Binding of a surfactant counterion to low-charge-density poly(acrylic acid) and poly(methacrylic acid)

The binding of a cationic surfactant, dodecylpyridinium (C12Py) chloride, with a low-charge-density poly (methacrylic acid) (PMA) was investigated in buffer solutions under the condition of constant pH. The binding isotherms with PMA consisted of two and three steps at a pH lower and higher than 3.2, respectively. Bindings in the first step were independent of pH and this step was considered to correspond to the solubilization of the hydrocarbon chains of C12Py into the nonpolar region of the compact form of PMA. This is the indication of the compact form from the binding isotherm. At pH higher than 3.2, the second step was discriminated and it depended on the pH. In the third step, a sharp rise in the degree of binding (β) was observed accompanying the solubilization of the precipitates of the PMA–C12Py complex. The binding with poly(acrylic acid) (PAA) and PMA in conventional unbuffered NaCl solutions was also examined and the pH profile of the solution during the binding process was determined. In the case of unbuffered NaCl solutions, the binding with PAA took place cooperatively at the critical association concentration (cac). The binding isotherm consisted of two steps and the pH decreased with the increase in β. The binding isotherm of PMA, on the other hand, consisted of three steps: the pH decreased slightly in the first step and considerably in the second step with the increase in β but it increased with β in the third step, exhibiting a pH minimum around 3.2. The binding in the first step coincided with that obtained in the buffered solutions. Linear relationships between β and the pH were found for both polymers. In the case of PMA, no cac was observed in both buffered and unbuffered NaCl solutions. Received: 24 January 2001 Accepted: 23 May 2001     

Molecular modeling of polymers. 10. Characterization of conformational transitions of poly(acrylic acid) and poly(methacrylic acid) using dyad structures

The conformational profiles of nearest side-chain neighbors, methylene-dyad structures, of poly(acrylic acid), PAA, and poly(methacrylic acid), PMA, were determined as a function of tacticity, extent of ionization, and presence of counterion. The dominant backbone conformer states are quite similar for both isotactic and syndiotactic diads in a common charge state. Thus, the overall dimensional properties of isotactic syndiotactic and atactic chains of PAA or PMA, based upon dyad interactions, are predicted to be alike for a given charge state. Significant deviations from precise t, g⁺, and g^? states are found for the dyad minimum energy conformations. The rod-to-coil and coil-to-rod transitions observed in PAA and PMA, respectively, as a function of increasing counterion concentration can be explained, to a large extent, by the conformational profiles of the corresponding dyad model structures. © 1994 John Wiley & Sons, Inc.     

Synthesis of monodisperse poly(methacrylic acid) microspheres by distillation-precipitation polymerization

Monodisperse poly(methacrylic acid) (PMAA) microspheres were prepared by distillation-precipitation polymerization in acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as initiator. The polymeric microspheres were formed simultaneously via a precipitation polymerization manner during the distillation of the solvent out of the reaction system in the absence of any surfactant and crosslinker. Monodisperse PMAA microspheres with spherical shape and smooth surface were synthesized with diameters ranging from 60 to 290 nm below the glass transition temperature of PMAA without any stabilizer. The particle size increased with increasing monomer concentration, which may be resulted from the higher molecular weight for the polymerization. To investigate the growth procedure of PMAA microspheres, the morphology of microspheres over the distillated acetonitrile volume was conducted by monitoring the morphologies with TEM. GPC and FTIR provide key insights into the particle growth mechanism. The PMAA microspheres may be formed by an internal contraction due to the marginal solvency of the continuous phase with the aid of the hydrogen-bonding interaction between the carboxylic acid unit, in which the particles were stabilized by the steric effect of the pendent chains and surface gel as well as the electrostatic repulsion from the carboxylic acid group.     

Preparation and characterization of poly(acrylic acid)-based nanoparticles

The present investigation describes the synthesis and characterization of nanoparticles based on poly(acrylic acid) (PAA) intramolecularly cross-linked with diamine, 2,2′-(ethylenedioxy)bis(ethylamine), using water-soluble carbodiimide. The aqueous colloid dispersions of nanoparticles were clear or mildly opalescent depending on the ratio of cross-linking, pH of the solution, and the molecular weight of PAA, finding consistent with values of transmittance between 3% and 99%. The structure was determined by nuclear magnetic resonance spectroscopy, and the particle size was identified by dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements. It was found that particle size depends on the pH, and at a given pH, it was caused by the ratio of cross-linking and the molecular weight of PAA. Particle size measured by TEM varied in the range of 20 and 80 nm. In the swollen state, the average size of the particles measured by DLS was in the range of 35–160 nm.     

Swelling-assisted modification of poly(ethylene terephthalate) by methacrylic acid

When a poly(ethylene terephthalate), PET, film is heated in an aqueous solution of methacrylic acid in the presence of hydrogen peroxide as an initiator, it is found that the weight of the film is increased. The amount of methacrylic acid that may be added onto the film is dependent upon the concentration of the monomer, the initiator, and the temperature at which the reaction occurs. Pretreatment of the film with 1,1,2,2,tetrachloroethane causes swelling and the amount of add-on is increased as the swelling level increases. Methacrylic-acid-modified PET films hydrolyze at room temperature in aqueous sodium hydroxide; the rate of hydrolysis is dependent upon the amount of add-on and the concentration of the base. This procedure leads to a chemically induced blend of polymethacrylic acid and poly(ethylene terephthalate), and grafting of the monomer onto the polymer film does not occur. © 1995 John Wiley & Sons, Inc.     

Interpenetrating polymer network (IPN) nanogels based on gelatin and poly(acrylic acid) by inverse miniemulsion technique: synthesis and characterization

Novel interpenetrating polymer network (IPN) nanogels composed of poly(acrylic acid) and gelatin were synthesised by one pot inverse miniemulsion (IME) technique. This is based on the concept of nanoreactor and cross-checked from template polymerization technique. Acrylic acid (AA) monomer stabilized around the gelatin macromolecules in each droplet was polymerized using ammonium persulfate (APS) and tetramethyl ethylene diamine (TEMED) in 1:5 molar ratio and cross-linked with N,N-methylene bisacrylamide (BIS) to form semi-IPN (sIPN) nanogels, which were sequentially cross-linked using glutaraldehyde (Glu) to form IPNs. Span 20, an FDA approved surfactant was employed for the formation of homopolymer, sIPN and IPN nanogels. Formation of stable gelatin-AA droplets were observed at 2% surfactant concentration. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) studies of purified nanogels showed small, spherical IPN nanogels with an average diameter of 255 nm. In contrast, sIPN prepared using the same method gave nanogels of larger size. Fourier-transform infrared (FT-IR) spectroscopy, SEM, DLS, X-ray photoelectron spectroscopy (XPS) and zeta potential studies confirm the interpenetration of the two networks. Leaching of free PAA chains in sIPN upon dialysis against distilled water leads to porous nanogels. The non-uniform surface of IPN nanogels seen in transmission electron microscopy (TEM) images suggests the phase separation of two polymer networks. An increase of N/C ratio from 0.07 to 0.17 (from PAA gel to IPN) and O/C ratio from 0.22 to 0.37 (from gelatin gel to IPN) of the nanogels by XPS measurements showed that both polymer components at the nanogel surface are interpenetrated. These nanogels have tailoring properties in order to use them as high potential drug delivery vehicles for cancer targeting.     

PMAA纳米水凝胶的水相制备

利用表面活性剂间的疏水作用以及表面活性剂与单体间的氢键作用,促使甲基丙烯酸(MAA)单体在原位生成的聚甲基丙烯酸甲酯(PMMA)种子乳胶表面的选择性聚合,实现了PMAA纳米水凝胶的水相"绿色"制备。利用动态光散射、傅里叶红外光谱、透射电子显微镜表征了PMAA纳米水凝胶的尺寸、组成、形貌和pH响应性。研究了聚氧乙烯失水山梨醇单月桂酸酯(吐温20)的用量、N,N’-亚甲基双丙烯酰胺(MBA)的用量、MAA的用量和加入方式、十二烷基硫酸钠(SDS)的补加速率等对PMAA纳米水凝胶的尺寸和溶胀性能的影响。结果表明:PMAA纳米水凝胶为核-壳结构;随着MBA用量的减小、吐温20用量的增加、MAA用量的增加,PMAA纳米水凝胶的尺寸和溶胀比均增大;当采用半连续加入MAA时,PMAA纳米水凝胶的尺寸和溶胀比变小;当SDS的补加时间由60min延长到100min时,PMAA纳米水凝胶的尺寸逐渐变小。PMAA纳米水凝胶具有良好的pH响应性,当介质的pH从1增加到6时,其流体力学体积扩张了64倍。     

Complexation of sequence-ordered methacrylic acid copolymers with poly(4-vinylpyridine)

The complexation of three kinds of sequence-ordered acid (co)polymers with a base homopolymer was studied. The acid polymers used are poly(methacrylic acid) 1 , alternating (1:1) ethylene-methacrylic acid copolymer 2 , and periodic (2:1) ethylene-methacrylic acid copolymer 3 , and the base polymer is poly(4-vinylpyridine) 4. When mixing a methanol solution of 1, 2 , or 3 with that of 4 (0.1 M of each functional group), precipitate was formed immediately for all polymer pairs. All the precipitates contained carboxyl and pyridyl groups in ca. 1:1 molar ratio and showed IR spectra indicating the hydrogen bonding between carboxyl and pyridyl groups. When mixing dilute methanol solutions (10⁻⁴M) of the above polymer pairs, no precipitation was observed, but the extinction coefficient (ϵ_B) at 255 nm of pyridyl groups in 4 was found to increase with an increasing acid polymer concentration. This is ascribed to hydrogen bonding between carboxyl and pyridyl groups in methanol. Based on the ϵ_B variation, the order of complexation constants for acid/base polymer pairs was estimated as follows: 1/4 pair ∼ 2/4 pair ≫ 3/4 pair. © 1996 John Wiley & Sons, Inc.     

pH-responsive poly(methacrylic acid)-grafted hollow silica vesicles

Poly(methacrylic acid)-grafted hollow silica vesicles (PMAA-g-hollow silica vesicles) were obtained through a grafting-from approach. PMAA brushes were formed by performing atom-transfer radical polymerisation of sodium methacrylate with an initiator attached to the hollow silica spheres. PMAA-g-hollow silica vesicles were characterised by using TEM, thermogravimetric analysis (TGA) and FTIR spectroscopy. pH-dependent ξ potential and (1)H NMR spectra of PMAA-g-hollow silica vesicles were measured, and the results indicated that MAA brushes in PMAA-g-hollow silica vesicles had a lower ionisation degree and low solubility in acidic aqueous solution, for example, pH 3.4, but a higher ionisation degree and high solubility when the pH was higher than 7. Also it was demonstrated that calcein blue and fluorescein isothiocyanate (FITC) labelled dextran (M(n):10 kDa) could be encapsulated in the interiors of the PMAA-g-hollow silica vesicles with a negligible amount in PMAA brushes at pH 2, and pH-triggered release of calcein blue and FITC-labelled dextran from PMAA-g-hollow silica vesicles was observed at pH 7.4.     

Complexation between poly(acrylic acid) and poly(vinylpyrrolidone): Influence of the molecular weight of poly(acrylic acid) and small molecule salt on the complexation

Poly(acrylic acid) (PAA) with different molecular weight and poly(vinylpyrrolidone) (PVP) were prepared by free radical polymerization using 2,2′-azoisobutyronitrile (AIBN) as initiator in anhydrous methanol for PAA, and in distilled water for PVP. Then, the complexation between PAA and PVP in aqueous solution was studied by UV transmittance measurement and fluorescence probe technique. The result shows that (1) at low pH, the formation of complexation between PAA and PVP bases on the intermacromolecular hydrogen bond and the composition of the formed complex is around 3:2 (the unit molar ratio of PAA to PVP) at pH 2.60 over the range of pH investigated. (2) The cooperative interaction through the formation of hydrogen bond among active sites plays an important role in complex formation, and depends on the pH of solution, the required minimum chain length of poly(acrylic acid). (3) The hydrogen bond is not affected by small molecular salt, which only affects those carboxylic groups without forming hydrogen bond on the PAA chain.     

Oxidative and photooxidative degradation of poly(acrylic acid)

The oxidative degradation of poly(acrylic acid) (PAA), a water soluble polymer, was studied at various temperatures with different concentrations of persulfates, potassium persulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS). The photodegradation of PAA was also examined with APS as oxidizer. The degraded samples were analyzed for the time evolution of molecular weight distribution by gel permeation chromatography. A theoretical model based on the continuous distribution kinetics was developed that accounted for the polymer degradation and the dissociation of persulfate. The rate coefficients for the oxidative and photooxidative degradation of PAA were determined from the parametric fit of the model with experimental data. The rate of degradation increased with increasing amount of persulfate in both oxidative and photooxidative degradation. The rate of degradation also increased with increasing temperature in the case of oxidative degradation.     

Efficient synthesis of branched poly(acrylic acid) derivatives via postpolymerization modification

The utility of pentafluorophenyl esters for the selective introduction of functional units and branch points in well-defined poly(acrylic acid) (PAA) derivatives is demonstrated using a combination of controlled radical polymerization and postpolymerization modification. Reversible addition-fragmentation chain transfer enables the synthesis of well-defined copolymers—poly(pentafluorophenyl acrylate-co-tert-butyl acrylate)—with the active ester repeat units serving as attachment points for reaction with primary amines, specifically tris(2-(t-butoxycarbonyl)ethyl)methyl amine (Behera's amine). Deprotection using trifluoroacetic acid removes both the backbone and side chain t-butyl esters to give a series of branched PAA derivatives containing novel tricarboxylic acid side chains that are well suited to complexation and multidentate interactions. Surprisingly, the active ester homopolymer is shown to have the highest reactivity with Behera's amine when compared to copolymers with lower incorporation of pentafluorophenyl esters, suggesting an intriguing interplay of neighboring group effects and steric interactions. The ability to tune the efficiency of postpolymerization modification gives a library of PAA derivatives.     

Novel synthesis of N‐substituted polyacrylamides: Derivatization of poly(acrylic acid) with amines using a triazine‐based condensing reagent

Poly(acrylic acid) (PAA) was derivatized through the reaction of its pendant carboxylic acid (CO₂H) groups with a wide range of amine‐terminated molecules. These molecules contained alkyl, hydroxyl, sulfonic acid, or perfluoroalkyl groups. N‐substitution of PAA was carried out by the simple addition of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methylmorpholinium chloride (DMTMM), a triazine‐based condensing reagent, to a mixture of PAA and amine‐terminated molecules. From proton nuclear magnetic resonance and infrared spectroscopy, it was confirmed that these functional molecules were introduced into the PAA side chain via amide bonds. By the alteration of the synthetic conditions, functional side‐chain contents of greater than 95% were achieved for aqueous reactions with taurine, ethanol amine, and butyl amine. Side‐chain conversion was limited to ≤80% for reactions with perfluoroalkyl amines in methanol. Thus, DMTMM is an attractive replacement for carbodiimide condensing reagents such as 1,3‐dicyclohexylcarbodiimide and 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 126–136, 2006     

Structural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) copolymer by nuclear magnetic resonance and mass spectrometry

Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have been combined to achieve the complete microstructural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) (PMAA-PMMA) copolymer synthesized by nitroxide-mediated polymerization. Various PMAA-PMMA species could be identified which mainly differ in terms of terminaisons. ¹H and ¹³C NMR experiments revealed the structure of the end-groups as well as the proportion of each co-monomer in the copolymers. These end-group masses were further confirmed from m/z values of doubly charged copolymer anions detected in the single stage mass spectrum. In contrast, copolymer composition derived from MS data was not consistent with NMR results, obviously due to strong mass bias well known to occur during electrospray ionization of these polymeric species. Tandem mass spectrometry could reveal the random nature of the copolymer based on typical dissociation reactions, i.e., water elimination occurred from any two contiguous MAA units while MAA-MMA pairs gave rise to the loss of a methanol molecule. Polymer backbone cleavages were also observed to occur and gave low abundance fragment ions which allowed the structure of the initiating end-group to be confirmed.     

Mechanism of preparing monodisperse poly(acrylamide/methacrylic acid) microspheres in ethanol. I

The precipitation polymerization of acrylamide/methacrylic acid (AAm/MAA) in ethanol (EtOH) was thoroughly investigated from detecting the homogeneity of the initial solution prior to polymerizations to the final products of the polymerizations. Dynamic light scattering and scanning electron microscopy were employed for the investigations. The solutions of AAm and AAm/acrylic acid (AAm/AA) were homogeneous. However, the solutions of AAm/MAA, AAm/poly(MAA) (PMAA), and AAm/poly(AA) (PAA) were not homogeneous as they are usually considered to be: entities with size distributions of around 150, 40, and 17 nm, respectively, were detected at the polymerization temperature of 60 °C. Accordingly, analogous to the entities that are similar to the structure of micelles formed in the solutions of AAm/PMAA and AAm/PAA because of polymer–AAm interactions, it was suggested that the complexes of AAm/MAA stemming from the molecular interactions, particularly the (lypo‐) hydrophobic interaction, aggregated to form minimonomer droplets at 60 °C. The monodisperse microspheres were prepared only in the AAm/MAA‐EtOH systems, whereas the microspheres were not prepared in the homogeneous AAm‐EtOH systems despite the precipitation of PAAm. The results obtained from various polymerizations showed that the microspheres originated from the polymerization within the minimonomer droplets. A new mechanism was established that describes the processes for the formation of all products possibly generated in the AAm‐MAA‐EtOH polymerization system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2823–2832, 2004     

Osmotic deswelling of weakly charged poly(acrylic acid) solutions and gels

The osmotic pressure of weakly charged aqueous poly(acrylic acid) (PAA) solutions and the swelling pressure PAA gels were studied by osmotic deswelling at different degrees of ionization (α). In solution, the osmotic pressure was found to scale linearly with concentration, whereas the scaling power of the swelling pressure of gels was higher (1.66). The effect of the ionization degree on the osmotic coefficient in PAA solutions was in agreement with the theory of Borue and Erukhimovich [Macromolecules, 21 , 3240 (1988)]. Ionization increases the swelling capacity of the PAA gels until a plateau is reached at about 35% neutralization. The concentration at equilibrium swelling scales as C_e ～ α^?0.6. The contribution of the network to the gel swelling pressure is evaluated by subtracting the osmotic pressure of the polymer solution at the same concentration and degree of ionization. In swollen gels the extended network opposes swelling. As the gel is osmotically deswelled, a state of zero network pressure exists at a certain concentration, below which the network elasticity favors swelling. The crossover concentration shifts to lower values as the degrees of ionization increases. © 1995 John Wiley & Sons, Inc.     

Effect of pH on Poly(acrylic acid) Solution Polymerization

The free-radical redox-initiated aqueous solution polymerization of fully and partially neutralized acrylic acid was carried out at room temperature under full exposure to air. The effect of neutralization degree on the polymerization rate and product properties was studied. Increasing neutralization of the reaction mixture with sodium hydroxide resulted in greater conversion of acrylic acid to sodium acrylate. The rate of polymerization, determined from a gravimetric off-line water removal technique, was shown to decrease significantly with decreasing degree of neutralization. Molecular weight also decreased with decreasing degree of neutralization. The glass transition temperature and hydrophilicity of the polymer product decreased with increasing degree of neutralization. In-line infrared monitoring was also used to monitor the reaction progress and was shown to be an effective tool for this purpose.     

Synthesis of anionic amphiphilic diblock copolymers of poly(styrene) and poly(acrylic acid) by reverse iodine transfer polymerization (RITP) in solution and emulsion

Reverse iodine transfer polymerization (RITP), offering the appealing potential of the in situ generation of transfer agents out of molecular iodine I₂, is employed in the synthesis of anionic amphiphilic diblock copolymers of poly(styrene) and poly(acrylic acid). Starting with well‐characterized poly(styrene) as macro‐transfer agents synthesized by RITP, diblock copolymers poly(styrene)‐b‐poly(tert‐butyl acrylate) of various lengths are successfully yielded in solution with a good architectural control. These blocks are then subjected to acid deprotection and subsequent pH control to give rise to anionic amphiphilic poly(styrene)‐b‐poly(acrylic acid). Besides, homopolymers of tert‐butyl acrylate are produced by RITP both in solution and in emulsion. Furthermore, a fruitful trial of the synthesis of diblock copolymers poly(tert‐butyl acrylate)‐b‐poly(styrene) is carried out through chain extension of the poly(tert‐butyl acrylate) latex as a macro‐transfer agent in seeded emulsion polymerization of styrene. Finally, the prepared block copolymer is deprotected to bring about its amphiphilic nature and a pH control caters for its anionic character. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4389–4398     

Needleless electrospinning of poly(acrylic acid) superabsorbent: Fabrication,characterization and swelling behavior

In this work, nanofibrous hydrogel has been fabricated from needleless electrospinning of Poly(acrylic acid) (PAA) in an aqueous solution with different concentrations. First, all solution samples were characterized for pH, surface tension, conductivity and viscosity. Next, electrospinnability of the PAA-water dope solution was investigated using the needleless electrospinning technique under constant conditions. Results indicated that the PAA-water solution was not electrospinnable. Therefore, the neutralization of carboxylic groups in the PAA chemical structure using the NaOH solution was investigated to enhance the PAA electrospinnability. Morphology observation revealed that the fiber diameters ranged from 40 to 250 nm and increased with increasing the solution concentrations. Increasing the neutralization degree (10%, 15% and 20% with 50 wt% NaOH solution) led to increase the dope viscosity and conductivity. The resultant nanofibers could be rendered water-insoluble by incorporating 1,4-butanediol diglycidyl-ether in the PAA-water dope solution, then heat-induced crosslinking was performed using a microwave at different curing times (1–5 min) and temperatures (45–105 °C). The nanofibrous hydrogel mat was then characterized by FTIR. The resulting nanofibrous hydrogel showed remarkable water absorption capacity up to 17,000% and 51,000% (within 15 min) in the standard saline solution and distilled water, respectively.