Aqueous Redox Polymerization of Acrylamide Initiated by Lactic Acid/Permanganate

Acrylamide was polymerized in aqueous solution at 35 ± 0.2°C with the redox pair potassium permanganate/lactic acid. The kinetics of polymerization was followed iodometrically. The effect of monomer, potassium permanganate, and lactic acid concentration and temperature on the rate of polymerization was studied. The dependence of the number-average degree of polymerization on the initial rate of polymerization and temperature was also determined.     

Polymerization of Acrylamide Initiated by Hydroxy Terminated Polybutadiene-ceric Ammonium Nitrate Redox System

Amphiphilic copolymer of acrylamide (AAm) and butadiene was synthesized by radical initiation using the hydroxy terminated polybutadiene (HTPB) and ceric ammonium nitrate (CAN) macroredox initiator in heterogenous medium in the presence of nitric acid at 35°C in air. The resulting product was characterized by IR, NMR, viscosity and swelling measurements. Imidization of some AAm units was inferred from NMR spectroscopy and swelling measurement. The product adsorbed Ni(II) and Fe(II) ions from aqueous solution and selectively released Ni(II) only. The release pattern for hydrophilic dye was similar to the usual fractional release behavior of drug release observed for hydrogel systems.     

Aqueous Polymerization of Acrylamide Initiated by Glycolic Acid/Ce4+ Redox System

The aqueous polymerization of acrylamide initiated by the glycolic acid/Ce⁴⁺ redox system was studied in sulfuric acid medium at 35 ± 0.2°C under a nitrogen atmosphere. The initiation was carried out by the free radical generated in the decomposition of the complex formed between the oxidant and the reductant. The monomer disappearance was found to be proportional to [GA]^0,89[Ce⁴⁺]^0.57[M]^1.0, and the rate of ceric ion disappearance was found to be directly proportional to [Ce⁴⁺] and [GA] but independent of [M]. The activation energy of the system was found to be 7.21 kcal/deg/mol. The molecular weight of polyacrylamide increased with increasing [monomer] and decreased with increasing [catalyst]. The effect of pH was also studied in the pH range 2.22 to 1.44.     

Polymerization of Methacrylamide Initiated by Ceric Ion-Citric Acid Redox System

Homogeneous polymerization of methacrylamide initiated by the ceric ammonium sulfate-citric acid (CA) redox pair has been investigated and reported at 35 ± 0.2°C under nitrogen atmosphere. The initiation was caused by the free radical generated by the decomposition of the complex formed between ceric ion and citric acid. The rate of monomer disappearance was found to be proportional to [CA]^0.4, [Ce^0.4+]^0.65, and [Monomer]¹ The rate of ceric ion disappearance was directly proportional to the ceric ion concentration but independent of the monomer concentration. The initial rate was independent of [H₂SO₄]. The activation energy of the system was found to be 21.4 kJ/mol.     

过硫酸钾-脲氧化还原引发下的丙烯酰胺水溶液聚合

为制备高分子量聚丙烯酰胺(PAM),对其引发体系,尤其是对氧化还原引发做了许多探索^[1]。     

Aqueous Polymerization of Methyl Methacrylate Initiated by the Bromate-Thiourea Redox System

The aqueous polymerization of methyl methacrylate initiated by the bromate-thiourea redox system in dilute HC1 has been investigated under nitrogen atmosphere. The rate of polymerization increases with increasing concentration of thiourea in the range 5 × 10^?3?10 × 10^?3 M. The percentage of conversion increases with increasing concentration of the catalyst, but beyond 1.5 × 10^?2 M, there is a decreasing trend in the rate of polymerization. The rate of polymerization increases with increasing monomer concentration, but beyond 0.184 M the polymerization rate decreases due to gel effect. The rate of polymerization increases with temperature up to 35°C and beyond 40°C a decreasing trend is noticed. The effect of water miscible organic solvents, certain neutral salts on the rate of polymerization has also been investigated.     

Aqueous Polymerization of Methyl Methacrylate Initiated by Potassium Peroxydisulfate-Ascorbic Acid Redox System

The aqueous polymerization of methyl methacrylate initiated by the redox system K₂S₂O₈-ascorbic acid has been studied at 35°C under the influence of oxygen. The rate of polymerization increases with increasing ascorbic acid concentration at low activator concentration, remains constant within the range 4.375 × 10^?3 to 11.25 × 10^?3 mole/liter, and at higher ascorbic acid concentration again decreases. The rate varies linearly with monomer concentration. The initial rate and the limiting conversion increase with increasing polymerization temperature. Organic solvents (water-miscible only) and small amounts of neutral salts like KC1 and Na₂SO₄ depress the initial rate and the maximum conversion. The addition of small amounts of salts like Cu²⁺ and Mn²⁺ increases the initial rate, but no appreciable increase in the limiting conversion is observed.     

3-甲基丙烯酰胺基-9-乙基咔唑-过硫酸钾氧化还原体系引发丙烯酰胺聚合

合成了可聚合芳香叔胺-3-甲基丙烯酰胺基-9-乙基咔唑,并与过硫酸钾组成氧化还原引发体系引发丙烯酰胺水溶液聚合,测定了聚合反应动力学,得到了超高分子量的聚丙烯酰胺.     

3—甲基丙烯酰胺基—9—乙基咔唑—过硫酸钾氧化还原体系引发 …

合成了可聚合芳香叔胺－３－甲基丙烯酰胺基－９－乙基咔唑,并与过硫酸钾组成氧化还原引发体系引发丙烯酰胺水溶液聚合,测定了聚合反应动力学,得到了超高分子量的聚丙烯酰胺。     

Polymerization of Acrylamide Initiated by the Redox System Potassium Persulfate/Lactic Acid,Catalyzed by Silver Ions

The aqueous polymerization of acrylamide initiated by the potassium persulfate/lactic acid system catalyzed by Ag⁺ ions has been studied iodometrically over the temperature range from 35 to 50 ± 0.2°C. The rate of polymerization is governed by the expression R_p ∞ [M]^0.8[K₂S₂O₈]^1.0[Ag]^1.0 The deviation from normal kinetics has been studied. A tentative mechanism of initiation is suggested. The overall energy of activation is 5.52 kcal/mol.     

Aqueous Polymerization of Methyl Methacrylate Initiated by the Potassium Bromate-Thiomalic Acid Redox System

The redox system composed of potassium bromate and thiomalic acid was used to initiate the aqueous polymerization of methyl methacrylate under nitrogen atmosphere at 35 ± 0.2°C. The initial rates of polymerization have been found to be approximately proportional to the first power of the initiator concentration in the range of 2.5 to 6.0 ± 10^?3 M and to the first power (1.15) of monomer concentration in the range of 3.72 to 11.16 ± 10^?2 M The overall rate was independent of activator concentration, approaching a maximum at 10 × 10^?3 M. The overall energy of activation was found to be 8.80 kcal/mol. The initial rate and the maximum conversion attained a maximum value at 35°C in the temperature range of 20 to 45°C.     

Surface Grafting onto Barium Sulfate: Polymerization of Acrylamide Initiated by the System Consisting of Alcoholic Hydroxyl Groups on the Surface and Ceric Ion

Abstract

To modify the surface of barium sulfate, the grafting of polymers onto the surface by the polymerization of acrylamide (AAm) initiated by the system consisting of eerie ion and alcoholic hydroxyl groups on the surface was investigated. Barium sulfate modified by 12-hydroxystearate (BaSO₄-HS) was prepared by the reaction of barium chloride with sodium sulfate containing a small amount of sodium 12-hydroxystearate. The presence of 12-hydroxystearate groups on the BaSO₄ surface was confirmed by XPS analysis and infrared spectra. It was found that the graft polymerization of AAm is initiated by the system consisting of eerie ion and BaSO₄-HS to give poly (AAm)-grafted BaSO₄. This indicated that the grafted polymer chains are propagated from surface radicals formed by the redox reaction of eerie ion with 12-hydroxystearate groups on the surface. The polymerization rate (R _p) of AAm initiated by the redox system was given by R _p = k[AAm][Ce(IV)][BaSO₄-HS] where k is constant, [AAm] is AAm concentration, [Ce(IV)] is cerie ion concentration, and [BaSO₄-HS] is BaSO₄-HS concentration. The result suggested that in such an initiating system, the unimolecular termination of growing polymer radicals from the surface of BaSO₄ proceeds preferentially. Furthermore, by grafting of poly(AAm) onto the BaSO₄-HS surface, the wettability of the surface was found to turn from hydrophobic to hydrophilic.     

Acrylonitrile Polymerization by Ceric lon-Primary Alcohol Redox Systems in Aqueous Nitric Acid

The polymerization of acrylonitrile (AN) initiated by Ce^IV-primary alcohol redox systems has been studied in aqueous nitric acid under nitrogen in the temperature range 0 to 45° C. Taft's correlation can be applied to fit the kinetic results relative to a series of differently substituted primary alcohols. The polymerization is initiated by primary radicals formed in water from the dismutation of the Ce^IV -alcohol complex, This process has a high activation energy (21 kcal/mol) and gives rise to an induction period at temperatures lower than 40° C. PAN chains containing the alcohol residue are terminated predominantly on metal ions. The alcohol enhances the AN solubility in water and accordingly influences the polymerization kinetics. Variations in temperature and concentration of both components of the redox system allow control of the polymerization rate and of the molecular weight of the resulting PAN.     

辣根过氧化物酶酶促体系引发丙烯酰胺聚合的研究

对辣根过氧化物酶(HRP)、H2O2和乙酰丙酮(ACAC)组成的三元醇促体系引发的丙烯酰胺(AAM)聚合进行了研究。在膨胀计中考察了反应温度和HRP、ACAC、H2O2及AAM初始浓度对酶促体系引发AAM聚合动力学行为的影响,确定了适宜的反应条件。用FTIR和GPC对聚合产物进行表征,得到的聚丙烯酰胺的数均分子量为10^5-10^6,分子量分布指教DI为2-3。     

Aqueous Polymerization of Methyl Methacrylate Initiated by Ce4+-Glycolic Acid Redox System

The aqueous heterogeneous polymerization of methyl methacrylate (MMA) initiated by the Ce⁴⁺-glycolic acid (GA) redox system was studied at 35 × 0.2°C under a nitrogen atmosphere. The rate of monomer disappearance was proportional to [MMA]¹[GA]¹[Ce⁴⁺]°, and the rate of eerie ion disappearance was found to be directly proportional to [Ce⁴⁺] and [GA] but independent of [MMA]. The activation energy was found to be 34 kJ/mol. The molecular weight of polymethyl methacrylate increased with increasing [MMA] and decreased with increasing [oxidant]. The effect of increasing [H₂SO₄] on polymerization was also studied. The results are compared with those obtained for the aqueous homogeneous polymerization of acrylamide with the same redox pair.     

Polymerization of Acrylonitrile: Kinetics of the Reaction Initiated by the Redox System Mn3/Mannitol

Polymerization of acrylonitrile initiated by the redox system Mn³⁺/mannitol has been investigated in aqueous sulfuric acid in the temperature range 35–50°C. The rate of polymerization R_p and the rate of disappearance of Mn⁺³ (?R_M) were measured. The effect of certain water-miscible organic solvents, inorganic salts and complexing agents on the rate of polymerization have been investigated. Based on the experimental results, a suitable reaction mechanism is suggested involving the formation of complex between Mn³⁺ and the hydroxyl group of the substrate molecule, whose decomposition yields the initiating free radical; the polymer chain is terminated by the mutual combination of growing chains.     

Aqueous Polymerization of Methyl Methacrylate Initiated by the Mn(lll)-Fructose Redox System

The kinetics of vinyl polymerization of methyl methacrylate initiated by the redox system Mn³-fructose were investigated in aqueous sulfuric acid in the temperature range of 20-25°C, and the rates of polymerization and disappearance of Mn³⁺ were measured. The effect of certain water-miscible organic solvents and certain cationic and anionic surfactants on the rate of polymerization has been investigated. A mechanism involving the formation of a complex between Mn³⁺ and fructose whose decomposition yields the initiating free radical with the polymerization being terminated by the metal ion has been suggested.     

Vinyl Polymerization Initiated by Peroxydiphosphate. IV. Polymerization of Acrylonitrile Initiated by Peroxydiphosphate-Thioacetamide Redox System

Abstract

The kinetics of the aqueous polymerization of acrylonitrile initiated by the peroxydiphosphate-thioacetamide redox system was investigated at 35, 40, and 50°C. The rates of polymerization were measured at different concentrations of oxidant, activator, and monomer. Peroxydiphosphate alone did not initiate polymerization under deaerated and undeaerated conditions. Addition of certain water-miscible organic solvents and neutral salts depress the rate and conversion. On the basis of experimental observations of the dependence of the rate of polymerization on various variables, a suitable kinetic scheme has been proposed.     

Polymerization of Methacrylamide Initiated by the Persulfate/Thiolactic Acid Redox System

The aqueous polymerization of methacrylamide initiated by the ammonium persulfate/thiolactic acid redox system has been studied at 35 ± 0.2°C. The rate of polymerization is governed by the expression, R_p + K_p [MAA] ^1.33 [TLA]^0.22 [ammonium persulfate]^0.6. The deviations from normal kinetics are discussed. A tentative mechanism of initiation is given. The temperature dependence of the rate of polymerization has been studied over the range 30–55°C. The overall activation energy of polymerization is 10.4 kcal/mole.     

胶囊固定化辣根过氧化物酶酶促体系引发丙烯酰胺聚合研究

研究了以海藻酸钠／壳聚糖／海藻酸钠为囊壁材料的胶囊固定化辣根过氧化物酶的制备及其影响因素,并将肢囊固定化辣根过氧化物酶／乙酰丙酮／H2O2酶促体系用于引发丙稀酰胺的聚合。结果表明,作为囊壁材料之一的壳聚糖的平均分子量以1万左右为宜,以柠檬三酸钠溶液为溶芯荆的溶芯时间控制在2～4min时,固定化率可达60％,相对于游离酶,其相对活力约为60％。胶囊固定化辣根过氧化物酶／乙酰丙酮／H2O2酶促体系可引发丙稀酰胺的聚合。