Polymerization of methyl methacrylate in water in presence of some egyptian sands and quartz pegmatite

The polymerization of methyl methacrylate was carried out in water in presence of some Egyptian sands and quartz pegmatite using sodium bisulphite as initiator. The polymerization was performed at 30, 40, 50 and 60°C using initiator concentrations varying from 0.05 to 0.3 mol/l. The overall rates of polymerization increased from 2.0 × 10^?5 mol/l·s to 4.8 × 10^?5 mol/l·s in presence of quartz pegmatite, to 5 × 10^?5 mol/l·s when Natron sand was used and to 6.4 × 10^?5 mol/l·s in the presence of Ahram sand, as the concentration of each was varied from 0 to 30 g/l. The effect of change of temperature, initiator and monomer concentration on the overall rate of polymerization was studied. The molecular weights were determined viscosimetrically. It was found that the average molecular weights of the obtained polymers increase with the increase of both monomer and initiator concentrations and decrease with rise of temperature. Ahram sand leads to a higher polymer yield and a lower average molecular weight than in case of Natron sand. The stereoregularity of the obtained polymers was determined with a 60 MHz NMR spectrometer.     

Iron (II) chloride catalyzed emulsion polymerization of methyl methacrylate using different initiators

The emulsifier and emulsifier-free emulsion polymerization of methyl methacrylate (MMA) using sodium bisulphite, acetaldehyde sodium bisulphite (ACSB), octyladehyde sodium bisulphite (OSB), benzaldehyde sodium bisulphite (BSB), and acetone sodium bisulphite (ASB) as different initiators, and dodecyl benzene sodium sulphonate (DBSS) as an emulsifier, were carried out at 30, 40, and 50°C. The effect of iron (II) chloride on the rate of polymerization and on the viscosity-average molecular weight was investigated. The effect of temperature, iron (II) chloride, and the type of initiator on the tacticity of the obtained polymers was investigated by means of nuclear magnetic resonance (NMR) spectroscopy. The effect of iron (II) chloride and the four carbonyl adducts (ACSB, OSB, BSB, and ASB) on the volume-average diameter and the number of polymer particles per unit volume was investigated. It was found that iron (II) chloride has a pronounced catalytic effect on the emulsion polymerization. The initiating powers of the four carbonyl adducts, ACSB, BSB, OSB, and ASB, were found to be 3.27, 0.6, 1.78, and 0.23, respectively. The rate of emulsion polymerization and viscosity-average molecular weight were found to be dependent on the emulsifier concentration, initiator type and concentration, temperature, and amount of the catalyst (FeCl₂). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1725–1738, 1998     

Thiol–Disulphide Interchange Reactions in the Setting of Single Wool Fibres

Wool fibres pretreated with fluoro–2, 4–dinitrobenzene, N–ethylmaleimide, peracetic acid, or nitrous acid set less readily than untreated fibres when stretched for 1 h at 100C in water or acetate buffer at pH 5. Incorporation of sodium bisulphite in the setting solution at concentrations greater than 0005 M eliminated these differences, except for fibres that had been treated with nitrous acid. The set retained by both untreated and modified fibres was increased by the addition of bisulphite to the setting solution. The presence of bisulphite in the solution used for releasing (1 h at 100C) the fibres set in the absence of bisulphite decreased the set retained, but had no effect if the fibres were set in the presence of bisulphite. Treatment of the unmodified wool fibres with solutions of bromine, peracetic acid, or methyl mercuric iodide before and during release at 100C greatly increased the set retained in an acetate buffer. Similar aftertreatments of the modified fibres caused a relatively small increase in set. Setting in buffer solutions at pH 9, when followed by release in the same solution, was only slightly decreased in extent by pretreatment of the fibres with N–ethylmaleimide or peracetic acid, whereas setting was prevented by pretreatment with fluoro–2, 4–dinitrobenzene or nitrous acid. The presence of sulphite in the solutions used for setting or releasing the fibres did not affect the result. It is suggested that rearrangement of disulphide bonds by a thiol–disulphide interchange reaction is chiefly responsible for setting of wool fibres at pH 5 in the absence of a reducing agent, but that a second type of interaction, possibly the formation of β–keratin, assumes great importance when the fibres are set in bisulphite solution. Setting at pH 9 probably takes place by the formation of new covalent linkages. Lysine side–chain groups may participate in the formation of these linkages.     

Characterization of some poly(methyl methacrylate) prepared by emulsion polymerization in presence of egyptian delta titano magnetite ore (EDTMO)

The emulsion polymerization of methyl methacrylate was studied in water using potassium persulphate as initiator and dedocyl–benzene sodium sulphonate as emulsifying agent at 85°C. The effect of Egyptian delta titano magnetite ore (EDTMO) upon the activation energy and on the mean average molecular weights of the obtained polymers was studied. It was found that the viscosity average molecular weights increase with decrease of reaction temperature and initiator concentration but increase with increase of monomer concentration in the reaction medium. Some of the polymer samples prepared in absence and in presence of some (EDTMO) were separated on tlc plates according to molecular weight in binary mixture, benzene:methanol (1:1.4 by volume) at 30°C. The tlc techniques were performed to give an idea about the molecular weight distribution of the polymer samples obtained.     

Synthesis and Characterization of Starch-Poly(vinyl Acetate) Graft Copolymers and their Saponified Form

A redox initiation system based on potassium persulfate/acetone sodium bisulphite (KPS/ASBS) was developed to initiate the graft copolymerization of vinyl acetate (VAc) monomer onto corn starch in aqueous solution. The grafting reaction was studied with respect to grafting yield (GY), grafting efficiency (GE) and total conversion (TC) and results obtained were compared with those a well-established redox initiation system namely potassium persulfate/sodium bisulphite (KPS/SBS). The effect of reaction variables such as redox initiator concentration, liquor ratio, reaction time and temperature as well as VAc concentration were investigated. The GY, GE and TC increased significantly with increase of the redox initiation concentration up to 8/16 mmol/l irrespective of the initiation system used. Moreover, optimal grafting was obtained at 60 ^○C for KPS/ASBS redox system and 70 ^○C for KPS/SBS redox system. Saponification of poly (vinyl acetate)-starch graft copolymers were effected using NaOH in three different bath media (n-hexane, acetone or methanol) to convert starch-g-poly(vinyl acetate) to starch-g-poly(vinyl alcohol). Higher extent of solubility in hot water of the saponified form was achieved by using a bath containing n-hexane/sodium hydroxide; however, increasing the graft yield higher than 26.3% decreases the solubility. The structures and thermal stability of starch, grafted starch copolymer and saponified grafted starch copolymer were characterized by infrared spectroscopy and thermogravimetric analysis. Moreover, the rheological behavior as well as sizing performance of the saponified grafted starch copolymers were evaluated and compared with the native starch and commercial polyvinyl alcohol.     

Graft copolymerisation of vinyl monomers on modified cottons. VII. Grafting by chain transfer

Grafting of methyl methacrylate on cellulosic materials by chain transfer under the catalytic influence of azobisisobutyronitrile (AIBN) was extensively studied. The graft yield is influenced by reaction time, temperature, monomer and initiator concentration, reaction medium and nature of the substrate. In general, the grafting reaction shows an induction period after which the polymerisation proceeds rapidly. The graft yield increases and the induction period decreases by rising the reaction temperature from 50 to 70°C. This is also the case when the monomer concentration was increased from 2 to 6%. Increasing the AIBN concentration up to 0.01 M causes a significant enhancement in grafting while further increase brings about a marked fall in the graft yield. Among the reaction media studied, a water/solvent mixture containing 25% of either methanol, ethanol, propanol, butanol or acetone seems to constitute a reaction medium where the monomer and initiator are completely miscible and the swelling of cellulose by water is not hindered by the presence of these solvents. Increasing the solvent ratio in the water/solvent mixture causes a considerable decrease in the graft yield. The polymer content of the cellulosic materials, i. e. the graft yield, follows the order: partially carboxymethylated cotton > cotton treated with 12N sodium hydroxide > cyanoethylated cotton > cotton treated with 0.5 N sodium hydroxide > purified cotton. In addition, proof of grafting was provided by the fractional precipitation method.     

Reactions catalyzed by soda lime glass. II. Polymerization of methyl methacrylate

Rates of sodium bisulfite-initiated polymerization of methyl methacrylate (MMA) in water were determined in the presence and absence of colorless and colored soda lime glass (amber glass). The rate of polymerization increased in the presence of glass. For example, the rate of polymerization increased from 1.3 × 10^?5 mole/(1.sec) to 3.9 × 10^?5 mole/(1.sec) when amber glass (200 mesh) concentration was varied from 0 to 30 g/l. of the reaction mixture at 40°C. It was found that the finer the particle size of the soda lime glass, the higher was the conversion percentage of monomer to polymer. A glass–polymer combination containing 20 g glass was prepared and subjected to Soxhlet extraction with benzene; the insoluble polymer part was found to increases as initiator concentration was decreased.     

Photopolymerization of butyl acrylate-in-water microemulsions: Polymer molecular weight and end-groups

Solubilization of butyl acrylate in water using sodium dodecyl sulfate (SDS) and 1-pentanol produced transparent oil-in-water microemulsions stable at room temperature. These microemulsions were polymerized using a two-component water-soluble initiator system comprising of Rose Bengal (RB) and methyldiethanolamine (MDEA). These compounds undergo photo-induced electron transfer upon absorption of visible light to produce amine radicals active in free radical polymerization. Analysis of the NMR spectra of polymers revealed only monomer peaks and amine fragments which were incorporated as the polymer ends. Effect of initiator composition on polymer length was also investigated using GPC. When RB concentration was increased with constant concentration of excess MDEA, the average chain length decreased up to a specific concentration where after the polymer length reached an asymptotic value. Experiments were performed to identify this asymptotic value and it was observed that as the MDEA concentration was increased, the asymptotic values of number average degree of polymerization decreased.     

Cure‐on‐demand wood adhesive based on the frontal polymerization of acrylates

We demonstrated for the first time a cure‐on‐demand wood adhesive using thermal frontal polymerization with Southern Pine wood. Monomer structure, initiator loading, and filler loading all had an impact on the strength of the adhesive and the cure‐on‐demand ability. More flexible, ethoxylated monomers produced stronger adhesives; though, the ethoxylate groups reduce the ability of the system to be polymerized frontally. Addition of a highly reactive comonomer (acrylic acid) to increase molecular weight between crosslinks along with the ethoxylated triacrylate increased the propensity for frontal polymerization and made a tougher polymer. Increasing initiator loading could help ensure front propagation, but a maximum initiator loading was reached where the gaseous byproducts of the peroxide initiator made the network highly porous and thus lacking strength. Fillers such as kaolin and sawdust helped overcome decreases in strength at high initiator loadings. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44064.     

Water‐soluble copolymers. V. Synthesis of low molecular weight amphoteric polyacrylamide by foamed copolymerization

Amphoteric polyacrylamide of acrylamide, acryloyloxyethyl trimethylammonium chloride, sodium acrylate, and acrylic acid was synthesized by foamed copolymerization. The effects of monomer concentration and composition, initiator concentration and composition, sodium bicarbonate and stabilizer content on the polymer intrinsic viscosity and monomer conversion were examined. The monomer conversion increased with increasing initiator concentration, sodium bicarbonate and stabilizer content. The polymer intrinsic viscosity decreased with increasing initiator concentration. The structure and low molecular weight of the amphoteric polymer were identified by fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC), respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polycarbamoyl Sulphonates: Water-soluble Shrink-resist Polymers for Wool

Water-soluble polymers suitable for shrink-resisting wool fabric by a pad–dry sequence can be prepared by the reaction of polyisocyanates with bisulphite salts. This paper examines the relationship between polymer structure and textile properties in these bisulphite adducts, or polycarbamoyl sulphonates (PCS). The reaction of various polyisocyanates with sodium bisulphite was examined. PCS could be prepared only from polyisocyanates with polyether backbones but not from those with polyester, polybutadiene or polycaprolactone backbones. Stable PCS were obtained from aliphatic isocyanates but those from aromatic isocyanates were relatively unstable. The PCS shrink-resisted wool fabric and behaved similarly to the parent polyisocyanates on wool. The polyureas formed on curing were somewhat susceptible to thermal and photo-oxidative degradation but this was improved to an acceptable level by the addition of hindered phenolic antioxidants.     

新水溶液均相法制备两性聚丙烯酰胺的研究

采用氧化还原引发体系与AIBA为复合分段引发剂,在绝热水溶液体系中进行丙烯酸钠／丙烯酰胺／丙烯酰氧基乙基三甲基氯化铵自由基共聚合。研究了聚合温度、氧化还原引发体系用量、AIBA用量、单体浓度、共聚单体中DAC、AM含量,复合分散剂用量及其HLB值等对聚合反应单体转化率和聚合物特性黏度的影响。聚合物特性黏度随引发剂用量和单体浓度的增大而增大的实验结果证实了该两性聚丙烯酰胺水溶液均相制备过程中凝胶效应的存在。     

Polymerization of ethyl methacrylate,methyl methacrylate,and vinyl acetate using sulfonated polystyrene as the initiator

Polymerization of ethyl methacrylate (EMA) and methyl methacrylate (MMA) was achieved in glass dilatometers, at 86°C, using polystyrene sulfonate (Na⁺ and H⁺ forms) as initiators. The conversion of EMA to PEMA and MMA to PMMA increased with the time of polymerization, quantity of initiator, and size of dilatometer but decreased with volume of water. The polymer yield was higher for the Na⁺ than for the H⁺ form of the resin initiator. The average degree of polymerization increased with increase in the volume of water, but decreased with the quantity of initiator. Vinyl acetate could not be polymerized using either the Na⁺ or H⁺ forms of the polystyrene sulfonate as the initiator under the conditions of EMA or MMA polymerization.     

Graft copolymerization of acrylamide onto carboxymethylcellulose with the xanthate method

Acrylamide was grafted to an xanthate mixture of carboxymethylcellulose with a sodium bisulfate/ammonium persulfate redox initiator system in water, sodium hydroxide, potassium hydroxide, and dioxane at 40, 50, 60, 70, and 80°C during a reaction period of 2 h. The grafted polymer and homopolymer were isolated with diethyl ether from the reaction mixture, dried, and weighed. The grafted polymer was characterized with IR and mass spectrometry methods, and the microscopic morphology was detected with electron scanning microscopy. The graft level percentage distinctly increased with the use of sodium hydroxide, potassium hydroxide, and dioxane over that of a reaction carried out completely in an aqueous medium. Also, the graft level decreased as the reaction temperature increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 271–278, 2004     

反相乳液聚合合成聚丙烯酰胺

以甲苯为介质,Span80/Span20为乳化剂,叔丁基过氧化氢/亚硫酸氢钠氧化还原体系为引发剂,采用反相乳液聚合制备了分子量高达9.4×106的聚丙烯酰胺乳液。研究了乳化剂种类及用量、引发剂种类及用量、油水比、单体浓度,反应温度对共聚物相对分子量、聚合转化率以及聚合反应速率的影响。其最佳聚合配方及工艺条件为:油水体积比为1.4,单体浓度30%,引发剂用量0.003%,乳化剂用量12%,聚合温度30℃。     

植物栽培多彩吸水聚合物制备

采用丙烯酸、氢氧化钠、丙烯酰胺为原料,以N,N-亚甲基双丙烯基酰胺为交联剂,以过硫酸铵、无水亚硫酸钠为引发剂,选择颜色鲜艳又具有水不溶性的颜料为着色剂,采用溶液聚合法合成具有色彩晶莹、吸水不褪色的多彩吸水聚合物。并讨论了交联剂用量、单体浓度、引发剂用量等因素对产品吸水倍数的影响以及颜料的选择、水不溶性颜料的用量对产品着色、褪色的影响。结果表明,适宜的合成条件为:丙烯酸14.2 g,氢氧化钠17.2 g,蒸馏水43.8 g,丙烯酰胺26.6 g,N,N-亚甲基双丙烯基酰胺0.15 g,5%过硫酸溶液2 mL,5%无水亚硫酸钠溶液2 mL,颜料8 mL。     

Ultrasonic degradation of poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water‐soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates—potassium persulfate, ammonium persulfate, and sodium persulfate—were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Emulsion polymerization of methyl methacrylate in the presence of burnt mazote boiler deposit

The emulsion polymerization of methyl methacrylate (MMA) using different initiators was carried out in the absence and presence of burnt mazote boiler deposit (BMBD). When sodium persulfate or potassium persulfate was used, the initial rate of polymerization was found to decrease with increase of the burnt mazote boiler deposit concentration but to increase when sodium bisulfite was used as initiator. The initial rate of polymerization was found to be higher in nitrogen atmosphere than in air. The apparent activation energy (E_a) was found to be 12.4 × 10⁴ J/mol and 16.3 × 10⁴J/mol in the absence and presence of burnt mazote boiler deposit when potassium persulfate was used as initiator and 5.9 × 10⁴ J/mol and 5.1 × 10⁴ J/mol when sodium bisulfite was used as initiator, respectively. The mean average molecular weights for PMMA were found to increase with increase of the burnt mazote boiler deposit when sodium bisulfite was used as initiator.     

星形杂臂异戊二烯-丁二烯-苯乙烯橡胶的结构与性能

采用负离子溶液聚合法,以正丁基锂为引发剂、环己烷为溶剂、十二烷基苯磺酸钠/四甲基乙二胺为复合结构调节剂、二乙烯基苯为偶联剂制备了具有高抗湿滑性和低滚动阻力的星形杂臂异戊二烯-丁二烯-苯乙烯橡胶,考察了聚合温度及结构调节剂和偶联剂用量对聚合物微观结构、动态力学性能及力学性能的影响.结果表明,聚合物中非1,4-结构链节的含...     

氧化还原引发AA/AM/AMPS超浓反相乳液聚合及乳液稳定性的研究

以丙烯酸（AA）、丙烯酰胺（AM）、2-丙烯酰胺-2-甲基丙磺酸（AMPS）作为混合单体,Span-80和Tween-60作为复合乳化剂,采用氧化还原引发体系,在30℃下制备了稳定的超浓反相聚合物乳液。研究了油相体积分数和引发剂用量对乳液稳定性的影响,分别用离心、加热方式对超浓反相聚合物乳液进行了稳定性的表征。结果表明,在乳化剂浓度一定的条件下,一定量的水相形成稳定结构的乳液所需要的油相量是一定的。聚合物乳液的稳定性随着油相体积分数的减小而增大,随着引发剂用量的增加先增大后减小。