Aspects regarding the grafting of some lignosulfonates with acrylamide under a magnetic field

The kinetics of the graft polymerization of acrylamide onto some lignosulfonate products in a continuous external magnetic field was studied. The registered magnetokinetic effects were correlated and associated with the conditions of the classic reaction. The grafting process of acrylamide onto the macromolecular chains depending on the cation (Ca²⁺, Cr²⁺, Fe²⁺, Fe³⁺ and NH₄⁺) present in the lignosulfonate structure and the magnetic field influence were corroborated and explained through the radical pairs mechanism. The augmentation of the graft polymerization rate in magnetic field and conversion was ascribed to the singlet-triplet transitions in the radical pairs as a result of the presence of the magnetic field.     

A new polymerization method and kinetics for acrylamide: Aqueous two‐phase polymerization

The concept of aqueous two‐phase polymerization and a new polymerization method for the preparation of water‐soluble polymers are presented. The phase diagram of poly(acrylamide) (PAAm)‐poly (ethylene glycol) (PEG)‐water two‐phase system was measured by the gel permeation chromatography (GPC). The aqueous two‐phase of PAAm‐PEG‐water system can be easily formed. The critical concentration of phase separation was affected by the molecular weight of PEG. The aqueous two‐phase polymerization of acrylamide (AAm) has been successfully carried out in the presence of PEG by using ammonium persulfate (APS) as the initiator. The polymerization behaviors with varying concentration of AAm, initiator and PEG, the polymerization temperature, the molecular weight of PEG, and emulsifier types were investigated. The activation energy of aqueous two‐phase polymerization of AAm was 132.3 kJ/mol. The relationship of initial polymerization rate (R_p0) with APS and AAm concentrations was R_p0 ∝ [APS]^0.72 [AAm]^1.28. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Inverse micro-emulsion polymerization of acrylamide in the presence of a mixture of oleophilic/hydrophilic surfactants

The effect of sodium dodecyl sulphate (SDS) on the formation of inverse micro-emulsion toluene/sodium bis(2-ethylhexyl)sulphosuccinate (AOT)/water/acrylamide (AAm)/SDS and on polymerization of acrylamide initiated by oil soluble dibenzoyl peroxide was studied. The presence of SDS shifts the value of the volume fraction of aqueous phase (Φ_aw) at which a two-phase Winsor II system forms, to higher values. It was shown that an increase of the mass ratio of SDS/water led to a decrease of acrylamide polymerization rate, of polyacrylamide particle size and of polyacrylamide molecular mass distribution. It was also found that in the presence of SDS, a nearly constant value for acrylamide polymerization rate in inverse micro-emulsion in the range of Φ_aw values between 5% and 50% can be obtained. The polymerization kinetics and polymer particle formation were explained as consequences of the initiation of acrylamide polymerization in two reaction loci—in inverse micelles and in the oil macrophase of the inverse micro-emulsion. © 1998 SCI.     

Radiation-induced solid-state polymerization in binary systems. IX. Polymerization and foaming of multicomponent systems including inorganic acid and acrylic monomers

It was found that binary systems consisting of inorganic acid and organic amide or nitrile form a stable glassy phase owing to the large molecular interaction between the components. The change in T_g values with change in composition of these binary systems was studied. Gamma ray-induced polymerization of inorganic acid and acrylamide or acrylonitrile systems was carried out in a supercooled phase. The polymerization rates in acrylamide–inorganic acid systems had a maximum at a temperature T_v (30°–50°C higher than the glass transition temperature), but in acrylonitrile–inorganic acids systems there was no maximum rate at any temperature. Foaming occurred during irradiation in the polymerization of acrylamide–urea–sulfuric acid system. The insource foaming was attributed to the promoting effect of sulfuric acid for the decomposition of urea and the heat accumulation by the acceleration of the polymerization.     

Polymerization of acrylamide and methacrylamide initiated by a potassium peroxydiphosphate/Mn(II) system

The kinetics of aqueous polymerization of acrylamide (AM) and methacrylamide (MAM) have been studied using a potassium peroxydiphosphate (PDP/Mn(II) system in an inert atmosphere at 40°C and at constant pH (1·30). The polymerization rate R_p has been found to be proportional to the half power of PDP and Mn(II) concentrations. The overall energy of activation (ΔE) was found to be 40·2±0·1kJmol^-1 and 45·0±0.1kJmol^-1 for AM and MAM, respectively. Intrinsic viscosity [η], viscometric average molecular weight (M_v) and number average degree of polymerization (P_n) at different concentrations of PDP, Mn(II) and monomer are reported. © 1998 SCI.     

Kinetic study of radical polymerization. III. Solution polymerization of acrylamide by 1H‐NMR

Solution and radical polymerization of acrylamide in the presence of potassium persulfate in D₂O was investigated up to high conversion by high‐field ¹H‐NMR spectroscopy. The kinetics of reaction was studied according to the data obtained from the corresponding spectra at various times during the polymerization reaction progress. Processing of the data led us to derive the rate equation of this polymerization reaction and determine the reaction order of each component in the rate equation. The order, with respect to initiator, was consistent with the classical kinetic rate equation (0.45), whereas the order with respect to monomer was greater than unity (1.49). The effect of temperature on the polymerization rate was also investigated and the activation energy of 48.4 kJ mol^?1 was obtained over the temperature range of 60–75°C. Also some mechanistic studies were discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2007–2013, 2004     

Study of microwave irradiation polymerization mechanism in the presence of carriers

Microwave irradiation polymerization was studied in the presence of a carrier. The influence of different carriers, such as Al₂O₃, SiO₂, and MgO on the microwave irradiation polymerization mechanism of acrylamide and 2‐ethylhexyl acrylate was studied by adopting polymerization inhibitors such as an anionic inhibitor, cationic inhibitor, and radical inhibitor hydroquinone. When the system contains the carriers Al₂O₃ and SiO₂, the polymerization mechanism occurs according to a radical mechanism, but when the system contains MgO, the polymerization mechanism occurs according to not only a radical mechanism but also an anionic polymerization mechanism with superficial grafting occurring. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1519–1524, 2004     

Polymerization of acrylamide in single-phase in-verse dispersion systems at high volume fractions of dispersed phase

The preparation of single-phase inverse microemulsions of toluene/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water/acrylamide (AAm) is described and their properties prior to polymerization (macro and microviscosity as a function of volume fraction Φ_aw of the dispersed aqueous (water + acrylamide) phase, of the [to-luene]/[AOT] molar ratio and of the acrylamide/water mass ratio) were studied. The polymerization of acrylamide in dispersion systems was initiated by the oilsoluble initiator dibenzoyl peroxide at 60°C. The polymerization rate of acrylamide for a given [toluene]/[AOT] molar ratio and AAm/water mass ratio monotonically decreases beyond a Φ_aw value of 20%. The polymer particle size in polymerized systems as well as the molecular mass of polymer in the polymer particles increase on increasing the acrylamide concentration in the aqueous phase and/or the Φ_aw values of the dispersion system. On increasing the surfactant AOT concentration both polymer particle size and polymer molecular mass decrease for a given set of other relevant parameters of the dispersion system (i.e. [toluene]/[AOT] and AAm/water ratios). The polymerized inverse dispersion system can be converted to an oil-in-water dispersion by addition of water.     

Studies of inverse emulsion copolymerization of (2-methacryloyloxyethyl) trimethyl ammonium chloride and acrylamide

Inverse emulsion copolymerization of (2-methacryloyloxyethyl) trimethyl ammonium chloride with acrylamide initiated with potassium persulfate has been studied dilatometrically. Aqueous monomer solutions were emulsified in kerosene with a blend of two surfactants (Span80 and OP10). The gel effect is evident from the increase of the molecular weight with conversion and also from the percentage of conversion versus time curves. Monomer reactivity ratios have been derived as r_AM = 0.38 and r_DMC = 1.69 at pH 6.8. The effects of initiator concentration, concentration, and composition of the monomer, emulsifier concentration, etc., on the polymerization rate and intrinsic viscosity of polymer have been examined. The rate of polymerization (R_p) can be represented by R_p I^0.52[M]^1.50[E]^0.38. The overall activation energy for the rate of polymerization is 66.0 kJ mol (40–65°C). Based on these experimental results, some aspects of the polymerization mechanism are discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1005–1010, 1998     

Development of environmentally responsive hydrogels with metal affinity behavior

This work describes initial efforts to incorporate affinity ligands within an environmentally responsive hydrogel. Metal affinity ligands were chosen as model affinity groups and thermally responsive N‐isopropyl acrylamide/acrylamide copolymers were used as the base hydrogels. The ? NH₂ group of the acrylamide serves as a reactive group for functionalization with metal affinity ligands. The gels were synthesized by free radical polymerization and Cu²⁺ was bound to the gel via 1,4‐butanediol diglycidyl ether (BDE) as a linker and iminodiacetic acid (IDA) as a chelating ligand. The base acrylamide gels were also functionalized with metal affinity ligands to allow for comparison with thermally responsive affinity gels. The results show the effectiveness of this technique for both these types of gels, and an improved method to immobilize metal affinity groups on to thermally sensitive N‐isopropyl acrylamide gels was also developed. It was seen that the yields for the reaction with BDE decreased with increased reaction time in both kinds of gels, whereas reaction with IDA showed a decrease in yields with increase in temperature for N‐isoporpyl acrylamide gels and increase in yields for acrylamide gels. Further techniques were developed to overcome diffusional resistances and stresses in the thermally responsive N‐isopropyl acrylamide gels so as to improve the distribution of Cu²⁺ ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

On the synthesis of acrylamide oligomers

The synthesis of low-molecular-weight poly(acrylamide)s (M?_n = 500 – 1 000) is described. Metal-activated and non-activated polymerization in aqueous solution was investigated employing hydrogen peroxide as initiator. Among four transition metal salts considered, Cu²⁺ cations proved to be the most efficient in decomposing H₂O₂ molecules and were used as activator. The experiments were run at three reaction temperatures (60, 80 and 95°C), at three H₂O₂ levels (4, 5 and 6 wt.-% on monomer), and at four Cu₂₊ levels (900, 600, 300 and 0 ppm by weight of metal on monomer). Thus, ist was possible to prepare acrylamide oligomers with monomer conversions exceeding 95%, and with M_n values covering the narrow range indicated above. Within these low limits a molecular weight control is impossible, even with inclusion of the differentiated levels of Cu²⁺cations. Intrinsic viscosities are very low, too ([η]) = 20 – 50 cm³/g, without any relations of the individual values to variations of the given process parameters. The work provides an industrial route to very-low-molecular-weight acrylamide oligomers.     

Self-condensing vinyl polymerization of acrylamide

Summary A novel approach to branched polyacrylamide was described. The branched structure resulted from the amidyl radicals which were formed by the reaction of amide groups with Cu(III) of potassium diperiodatocuprate, K₅[Cu(HIO₆)₂], in alkaline medium and capable of initiating the vinyl polymerization of acrylamide monomer. The obtained polymer was characterized by ¹H NMR, FT-IR and intrinsic viscosity measurements. Received: 8 January 1999/Revised version: 26 May 1999/Accepted: 25 June 1999     

Synthesis and polymerization of the acrylamide derivatives of fatty compounds

The Ritter reaction of plant oil triglycerides (such as soybean and sunflower oil) with acrylonitrile was used to introduce acrylamide functionality on the triglyceride. Acrylonitrile and triglycerides were reacted in the presence of H₂SO₄, and acrylamide derivatives were obtained in yields of 45 and 50% for sunflower oil and soybean oil, respectively. Radical initiated copolymerization of the acrylamide derivatives of the triglycerides with styrene produced semirigid polymers. Characterization of new monomers and polymers was done by ¹H‐NMR, ¹³C‐NMR, IR, and MS. The swelling behavior of the crosslinked network polymers was determined in different solvents. Glass transiton temperature (T_g) of the cured resin was also determined by differential scanning calorimeter to be 40°C for soybean based polymer and 30°C for sunflower‐based polymer. Homo‐ and copolymerization behavior of acrylamide derivatives of methyl oleate (MOA) and methyl 10‐undecenoate (MUA) were also investigated. The reactivity ratios of these monomers with respect to styrene were determined by the Fineman–Ross method using ¹H‐NMR spectroscopic data. The reactivity ratios were r_sty = 1.776; r_moa = 0512 for MOA, and r_sty = 1.142; r_mua = 0.507 for MUA, respectively. Photopolymerization behaviors of MOA and MUA were also investigated using the photoDSC technique and the rate of polymerization of MUA is higher than that of MOA under the same conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2264–2272, 2005     

Polymerization of acrylamide in inverse microemulsion in the presence of mixtures of oleophilic and hydrophilic surfactants

The preparation of single-phase toluene/sodium bis(2-ethylhexyl)sulfosuccinate(AOT)/water/acrylamide/sodium dodecyl sulfate(SDS) inverse microemulsions is described and their properties prior to polymerization (macroviscosity as a function of volume fraction Φ_aw of the dispersed aqueous (water + acrylamide(AAm) + SDS) phase, and of SDS/AAm mass ratio) are studied. At 20°C three viscosity maxima are observed. At 50°C all three peaks remain, the viscosity of the first and third peak, respectively, is lowered to 5–8 mPa· s while the second, most prominent peak still marks the level of ca. 250 mPa· s. The polymerization of acrylamide in dispersion systems is initiated by water-soluble ammonium peroxodisulfate (APS) and oilsoluble dibenzoyl peroxide (DBP) at 60°C. The polymerization rate of acrylamide for a given [toluene]/[AOT] molar ratio and AAm/water mass ratio monotonically decreases for Φ_aw values greater than 20%. The polyacrylamide viscosity molecular mass increases up to a Φ_aw value of ca. 30%, irrespective of the nature of initiator. For Φ_aw values over 30% the viscosity molecular mass of polyacrylamide seems to level off with some sings of shallow minimum close to Φ_aw of 50%.     

Photo‐mediated metal free atom transfer radical polymerization of acrylamide in water

Photo‐mediated metal free atom transfer radical polymerization of acrylamide was conducted at 25 °C in water under visible light irradiation with water soluble 2‐hydroxy‐3‐(4‐benzoylphenoxy)‐N,N,N‐trimethyl‐1‐propaminium chloride (HBTPC) as photoredox catalyst and 2‐hydroxyethyl 2‐bromoisobutyrate as alkyl halide. The polymerization followed first‐order reaction kinetics. The living character of photo‐mediated atom transfer radical polymerization of acrylamide was verified by the linear development of the polymer number average molar mass (M_n,GPC) with monomer conversion and narrow molecular weight distributions (?). The effects of acrylamide concentration, light intensity, amount of HBTPC, and tris(2‐dimethylaminoethyl)amine on polymerization were investigated. Increasing monomer concentration led to a higher M_n,GPC values with narrow ?. The polymerization rate increased with increasing the amount of monomer, light intensity, HBTPC and tris(2‐dimethylaminoethyl)amine. The polymerization was monitored by the periodic light on/off. The structure of polyacrylamide was analyzed by proton nuclear magnetic resonance spectrometer and gel permeation chromatography. Successful chain extension experiments show the controlled nature of the polymerization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46567.     

Synthesis of high molecular weight polyacrylamide flocculant by radiation polymerization

The radiation-induced polymerization of acrylamide was studied to prepare a high molecular weight and highly effective polyacrylamide flocculant. Among various solvents, mixtures of water–tert-butyl alcohol and water–acetone were found to be suitable for the synthesis of the high molecular weight polyacrylamide. For polymerization in acetone–water mixtures, the molecular weight of polymer increases with monomer concentration; but at the high concentration, intermolecular imidation of amide groups tends to take place during the polymerization to from crosslinked and water-insoluble polymer. The water-soluble polymer with the largest molecular weight of 6.7 × 10⁶ is produced in the polymerization with monomer concentration of 2.91 moles/1. at 0°C at a dose rate of 6.2 × 10² rad/hr in acetone–water mixture containing 60 vol-% water. The crosslinking of polymer of the formation of water-insoluble polymer could be avoided by the addition of K₂CO₃ or NaOH to raise the pH of the reaction mixture above 6.5. The flocculation effects were evaluated from sedimentation speed of kaolin suspension and transparency of the separated water. The sedimentation speed is proportional to the intrissic viscosity of the polymer in the range of 4 to 23 dl/g. The polymers prepared in this study show much higher sedimentation speed than commercial polyacrylamide flocculants. The transparency of the separated water is higher than 93%, similar to the results with commercial flocculants.     

Miniemulsion polymerization of fluorinated siloxane‐acrylate latex and the application as waterborne textile finishing agent

Fluorinated siloxane–acrylate polymer latex was synthesized via miniemulsion polymerization, which was carried out by pseudo one‐step method. In the synthesis protocol, the monomers of octamethylclotetrasiloxane (D₄), tetravinyltetramethylcyclotetrasiloxane (D₄^v), methyl methylacrylate, butyl acrylate, N‐methylol acrylamide, and dodecafluoroheptyl methacrylate (DFMA) were first mixed and homogenized into a miniemulsion, which was stabilized by dedecybenzene sulfonic acid. The ring‐opening polymerization of cyclosiloxane was then steadily performed under miniemulsion conditions and followed by the postaddition of radical initiators to initiate the polymerization of acrylate and DFMA monomers. The influences on the emulsion properties by acrylic monomer with different addition protocol were investigated in this work. In addition, the synthesized latexes were characterized by using dynamic laser scattering, transmission electron microscope, differential scanning calorimetry, and Fourier transform infrared spectroscopy. These results indicated that the introduction of D₄^v in the latex can successfully suppress the phase separation between the thermodynamically incompatible components for the formation of uniform hybrid latex particles. The further application of the as‐synthesized latex was investigated as a new kind of waterborne textile finishing agent. Moreover, the influences of the content of D₄^v and DFMA on the finishing properties, especially for the softness, the water repellence, and the antimoisture properties, were systematically studied in this work. With a proper design on the content of the D₄^v and DFMA, stable textile finishing emulsion was prepared, which can endow the fabric both desirable softness and excellent water resistances. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40161.     

Particle number and size of polystyrene‐dependent micellar crosslinking polymerization of acrylic acid

The effect of the number and size of polystyrene particles and the concentration of ammonium persulfate used as the initiator on the micellar crosslinking polymerization of acrylic acid was studied by real‐time monitoring of the storage modulus (G ′), the damping factor (tanδ), and the ratio of the complex modulus (G*) to the maximum G* (G*_max) during 1 h of polymerization. The molar ratio (5.83 × 10^?4) of N,N′‐methylenebis‐acrylamide to acrylic acid was fixed. Polystyrene particles were prepared by emulsifier‐free emulsion polymerization. The diameter of the particles ranged from 233 to 696 nm. The results show that crosslinking polymerization was most effective when 1.31 × 10¹² particles were incorporated into the system, while crosslinking polymerization was less effective in the particle‐filled system than in the unfilled polymerization system if the particle number was 50% lower or higher. Crosslinking was also more effective with the use of uncrosslinked firmer and larger particles at the fixed particle number, except for the anomalous behavior observed with 696 nm polystyrene particles. Increasing the feed concentration of the initiator resulted in more efficient crosslinking up to a limiting concentration of 0.765 mg mL^?1 (the molar ratio of initiator to monomer was 8.52 × 10^?4). When this initiator concentration was doubled, the rate of increase of G ′ in the deceleration phase was slower after the network was formed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42851.     

Magnetic field effects on the free radical solution polymerization of acrylamide

Systematic polymerization experiments quantified magnetic field (MF) influences on the free radical solution polymerization of acrylamide for various polymerization conditions. The type of initiation, the initiator concentration, the monomer concentration, and the viscosity of the aqueous medium were the subject of variation. The initiator efficiency (Φ) increased up to 60% and the initiator exponent of the overall rate expression raised from 0.1 to 0.28 when a weak MF of 0.1 T was applied to photochemical initiation. However, no appropriate effect was observed for thermal initiation. Kinetic analysis proved a reduction of the termination rate coefficient (k_t) up to 40%. Photochemically initiated polymerizations in media of enhanced viscosity revealed the highest increment of the initiator efficiency ratio Φ^MF/Φ and the most pronounced reduction of k_t^MF/k_t. On the contrary, the propagation rate coefficient (k_p) and the monomer exponent were not influenced by MF. Despite considerable increase of the polymerization rate in MF, no reduction of the molar mass was found. Compensation of increased Φ^MF and decreased k_t^MF are suggested as explanation. The singlet-triplet intersystem crossing mechanism for radical pairs served to explain the MF effects.