Water-soluble complexes of star-shaped poly(acrylic acid) with quaternized poly(4-vinylpyridine)

The interaction of star-shaped poly(acrylic acid) having various numbers of arms (5, 8, and 21) and a strong cationic polyelectrolyte, viz., poly( N-ethyl-4-vinylpyridinium bromide), was examined at pH 7 by means of turbidimetry and dynamic light scattering. Mixing aqueous solutions of the oppositely charged polymeric components was found to result in phase separation only if their base-molar ratio Z = [N+]/[COO (-) + COOH] exceeds a certain critical value ZM ( ZM < 1); this threshold value is determined by the number of arms of the star-shaped polyelectrolyte and the ionic strength of the surrounding solution. At Z < ZM, the homogeneous aqueous mixtures of the oppositely charged polymeric components contain two types of complex species clearly differing in their sizes, with the fractions of these species appearing to depend distinctly on the number of arms of the star-shaped poly(acrylic acid), the base-molar ratio of the oppositely charged polymeric components in their mixtures, and the ionic strength of the surrounding solution. The small complex species (major fraction) are assumed to represent the particles of the water-soluble interpolyelectrolyte complex whereas the large complex species (minor fraction) are considered to be complex aggregates.     

Assembly of nanotubes of poly(4-vinylpyridine) and poly(acrylic acid) through hydrogen bonding

Nanotubes of poly(4-vinylpyridine) (PVP) and poly(acrylic acid) (PAA) were fabricated by hydrogen bonding based on layer-by-layer (LbL) assembly. The uniform and flexible tubular structures were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). FTIR and X-ray photoelectron spectroscopy (XPS) measurements confirm the formation of hydrogen bonds in the assembled nanotubes. PAA can be released from the assembled PAA/PVP nanotubes in a basic aqueous solution to give the walls of the tubes a porous structure. Such assembled nanotubes can be considered as carriers for catalysts or drugs, especially in aqueous solution against capillary force.     

Association of copolymers of methacrylic acid and 4-vinylpyridine in comparison with an intermacromolecular complex of poly(methacrylic acid) with poly(4-vinylpyridine)

Solution properties of copolymers [C(MA-Py)x] of methacrylic acid and 4-vinylpyridine and intermacromolecular complexes of poly(methacrylic acid) (PMAA) and poly(4-vinylpyridine) (PVP) in the presence or absence of a proton-accepting water-soluble polymer such as poly(ethylene glycol) (PEG) in water/methanol mixed solvent are studied by potentiometric titration, turbidity and viscosity methods. These copolymers behave like polyampholytes and their solubilities are strongly dependent with pH changes. The pH regions where they are precipitated around their isoelectric points are narrower than those of the intermacromolecular complex of PMAA with PVP. The polyampholyte can form an intermacromolecular complex with PEG in acidic solution but this complex is soluble in the medium.     

Structure of the polyion complex between poly(sodium P-styrene sulfonate) and poly(diallyl dimethyl ammonium chloride)

Stoichiometric and nonstoichiometric polyion complex films were prepared from poly(sodium p-styrene sulfonate) and poly(diallyl dimethyl ammonium chloride). X-ray photoelectron spectroscopy revealed that the ionic groups in the complex are more ionized than in each component polymer. Fluorescence measurements showed that the complex had a main emission peak around 300 nm, whereas the peak for its original polyanion occurred at 324 nm. With the monomer and excimer peaks of the phenyl rings taken to be at 294 and 324 nm, respectively, the ratio of excimer to monomer emission intensities increased in proportion to the mole fraction of polyanion in the observed range 0.44–0.59. There was no discontinuity at the stoichiometric composition. Furthermore, the change in peak position shows that the local aggregation of phenyl groups in the polyanion was destroyed by complexation with the polycation through Coulombic forces. These results, together with the visual observation of the transparency of the films, mean that the mixing between polyanion and polycation chains in the polyion complex is on the molecular level and that this polymer alloy is miscible.     

Physicochemical properties of pH-controlled polyion complex (PIC) micelles of poly(acrylic acid)-based double hydrophilic block copolymers and various polyamines

The physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted of electrostatic complexes of two oppositely charged polyelectrolytes. The pH-sensitive micelles were obtained with double hydrophilic block copolymers containing a poly(acrylic acid) block linked to a modified poly(ethylene oxide) block and various polyamines (polylysine, linear and branched polyethyleneimine, polyvinylpyridine, and polyallylamine). The pH range of micellization in which both components are ionized was determined for each polyamine. The resulting PIC micelles were characterized using dynamic light scattering and small-angle X-ray scattering experiments (SAXS). The PIC micelles presented a core–corona nanostructure with variable polymer density contrasts between the core and the corona, as revealed by the analysis of the SAXS curves. It was shown that PIC micelle cores constituted by polyacrylate chains and polyamines were more or less dense depending on the nature of the polyamine. It was also determined that the density of the cores of the PIC micelles depended strongly on the nature of the polyamine. These homogeneous cores were surrounded by a large hairy corona of hydrated polyethylene oxide block chains. Auramine O (AO) was successfully entrapped in the PIC micelles, and its fluorescence properties were used to get more insight on the core properties. Fluorescence data confirmed that the cores of such micelles are quite compact and that their microviscosity depended on the nature of the polyamine. The results obtained on these core–shell micelles allow contemplating a wide range of applications in which the AO probe would be replaced by various cationic drugs or other similarly charged species to form drug nanocarriers or new functional nanodevices.     

Miscibility of poly(butyl methacrylate-CO-methacrylic acid) or poly(styrene-CO-methacrylic acid) with poly(styrene-CO-4-vinylpyridine) or poly(butyl methacrylate-CO-4-vinylpyridine)

The miscibility of blends of copolymers of different compositions of butyl methacrylate-co-methacrylic acid or styrene-co-methacrylic acid with styrene-co-4-vinylpyridine or butyl methacrylate-co-4-vinylpyridine was studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. It was found that these blends were miscible in part as a result of specific favorable interactions between the carboxylic acid and pyridine groups within the polymer chains. Evidence of such interactions was obtained from the single composition-dependent glass transition temperature and the FTIR results.     

Gamma radiation synthesis of comb-type graft hydrogels based on poly(acrylic acid) and 4-vinylpyridine

A pH-sensitive comb-type hydrogel was obtained by gamma radiation polymerization and crosslinking of acrylic acid (AAc) in solution. The pH-sensitive 4-vinylpyridine (4VP) was then grafted to the poly acrylic acid (PAAc) hydrogel using gamma radiation from a ⁶⁰Co source. The comb type graft polymers obtained (net-PAAc)-g-4VP has been studied through determination of graft yield and swelling behavior. The critical pH value was found to be 5.6. The apparent mechanical properties appear to be qualitatively better than hydrogels of PAAc upon swelling. The new comb-type system presents faster swelling response (30 h) than the polyacrylic acid hydrogel (50 h). The increase in dose rate from 7.3 to 11.3 kGy h⁻¹, increase the radiation grafting percentage of 4VP in the system. Comb-type polymers were also characterized by DSC, TGA and FTIR-ATR.     

聚4-乙烯吡啶类高分子铑(I)化合物对甲醇羰化合成乙酸的催化性能

本文将聚4-乙烯吡啶(PVPy)、聚1-甲基-4-乙烯吡啶季铵碘(PVPyMe^+I^-)和4-乙烯吡啶/1-甲基-4-乙烯吡啶季铵碘共聚物[P(VPy-VPyMe^+I^-)]分别与四羰基二氯二铑反应制备成高分子铑(I)催化剂, 并考察了它们各自在甲醇羰化反应中的催化行为。结合IR光谱对这些催化剂结构的分析研究表明, 以上4-乙烯吡啶类高分子链上所含的功能基各自与铑(I)配合物离子之间以不同的链联方式所产生的不同结构的活性物种对催化反应性能有着显著的影响, 具有双配位的螯合型稳定结构的Rh(I)/PVPy催化剂, 表现出较差的催化反应活性, 而离子键合型的Rh(I)/PVPyMe^+I^-和杂键合型的Rh(I)/P(VPy-VPyMe^+I^-)催化剂均表现较佳的反应性能, 特别是Rh(I)/P(VPy-VPyMe^+I^-),由于其形成具有更强亲核性的五配位中间过渡态参与反应过程, 从而在较大程度上提高了催化反应速率。     

Stereoregularity of poly(2-vinylpyridine) and poly-(4-vinylpyridine)

In order to determine the stereoregularity of poly(4-vinylpyridine), 4-vinylpyridine-β,β-d₂ was synthesized from 4-acetylpyridine. The ¹H-NMR spectra of the deuterated and nondeuterated polymers were measured and analyzed. From the ¹H-NMR spectra of poly(4-vinylpyridine-β,β-d₂), triad tacticity can be obtained, while the ¹H-NMR spectra of nondeuterated poly(4-vinylpyridine) give the fraction of isotactic triad. The ¹³C-NMR spectra of poly(4-vinylpyridine) were also observed, and the spectra of C₄ carbon of polymers were assigned by the pentad tacticities. The fraction of isotactic triad of poly(2-vinylpyridine) and poly(4-vinylpyridine) obtained under various polymerization conditions were determined. The radical polymerization and anionic polymerizations with phenylmagnesium bromide and n-butyllithium as catalysts of 4-vinylpyridine gave atactic polymers.     

Surface polyion complex gel with poly(vinylphosphonic acid) and poly(N‐vinylamide)s

The surface polyion complex gel (sPIC gel), which possesses chemically bonded nonionic gel moiety, was designed using N‐vinylacetamide (NVA), N‐vinylforamide (NVF), and vinyl phosphonic acid (VPA). Taking advantage of the property of NVF as vinylamine (VAm) precursor, the cationic moiety was introduced only onto the surface of poly(NVA‐co‐NVF), producing surface hydrolyzed poly(NVA‐co‐NVF‐co‐VAm), and the successive polymerization of VPA inside the gel successfully produced sPIC gel. The swelling ratio of the sPIC gel was investigated under various pH conditions, and compared with that of the fully polyion complex gel (PIC gel), using totally hydrolyzed poly(NVA‐co‐VAm). The swelling ratio of sPIC gel ranged between 14 and 25, while that of the PIC gel ranged between 2 and 5. The anionic compound, AR, showed a sustained release from sPIC gel at pH 2, due to the electrostatic interactions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 562–566     

A new approach for the fabrication of an alternating multilayer film of poly(4-vinylpyridine) and poly(acrylic acid) based on hydrogen bonding

A new approach for the fabrication of a multilayer film assembly is explored, which is based on the alternating assembling of poly(4-vinylpyridine) and poly(acrylic acid) via hydrogen bonding. The homogeneous multilayer films were characterized by UV-Vis, X-ray diffraction and atomic force microscopy (AFM) measurements. The nature of interaction between the two polymers is identified as hydrogen bonding by IR spectroscopy.     

Complexation and rate of polymerization of acrylic acid and methacrylic acid in the presence of poly(4-vinylpyridine) in dilute methanol solution

A 1:1 hydrogen-bonded complex was formed between acrylic acid (AA) or methacrylic acid (MA) and the pyridine group of poly(4-vinylpyridine) (P4VP) in dilute solutions. A shift of infrared absorption of the hydrogen-bonded acid O? H to a lower energy direction and an upfield shift of acid proton in the NMR were observed when the monomers were added with pyridine. The equilibrium constants of the 1:1 complexation with P4VP measured by using a semipermeable membrane were 0.58 and 0.26 for AA and MA, respectively, at 25°C in methanol. The bromometrically measured initial rate of radical polymerization showed only a slight enhancement in the presence of P4VP, the rate being maximum at the 4VP unit:monomer mole ratio of 0.25 and 0.5 for AA and MA, respectively, in dilute methanol solution at 60°C.     

Polyelectrolyte complex nanoparticles from chitosan and poly(acrylic acid) and Polystyrene‐block‐poly(acrylic acid)

Interpolymer polyelectrolyte complexes of chitosan (CS) with poly(acrylic acid) homopolymers and polystyrene‐block‐poly(acrylic acid) diblock copolymers were prepared and characterized. The influence of the positive/negative charge balance (charge ratio), pH, and ionic strength were thoroughly studied by dynamic light scattering. The existence of a strong polyelectrolyte effect was also highlighted in this study. Domains of stability, in which nanoparticle sizes are smaller than 100 and 200 nm for complexes of CS with the homopolymer and copolymer, respectively, were identified and confirmed by scanning electron microscopy and atomic force microscopy. The charged nature of the surface of the nanoparticles was evidenced by Zeta potential measurements. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

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.     

Water-soluble hydrogen-bonding interpolymer complex formation between poly(ethylene glycol) and poly(acrylic acid) grafted with poly(2-acrylamido-2-methylpropanesulfonic acid)

Comb-type copolymers of poly(acrylic acid) grafted with poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPSA) side chains form with poly(ethylene glycol), at low pH, water-soluble hydrogen-bonding interpolymer complexes. Turbidimetry, viscometry, and dynamic light scattering measurements suggest that compact, negatively charged, colloidal nanoparticles are formed at pH<3.75. The influence of the structure of the graft copolymers and of the ionic strength of the solution on the size of these nanoparticles was investigated. It was found that their hydrodynamic radius decreases by increasing the molecular mass of the PAMPSA side chains of the graft copolymer and increases with increasing the ionic strength of the solution.     

Self-association effects on phase behavior and thermal properties of poly(styrene-co-itaconic acid)/poly(butyl methacrylate-co-4-vinylpyridine) blends

Blends based on poly(styrene-co-itaconic acid) containing 11 or 27 mol % of itaconic acid (PSIA11, PSIA27) and poly(n-butyl methacrylate-co-4-vinylpyridine) containing 26 or 37 mol% of 4-vinylpyridine (PBM4VP26, PBM4VP37) were prepared. Their phase behavior and thermal properties were investigated by several techniques. Specific interactions that occurred between these copolymers were evidenced by FTIR from the appearance of characteristic new bands. The different T _g-composition behaviors of these systems evidenced by DSC and interpreted in terms of different types and strength of interactions that occurred within these blends, were analyzed by Kwei and “BCKV” (Brostow, Chiu, Kalogeras, Vassilikou-Dova) approaches. The positive deviation from the weight average of their constituent T _g’s, observed with the PSIA11/PBM4VP26 and PSIA11/PBM4VP37 systems, is due to the presence of strong specific interactions that occurred within this system while the practically similar S shaped curves obtained with PSIA27/PBM4VP26 and PSIA27/PBM4VP37 blends indicate that, due to self-association of carboxylic groups within PSIA27, a reduced number of efficient specific interactions occurred within these blends even though containing relatively higher amounts of interacting species. A thermogravimetric analysis confirmed improved thermal stability of these blends over the individual copolymers.     

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.