Viscosity‐molecular weight relationship for cellulose solutions in either NMMO monohydrate or cuen

The intrinsic viscosities, [η], of nine cellulose samples, with molar masses from 50 × 10³ to 1 390 × 10³ were determined in the solvents NMMO*H₂O (N‐methyl morpholin N‐oxide hydrate) at 80°C and in cuen (copper II‐ethlenediamine) at 25°C. The evaluation of these results with respect to the Kuhn–Mark–Houwink relations shows that the data for NMMO*H₂O fall on the usual straight line in the double logarithmic plots only for M ≤ 158 10³; the corresponding [η]/M relation reads log ([η]/mL g⁻¹) = –1.465 + 0.735 log M. Beyond that molar mass [η] remains almost constant up to M ≈ 10⁶ and increases again thereafter. In contrast to NMMO*H₂O the cellulose solutions in cuen behave normal and the Kuhn–Mark–Houwink relation reads log ([η]/mL g⁻¹) = −1.185 + 0.735 log M. Possible reasons for the dissimilarities of the behavior of cellulose in these two solvents are being discussed. The comparison of three different methods for the determination of [η] from viscosity measurements at different polymer concentrations, c, demonstrates the advantages of plotting the natural logarithm of the relative viscosities as a function of c. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Oxo‐biodegradability of high‐density polyethylene films containing limited amount of isotactic polypropylene

Limited amount of isotactic polypropylene (iPP) is added to high‐density polyethylene (HDPE) containing 1% w/w an oxo‐biodegradable additive and extruded and converted to films. The films are put under UV irradiation for different periods of time. Irradiation of the films for 6 weeks imposes remarkable effects on viscosity average molecular weight (M_v) and carbonyl index (CI) of them. M_v decreases from 3.4 × 10⁵ to 4.7 × 10⁴ g mol^?1 for neat HDPE films; from 3.1 × 10⁵ to 3.3 × 10⁴ g mol^?1 for the films containing oxo compound, and from 1.5 × 10⁵ to 2.6 × 10⁴ g mol^?1 for the films containing oxo compound and 1% w/w iPP. Carbonyl index of the neat HDPE films increases from 4 to 8.7 while for the sample containing only the oxo compound it increases from 4.5 to 7.3 and for the sample containing both oxo compound and iPP it decreases from 12.0 to 8.8. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) indicate more cracks and uniform degradation in the samples containing iPP and oxo compound. Thermogravimetric analysis (TGA/DTG) of the samples shows that the samples containing iPP and oxo compound have lower decomposition temperature after UV irradiation. Finally, it can be said that the presence of iPP in HDPE matrix containing oxo compound can improve HDPE oxo‐biodegradablity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45843.     

Polybenzimidazole (PBI) molecular weight and Mark‐Houwink equation

The molecular weight, and intrinsic viscosity of polybenzimidazole (PBI) and its phosphonylated derivatives are reported. The relationship between intrinsic viscosity [η] and weight average molecular weight (M_w) for PBI has been established in H₂SO₄ and DMF‐LiCl. The Mark Houwink constants K_w of 5.2 × 10^?3 mL/g, α of 0.92 for H₂SO₄ solvent systems and, K_w of 3.2 × 10^?2 mL/g, α of 0.754 for DMF‐LiCl solvent system have been determined at M_w < 65,000. The intrinsic viscosity of PBI determined by the Huggins–Kraemer method was compared with a single point method, and found that both methods fit well for PBI in relatively low concentration solvent system, giving ～ 99% accuracy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of star‐shaped poly(ϵ‐caprolactone) by samarium‐based tetrafunctional initiator and its dilute‐solution properties

An in situ–generated tetrafunctional samarium enolate from the reduction of 1,1,1,1‐tetra(2‐bromoisobutyryloxymethyl)methane with divalent samarium complexes [Sm(PPh₂)₂ and SmI₂] in tetrahydrofuran has proven to initiate the ring‐opening polymerization of ?‐caprolactone (CL) giving star‐shaped aliphatic polyesters. The polymerization proceeded with quantitative conversions at room temperature in 2 h and exhibited good controllability of the molecular weight of polymer. The resulting four‐armed poly(?‐caprolactone) (PCL) was fractionated, and the dilute‐solution properties of the fractions were studied in tetrahydrofuran and toluene at 30°C. The Mark–Houwink relations for these solvents were [η] = 2.73 × 10^?2M_w^0.74 and [η] = 1.97 × 10^?2M_w^0.75, respectively. In addition, the unperturbed dimensions of the star‐shaped PCL systems were also evaluated, and a significant solvent effect was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 175–182, 2006     

Ceric ion‐induced graft copolymerization of acrylamide on cationic guar gum at low temperature

The solution polymerization of acrylamide (AM) on cationic guar gum (CGG) under nitrogen atmosphere using ceric ammonium sulfate (CAS) as the initiator has been realized. The effects of monomer concentration and reaction temperature on grafting conversion, grafting ratio, and grafting efficiency (GE) have been studied. The optimal conditions such as 1.3 mol of AM monomer and 2.2 × 10^?4 mol of CAS have been adopted to produce grafted copolymer (CGG1‐g‐PAM) of high GE of more than 95% at 10°C. The rates of polymerization (R_p) and rates of graft copolymerization (R_g) are enhanced with increase in temperature (<35°C).The R_p is enhanced from 0.43 × 10^?4 mol L^?1 s^?1 for GG‐g‐PAM to 2.53 × 10^?4 mol L^?1 s^?1 for CGG1‐g‐PAM (CGG1, degree of substitute (DS) = 0.007), and R_g from 0.42 × 10^?4 to 2.00 × 10^?4 mol L^?1 s^?1 at 10°C. The apparent activation energy is decreased from 32.27 kJ mol^?1 for GG‐g‐PAM to 8.09 kJ mol^?1 for CGG1‐g‐PAM, which indicates CGG has higher reactivity than unmodified GG ranging from 10 to 50°C. Increase of DS of CGG will lead to slow improvement of the polymerization rates and a hypothetical mechanism is put forward. The grafted copolymer has been characterized by infrared spectroscopy, thermal analysis, and scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3715–3722, 2007     

The influence of molar mass on rheological and dilute solution properties of poly(butylene succinate)

The fundamental rheological properties of a wide molar mass M_w range of poly(butylene succinate)s (PBSs) are investigated. For entangled samples and a reference temperature of 140°C, the shear viscosity is described by the Carreau–Yasuda model. The plateau modulus is estimated at 1.5 × 10⁵ Pa, the average activation energy of PBS melt is , and the critical molar mass for entanglement M_c is found to be 16,000 g mol^?1 (PS equivalent). The dilute solution properties of PBS are also studied. A size exclusion chromatography equipped with a triple detection system is used to estimate the Mark–Houwink–Sakurada (MHS) parameters of PBS in solution in chloroform at 30°C. The exponent a and the coefficient K of the MHS relationship are found to be 0.71 ± 0.1 and 39.94 × 10^?5 ± 6.31 × 10^?5 dL g^?1(g mol^?1)^?a, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40887.     

pH‐responsive polyzwitterions: A comparative study of acrylamide‐based polyampholyte terpolymers and polybetaine copolymers

A comparative study of pH‐responsive polyzwitterions (PZs) with polyampholyte or polybetaine architectures was conducted with well‐defined model polymer systems. Low‐charge‐density PZs, including ampholytic terpolymers composed of acrylamide (AM), sodium 3‐acrylamido‐3‐methylbutanoate, and (3‐acrylamidopropyl)trimethylammonium chloride and carboxybetaine copolymers composed of AM and 3‐(3‐acrylamidopropyldimethylammonio)propionate, were prepared via free‐radical polymerization in 0.5M NaCl to yield ter‐ and copolymers with random termonomer and comonomer distributions. Sodium formate was used as a chain‐transfer agent during the polymerizations to eliminate the effects of the monomer feed composition on the degree of polymerization (DP) and to suppress gel effects and broadening of the molecular weight distributions. The polymer compositions were determined via ¹³C‐NMR spectroscopy, and the residual counterion content was determined via elemental analysis for Na⁺ and Cl^?. The molecular weights (MWs) and polydispersity indices (PDIs) were determined via size exclusion chromatography/multi‐angle laser light scattering (SEC–MALLS); the polymer MWs ranged from 1.4 to 1.5 × 10⁶ g/mol, corresponding to DPs of 1.6–1.9 × 10⁴ repeat units, with all the polymers exhibiting PDIs less than or equal to 2.1. The intrinsic viscosities determined from SEC–MALLS data and the Flory–Fox relationship agreed with the intrinsic viscosities determined via low‐shear dilute‐solution viscometry. Data from the SEC–MALLS analysis were used to analyze the radius of gyration/molecular weight (R_g–M) relationships and the Mark–Houwink–Sakurada intrinsic viscosity/molecular weight ([η]–M) relationships for the PZs. The R_g–M and [η]–M relationships and viscometric data revealed that under size exclusion chromatography conditions, the poly[acrylamide‐co‐3‐(3‐acrylamidopropyldimethylammonio)propionate] betaine copolymers had more open, random‐coil conformations and greater polymer–solvent interactions than the ampholytic poly[acrylamide‐co‐sodium 3‐acrylamido‐3‐methylbutanoate‐co‐(3‐acrylamidopropyl)trimethylammonium chloride] terpolymers. The pH‐ and salt‐responsive dilute‐solution viscosity behavior of the PZs was examined to assess the effects of the polymer structure and composition on the solution properties. The polyampholyte terpolymers had greater solution viscosities and more pronounced stimuli‐responsiveness than the polybetaine copolymers because of their stronger intramolecular interactions and increased chain stiffness. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 24–39, 2004     

Degradation and biodegradation of polyethylene with pro‐oxidant aditives under compost conditions establishing relationships between physicochemical and rheological parameters

In the present work, an analysis is carried out to provide a relationship between the Molecular Weight (M_w) of degraded LDPE films (containing Mn stearate as pro oxidant (MnSt‐LDPE) and changes in viscosity, elongation at break (EB %) and carbonyl index (CI) occurring during thermal degradation in the thermophilic phase of the compost process. The thermal treatment comprised various temperatures (50°C, 60°C, and 70°C) and exposure times, and was characterized through a so‐called Energy‐Time Factor (the product of thermal energy and exposure time). Changes in viscosity, EB %, and CI were correlated to this factor. A modified Mark‐Houwink equation was used to relate the zero shear‐rate viscosity and M_w of the degraded LDPE films. Results indicate that the EB %, M_w and viscosity decrease simultaneously with an increase in the CI as the Energy‐Time Factor augments, allowing the assessment of the variation of these properties with M_w. Calculations of the percentage abiotic degradation (%D) of LDPE films indicate that a M_w of 6 kg mol^?1 corresponds to a maximum abiotic degradation degree of 91.85%, which is henceforth susceptible to biodegradation. The film treated with Energy‐Time Factor of 2.79E+09 J s mol^?1 reached a 74% of biodegradation in 90 days (average time of the composting process). Results exhibit clearly the correlation between abiotic and biotic degradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42721.     

Molecular weight determination of 83% degree of decetylation chitosan with non‐Gaussian and wide range distribution by high‐performance size exclusion chromatography and capillary viscometry

Molecular weight determination of 83% degree of deacetylation (DD) chitosan with non‐Gaussian and broad molecular weight distribution by high‐performance size exclusion chromatography (HPSEC) and by capillary viscometry were proposed. The relationships between weight average retention volumes (RVw) of HPSEC and intrinsic viscosities ([η]) measured by capillary viscometer and the weight average molecular weight (Mw) measured by static light scattering were established for routine molecular weight determination of chitosans either by HPSEC or by the capillary viscometry method, respectively. These results showed: relationships of RVw and Mw for different Mw of 83.0% DD chitosans can be expressed by the equation Log Mw = −0.433 RVw + 11.66. The RVw of other DD chitosans do not correlate well with this equation. It indicated that DD of chitosan affected the relationship of RVw and Mw of chitosans studied. The Mark–Houwink constant a decreased from 0.715 to 0.521, as the solution ionic strength increased from 0.01M to 0.30M, whereas constant k increased from 5.48 × 10⁻⁴ to 2.04 × 10⁻³ over the same range of ionic strength solutions. The established RVw and Mw equation and [η] and Mw equation (Mark–Houwink equation) can be routinely used to determine the molecular weight from RVw or [η] of chitosan by HPSEC or by capillary viscometer, respectively, without the need of expensive instrumentation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1905–1913, 1999     

Poly(acrylamide‐co‐maleic acid) hydrogels for removal of Cr(VI) from aqueous solutions,Part 1: Synthesis and swelling characterization

The swelling behavior of poly (acrylamide‐co‐maleic acid) hydrogels has been investigated in distilled water at 30°C. The gels were characterized with respect to structural parameters, Fourier transform infrared, and thermogravimetric analysis. The gels showed fair pH‐dependent swelling and exhibited double “s”‐shaped curve between equilibrium water uptake and pH of the swelling media. The two pK_a values, as determined from the curve, were found to be 2.46 and 6.58. The activation energy of the water uptake process for plain and acid containing gels was found to be 7.93 and 3.26 kJ mol^?1 respectively. Similarly, the enthalpy of mixing between dry polymer and solvent showed positive values, thus indicting endothermic nature of the process, and the values increased from 10.06 to 16.29 kJ mol^?1 with increase in acid content from 2.1 × 10^?1 to 4.7 × 10^?1 mM respectively. There was an optimum initiator concentration 24.0 × 10^?2 mM and reaction temperature 60°C at which gels synthesized showed maximum absorbency. The dilution of the reaction mixture resulted in the formation of hydrogels with enhanced absorbency. Finally, the gels with varying content of monomer acid in the feed mixture showed different swelling behavior when studied in the medium of pH 1.0 and 7.0. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2759–2769, 2006     

Poly‐α,β‐(3‐hydroxypropyl)‐DL‐aspartamide: A new drug carrier

Poly‐α,β‐(3‐hydroxypropyl)‐DL ‐aspartamide (PHPA) was synthesized by the ring‐open reaction of polysuccinimide (PSI) and 3‐hydroxypropylamine. The polymer was characterized by ¹H‐NMR, ¹³C‐NMR, FTIR, and GPC. Mark–Houwink coefficients were obtained from viscometry and GPC measurements, K = 5.53 × 10⁻³ and α = 0.78 in water. The acute toxicity of PHPA was examined and it revealed no death in ICR mice up to the dose treated of 15.3 kg/kg, and hematological parameters showed no significant difference between treated and control animals. The potential use of PHPA as a drug carrier was also investigated. In a typical case, a contraceptive drug, norethindrone (NET), was bonded to PHPA, and the drug sustained released as long as 120 days an in vitro test. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2411–2417, 2000     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

Universal one‐pot,one‐step synthesis of core–shell nanocomposites with self‐assembled tannic acid shell and their antibacterial and catalytic activities

Facile synthesis of metal@polymer nanocomposites were achieved using self‐assembled tannic acid (TA) shells without crosslinkers. The TA shell was assembled under mildly alkaline conditions in reaction time of 20 min under constant vortexing. Universal synthesis method was demonstrated by the synthesis of Ag@TA and Au@TA nanocomposites. We propose that the shell formation is due to TA undergoing oxidative self‐polymerization to poly(tannic acid) or a supramolecular aggregate of oxidized TA held together by charge transfer, hydrogen bond, and π–π interactions, similar to dopamine polymerization. Gibbs free energy calculations suggest that polymerization is energetically favorable. Synthesized Ag@TA exhibited antibacterial functionality with Escherichia coli minimum inhibitory concentration of 100 µg mL^?1 up to 48 h. The population of E. coli was also reduced by 99% within 5 h when incubated with 100 µg mL^?1 of Ag@TA nanocomposite. Au@TA also functions as a reduction catalyst. It reduces 4‐nitrophenol to 4‐aminophenol in the presence of NaBH₄ with a rate constant of k = 0.63 min^?1 μmol^?1. For comparison, using Au nanoparticles yields a rate constant of 0.14 min^?1 μmol^?1. The ease of synthesis renders the nanocomposites superior to others, with potential for large‐scale application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45829.     

Molecular architectures of four‐arm star‐shaped styrene‐butadiene copolymer

To understand the molecular architectures of styrene‐butadiene four‐arm star (SBS) copolymers, a size exclusion chromatography combined with laser light scattering (SEC‐LLS) has been used to determine their weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^1/2), and a new method for the establishment of the Mark‐Houwink equation from one sample has been developed. Based on the Flory viscosity theory, we successfully have reduced the 〈S²〉^1/2 values of numberless fractions estimated from many experimental points in the SEC chromatogram to intrinsic viscosities ([η]). For the first time, the dependences of 〈S²〉^1/2 and [η] on M_w for the four‐arm star SBS in tetrahydrofuran at 25°C were found, respectively, to be 〈S²〉^1/2 = 2.62 × 10^?2 M (nm) and [η] = 3.68 × 10^?2 M (mL/g) in the M_w range from 1.4 × 10⁵ to 3.0 × 10⁵. From data of [η] and 〈S²〉^1/2 for linear and star SBS, we have obtained the information about the branching, namely, the ratios (g and g′) of 〈S²〉 and [η] for star SBS to that of the linear SBS of the same molecular weight, which agree with theoretical predictions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 961–965, 2005     

Effects of molecular weight on dual light‐ and thermo‐responsive behaviors of homopolymers with azobenzene units and terminal oligo(ethylene glycol) units

A series of water‐soluble dual light‐ and thermo‐responsive homopolymers bearing azobenzene units and terminal oligo(ethylene glycol) units with well‐defined molecular weight (M _n = 0.69 × 10⁴ to 4.60 × 10⁴ g mol^?1) were synthesized via reversible addition–fragmentation chain transfer polymerization. All the homopolymers exhibited reversible photoisomerization and their lower critical solution temperatures showed an unusual increase with increasing molecular weight. Interestingly, by increasing the molecular weight, the aggregate morphology of these polymers was found to evolve from a spherical to a cylindrical shape. © 2017 Society of Chemical Industry     

Model of a polymer chain twisted inside a statistical segment. Poly(3‐hexylthiophene) in chloroform solutions

A set of hydrodynamic methods in extremely dilute solutions (determination of intrinsic viscosity [η ], translational diffusion D and flotation in a centrifugal field s ) was used in the studies of conformational properties, dimensions and equilibrium rigidity of individual molecules of a series of samples of poly(3‐hexylthiophene). Absolute molecular masses M _sD were determined. The Mark–Kuhn–Houwink equations for the range of M _sD from 2240 to 15 300 g mol^?1 are given. For the first time, an analysis of conformational properties and equilibrium flexibility of poly(3‐hexylthiophene) molecules was carried out using the model of a statistical segment containing a twisted polymer chain. © 2017 Society of Chemical Industry     

EDTA and pH‐sensitive crosslinking polymerization of acrylic acid, 2‐acrylamidoglycolic acid,and 2‐acrylamide‐2‐methyl‐1‐propanesulfonic acid

Network formation was monitored by shear storage modulus (G′) during free radical crosslinking polymerization to investigate the effects of pH and ethylenediaminetetraacetic acid (EDTA; a complex agent). Three types of acrylic monomers, acrylic acid (AAc), 2‐acrylamidoglycolic acid (AmGc), and 2‐acrylamido‐2‐methyl propanesulfonic acid (AmPS), were polymerized in the presence of a crosslinking agent. The ratio of crosslinking agent (methylene bis‐acrylamide; MBAAm) to monomer was varied as: 0.583 × 10^?3, 1.169 × 10^?3, 1.753 × 10^?3, and 2.338 × 10^?3. G′ of the hydrogel in crosslinking polymerizations of AAc and AmPS was effectively increased by addition of EDTA, which was not the case for the crosslinking polymerization of AmGc. The order of magnitude of G′ differed based on the acidity of monomer. The maximum values of G′ in crosslinking polymerizations of AAc, AmGc, and AmPS were ～20,000 Pa, 6000 Pa, and 400 Pa, respectively. G′ varied linearly with the molecular weight between crosslinks (M_wc). pH and EDTA‐complex affected the rate of intramolecular propagation during crosslinking polymerization. Our results indicated that G′ was primarily affected by the following factors in the order: (1) acidity of monomer, (2) M_wc, and (3) physical interactions induced by pH and EDTA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41026.     

Dependence of intrinsic viscosity and molecular size on molecular weight of partially hydrolyzed polyacrylamide

As a typical water-soluble polymer, ultra-high molecular weight (UHMW) partially hydrolyzed polyacrylamide (HPAM) has been widely used in various industries as thickeners or rheology modifiers. However, precise determination of its critical physical parameters such as molecular weight, radius of gyration (R_g) and hydrodynamic radius (R_h) were less documented due to their high viscosity in aqueous solution. In this work, the molecular structure of five UHMW-HPAM samples with different MW was elucidated by ¹H and ¹³C NMR spectroscopy, and their solution properties were characterized by both static and dynamic light scattering. It is found that all the second virial coefficient (A₂) values are positive and approaching zero, indicating of a good solvent of 0.5 M NaCl for UHMW-HPAM. The weight-average molecular weight (M_w) dependence of molecular size and intrinsic viscosity [η] for these series of HPAM polymers with MW ranging from 4.81 to 15.4 × 10⁶ g·mol⁻¹ can be correlated as R_g = 3.52 × 10⁻²M_w^0.51, R_h = 1.97 × 10⁻²M_w^0.51, and [η] = 6.98 × 10⁻⁴ M_w^0.91, respectively. These results are helpful in understanding the relationship between molecular weight and coil size of HPAM polymers in solution, and offer references for quick estimation of molecular weight and screening of commercial UHMW-HPAM polymers for specific end-users.     

Ceric(IV) ion‐induced graft copolymerization of acrylamide and ethyl acrylate onto cellulose

Graft copolymerization of acrylamide (AAm) and ethyl acrylate (EA) onto cellulose has been carried out from their binary mixtures using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 25 ± 1 °C. The extent of acrylamide grafting increased in the presence of the EA comonomer. The composition of the grafted chains (F_AAm = 0.52) was found to be constant during the feed molarity variation from 7.5 × 10^?2 to 60.0 × 10^?2 mol L^?1, whereas the composition of the grafted chains (F_AAm) was found to be dependent on feed composition (f_AAm) and reaction temperature. The effects of ceric(IV ) ion concentration, reaction time and temperature on the grafting parameters have been studied. The grafting parameters showed an increasing trend up to 6.0 × 10^?3 mol L^?1 concentration of CAN at a feed molarity of 30.0 × 10^?2 mol L^?1 and showed a decreasing trend on further increasing the concentration of CAN (>6.0 × 10^?3 mol L^?1) at a constant concentration of nitric acid (5.0 × 10^?2 mol L^?1). The composition of the grafted chains (F_AAm) was determined by IR spectroscopy and nitrogen content and the data obtained then used to determine the reactivity ratios of the acrylamide (r₁) and ethyl acrylate (r₂) comonomers by using a Mayo and Lewis plot. The reactivity ratios of acrylamide and ethyl acrylate were found to be r₁ = 0.54 and r₂ = 1.10, respectively, and hence the sequence lengths of acrylamide (m?M₁) and ethyl acrylate (m?M₂) in the grafted chains are arranged in an alternating form, as the product of the reactivity ratios of acrylamide and ethyl acrylate (r₁ × r₂) is less than unity. The rate of graft copolymerization of the comonomers onto cellulose was found to be dependant on the ‘squares’ of the concentrations of the comonomers and on the ‘square root’ of the concentration of ceric ammonium nitrate. The energy of activation (ΔE_a) of graft copolymerzation was found to be 5.57 kJ mol^?1 within the temperature range from 15 to 50 °C. On the basis of the results, suitable reaction steps have been proposed for the graft copolymerzation of acrylamide and ethyl acrylate comonomers from their mixtures. Copyright © 2005 Society of Chemical Industry     

Kinetics and crystallization in pH‐sensitive free‐radical crosslinking polymerization of acrylic acid

Free‐radical crosslinking polymerization and crystallization of acrylic acid (AAc) were investigated by shear storage modulus (G′) measurements in pH 2, as well as in pH 6 and pH 10, by varying the molar ratio of crosslinking agent (N,N′‐methylene bis‐acrylamide; MBAAm) to AAc (0.583 × 10^?3, 1.169 × 10^?3, 1.753 × 10^?3, and 2.338 × 10^?3). Our results showed that the pre‐gelation time was the same at pH 2, regardless of the concentration of MBAAm. The propagation time was determined by the initial feed concentration of AAc, and the length of the linear curve in the propagation was proportional to the concentration of MBAAm. The Avrami exponent (n), as an indicative of growing pattern of an infinite molecule, in the crystallization was increased in proportional to the concentration of MBAAm, and generally low at pH 2. In the deceleration phase, n was observed near 1.0 throughout the all specimens. These results indicated that (1) the length of the pre‐gelation period was determined by the ionization of AAc (or pH), (2) the polymerization rate of AAc was not affected by the concentration of MBAAm, and (3) the inhomogeneity of hydrogel was determined by the growing pattern of infinite molecule in propagation phase. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42195.