator, and monomer concentrations on both the number of polymer particles produced and the monomer conversion versus time histories. © 1993 John Wiley & Sons, Inc.     

Kinetics and mechanism of amyloid formation by the prion protein H1 peptide as determined by time-dependent ESR

Background: Peptides derived from three of four putative α-helical regions of the prion protein (PrP) form amyloid in solution. These peptides serve as models for amyloidogenesis and for understanding the α helix → β strand conformational change that is responsible for the development of disease. Kinetic studies of amyloid formation usually rely on the detection of fibrils. No study has yet explored the rate of monomer peptide uptake or the presence of nonfibrillar intermediate species. We present a new electron spin resonance (ESR) method for probing the kinetics of amyloid formation. A spin label was covalently attached to a highly amyloidogenic peptide and kinetic trials were monitored by ESR.Results: Electron microscopy shows that the spin-labeled peptide forms amyloid, and ESR reveals the kinetic decay of free peptide monomer during amyloid formation. The combination of electron microscopy and ESR suggests that there are three kinetically relevant species: monomer peptide, amyloid and amorphous aggregate (peptide aggregates devoid of fibrils or other structures with long-range order). A rather surprising result is that amyloid formation requires the presence of this amorphous aggregate. This is particularly interesting because PrP^Sc the form of PrP associated with scrapie, is often found as an aggregate and amyloid formation is not a necessary component of prion replication or pathogenesis.Conclusions: Kinetic analysis of the time-dependent data suggests a model whereby the amorphous aggregate has a previously unsuspected dual role: it releases monomer into solution and also provides initiation sites for fibril growth. These findings suggest that the β-sheet-rich PrP^Sc may be stabilized by aggregation.     

Recent developments in the design of functionalised polymeric microspheres

This paper is a brief survey on the preparation of latexes bearing covalently bonded functional groups using various routes. Recent methods are presented using water soluble functional (or surface active) initiators, monomers or macromonomers. For tailor synthesis, the copolymerisation approach of a basic monomer with a functional monomer under emulsifier-free conditions is generally the more suitable and versatile one. More progress should be pursued in this field in order to design better adapted chemical structures which will improve their use in radical-initiated heterogeneous conditions and favour surface incorporation.     

Polymerisation anionique de l'acroleine—I. Polymerisations amorcees par des organo-sodiques dans le tetrahydrofuranne

In tetrahydrofuran, with Na⁺ as counter-ion, the anionic polymerization of acrolein involves numerous transfer reactions to monomer and to polymer; on the other hand, termination of growing chains does not occur. The use of initiators, like carbanions or oxanions, does not affect the polymerization rate. The kinetic order of the reaction is unity for monomer and unity for initiator; these results indicate that the living ends are not associated at the studied concentrations of initiator. Without stating precisely the mechanism of the transfer reactions, we have proposed a kinetic scheme.In tetrahydrofuran, with Na⁺ as counter-ion, the anionic polymerization of acrolein involves numerous transfer reactions to monomer and to polymer; on the other hand, termination of growing chains does not occur. The use of initiators, like carbanions or oxanions, does not affect the polymerization rate. The kinetic order of the reaction is unity for monomer and unity for initiator; these results indicate that the living ends are not associated at the studied concentrations of initiator. Without stating precisely the mechanism of the transfer reactions, we have proposed a kinetic scheme.     

双官能度引发剂引发苯乙烯聚合微观动力学

采用 2 ,5 二甲基 2 ,5 二己酰基过氧化己烷 (DMDEHPH)为引发剂 ,在 5 5～ 80℃下引发苯乙烯聚合 .通过研究影响聚合速率的各种因素 ,得出了聚合速率对单体浓度和引发剂浓度的级数分别为 1 0和 0 5次、聚合活化能为 92 0kJ mol、引发效率为 0 5 5± 0 0 3.温度一定 ,引发效率随引发剂浓度的增加而减小 .求得 6 0和70℃下DMDEHPH向引发剂的链转移常数分别为 0 0 37和 0 0 4 8、向单体的链转移常数分别为 0 5 9× 10 - 4和0 75× 10 - 4.     

Mathematical Modeling of the Bulk Photopolymerization of Furfuryl Acrylate

Summary: Experimental data for the photopolymerization of furfuryl acrylate (FA) conformed satisfactorily to the kinetics model proposed for the photopolymerization of furfuryl methacrylate (FM). This model allowed the kinetic constants of the basic steps of the studied mechanism, namely propagation, degradative transfer, re‐initiation and cross‐termination, to be determined. The calculated values of these constants were in agreement with the chemical nature of FA. For each of these constants, the confidence intervals were determined, and the statistical dependence between some of them was analyzed using the ellipse error method. The equations of moments of the distribution of molecular sizes of the primary chains in the network with order greater than one were developed to describe different molecular averages, such as weight‐average chain length and size‐average heterogeneity of the primary chains. The results found for the monomer conversion, the cross‐link degree and number‐average length of the primary chains of the network for FA were compared with those obtained for FM, and it was shown that the process of polymerization of the former monomer was more retarded and produced gels with a greater degree of cross‐linking than the latter as expected.

Network structures with different heterogeneity in size of the primary chains.     

Butyl acrylate batch emulsion polymerization in the presence of sodium lauryl sulphate and potassium persulphate

The batch emulsion polymerization of butyl acrylate in the presence of sodium lauryl sulphate as emulsifier and potassium persulphate as initiator was investigated. The effects of emulsifier concentration, initiator concentration, and monomer/water ratio on the kinetic features were studied. The kinetic data showed that at the conditions studied, the number of particles is proportional to [KPS]^0.39 and [SLS]^0.54. The number of particles did not practically vary with monomer concentration at the high range of monomer and emulsifier concentrations. At low emulsifier concentration, particle coagulation occurred in the course of reaction, which increased with monomer concentration. Particle nucleation was found to occur during Interval III of the batch process if undissociated micelles exist. It was also confirmed that the zero-one kinetics system can better fit the experimental results, compared to the pseudobulk kinetics. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3957–3972, 1999     

An alternating copolymer of maleimide and atropic acid with narrow molecular weight distribution prepared by radical mechanism

Three basic conditions for preparation of alternating copolymer with narrow molecular weight distribution were derived from the element kinetic equations of binary radical copolymerization. Using maleimide (MI) and atropie acid (ATA) as model monomer pairs and dioxane as the solvent the alternating copolymer with molecular weight distribution in the range of 1.09--1.20 was prepared successfully by charger transfer complex (CTC) mechanism in the presence of benzoyl peroxide at 85℃. The monomer reactivity ratioes r_1(MI)=0.05±0.01 and r_2(ATA)=0.03±0.02 were measured. The alternating eopolymerization was carried out through formation of a contact-type CTG and then alternating addition of MI and ATA monomers. The molecular weight of the copolymers is nearly independent of the feed ratio in a large range and the polymerization rate dropped with an increase in ATA in feed ratio.     

铈离子/4-甲氧基丁二酰-对-甲苯胺或4-甲氧基马来酰-对-甲苯胺体系引发烯类聚合

研究了铈离子与四种不同结构的酰苯胺类化合物,如4-甲氧基丁二酰苯胺(MSA)-4-甲氧基丁二酰-对-甲苯胺(MST)、丁二酸单酰-对-甲苯胺(SAMT)和4-甲氧基马来酰-对-甲苯胺(MMT),组成的引发体系对丙烯酰胺聚合的影响,测定了聚合表现活化能和聚合反应动力学方程。由聚丙烯腈的红外光谱端基分析证实了MST组分与铈离子反应产生的自由基能引发烯类聚合。