Facile fabrication of tough and biocompatible hydrogels from polyvinyl alcohol and agarose

A polyvinyl alcohol (PVA)-agarose (agar) composite hydrogel (M-PVA-agar-60) was developed by simple three cycles of freeze-thawing, followed by successively soaking in ammonium sulfate aqueous solution to induce phase separation and dialyzing against deionized water to remove residual sulfate salts. Due to the synergy of crystalline regions, hydrogen bonding and phase separation domains, the obtained M-PVA-agar-60 hydrogel exhibits excellent mechanical properties (tensile strength = 1.1 MPa, tensile strain = 324% and compressive stress = 12.5 MPa), combined with a high water content of 87.0%. Moreover, the hydrogel hardly expands after immersing in the phosphate-buffered saline aqueous solution at 37°C for a week, and the tensile stress and toughness remain almost the same as their initial values, superior to most reported non-swellable hydrogels. Because of the biocompatible starting materials, absence of toxic chemicals, and dialysis in advance to remove ammonium sulfate, the hydrogel also shows excellent cell compatibility, making it an ideal candidate for tissue engineering materials.     

Original synthesis of polyvinyl butyral with a green deep eutectic solvent and a weakly polyacrylic acid from polyvinyl alcohol and the impacts of the chains structures of polyvinyl alcohol

In this work, an environmentally-friendly deep eutectic solvent (DES) was employed as a catalyst to generate polyvinyl butyral (PVB) resins from polyvinyl alcohol (PVA) with a weakly acidic polymer (polyacrylic acid [PAA]) as an emulsifier. Finally, high viscosity PVB resins with molecular weight of 110,000–200,000 g · mol⁻¹ and acetalization degree above 83% were successfully synthesized, which was found to satisfy the requirements for interlayer films between safety glass. Furthermore, it was well proved that the properties of PVB resins immensely depend on the molecular structures of the PVA. The molecular weight of the PVB, independent of alcoholic degrees of the PVA, indicated an upward trend with the increase of the molecular weight of the PVA. As for these four PVBs with high molecular weight, the T_g was sensitive to the content of hydroxyl and acetal groups rather than molecular weight, associated with the inter- or intra-molecule hydrogen bond between  OH. PVB-1799 and PVB-1797 had higher T_i and T_g than that of PVB-1788 and PVB-1795 because the former had low contents of vinyl acetate group (VAc) and alcohol hydroxyl group (VOH). The tensile strength of PVBs was all higher than 30 Mpa, and the elongation at break was about 300% due to their high molecular weights.     

Rheological properties of solutions of graft copolymers of polyvinyl alcohol and polyacrylic acid

Conclusions The activation energy of viscous flow of systems containing the PVA-PAA graft copolymer is considerably higher than that for solutions of PAA; the activation energy of viscous flow of solutions of mechanical mixtures of PVA and PAA is higher than that of mixtures of PVA with the graft copolymer. This fact is a convincing confirmation of the compatibility of the PVA-(PVA-PAA) graft copolymer system.The compatibility of this system is also shown by the high stability of the solutions. Thus, 12.5% solutions of the mixture of PVA and the graft copolymer in a ratio of 4/1 do not separate into layers during 3–4 days. The achievement of the compatibility of a mixture of the polymers mentioned by grafting is an important advantage obtained by the modification of polymers by the method of graft copolymerisation.All-Union Correspondence Institute of the Textile and Light Industries. Translated from Khimicheskie Volokna, No. 2, pp. 27–29, March–April, 1969.     

High‐tensile‐strength polyvinyl alcohol films prepared from freeze/thaw cycled gels

The mechanical properties and molecular structure of a poly(vinyl alcohol) (PVA) film, which was obtained by eliminating water from a PVA hydrogel using repeated freeze/thaw cycles, were investigated by tensile tests, thermal analysis, and X‐ray diffraction measurements. The mechanical properties of PVA with 99.9% saponification were measured as a function of the number of freeze/thaw cycles performed. The tensile strength and Young's modulus increased and the elongation at break decreased with increasing freeze/thaw cycles. The tensile strength and Young's modulus of PVA films obtained after seven freeze/thaw cycles were as high as 255 MPa and 13.5 GPa after annealing at 130°C. Thermal analysis and X‐ray diffraction measurements revealed that this is because of a high crystallinity and a large crystallite size. A good relationship between the tensile strength and the glass transition temperature was obtained, regardless of the degree of saponification and annealing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40578.     

Preparation and characterization of polyacrylic acid‐poly(vinyl alcohol)‐based interpenetrating hydrogels

Some structural features of hydrogels from poly(acrylic acid) (PAAc) of various crosslinking degrees have been investigated through mechanical and swelling measurements. Interpenetrating polymer hydrogels (IPHs) of poly(vinyl alcohol) (PVA) and PAAc have been prepared by a sequential method: crosslinked PAAc chains were formed in aqueous solution by crosslinking copolymerization of acrylic acid and N,N‐methylenebisacrylamide in the presence of PVA. The application of freeze–thaw (F–T) cycles leads to the formation of a PVA hydrogel within the synthesized PAAc hydrogel. The swelling and viscoelastic properties of the IPHs were evaluated as a function of the content of crosslinker and the application of one F–T cycle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5789–5794, 2006     

Sponge effects in polymers interacting with low‐molecular weight compounds

The competition between additives for a place in the polymer matrix are discovered when the blending components ensure the enthalpy of mixing to be nearly zero. The competition of the additives exists as the process of accelerated exudation of one another from glasslike or jellylike films. This is inconsistent with the entropic nature of the mixtures assumed for the homogeneous polymer solutions. The considered effects are beyond the statistical thermodynamics of solutions, and they are explained by the specificity of the chain‐sponge organization of a noncrystalline polymer matrix. The equilibrium sorption of volatile compounds by polymer samples is explained by the mechanism of structural entropic solvation and is described by the equation of the micropore volume filling theory. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2435–2442, 2000     

Photoluminescent and tough hydrogels from silk fibroin and polyacrylic acid complexed with europium

Biocompatible, tough, and photoluminescent hydrogels are highly desirable for biomedical applications in vivo. Herein, hybrid hydrogels prepared from silk fibroin (SF) and polyacrylic acid (PAA) and complexed with europium, named as SF-PAA-Eu³⁺ hydrogels, exhibit good comprehensive properties. Owing to the intensive molecular interactions among SF, PAA, and Eu³⁺, SF-PAA-Eu³⁺ hydrogels show a greatest tensile strength of 0.58 MPa, elongation of 443%, and work of fracture of 1.65 MJ/m. In vivo imaging experiment in a mouse subcutaneous implantation model revealed excellent and sustained photoluminescence of the SF-PAA-Eu³⁺ hydrogels for 24 h. The work provides a strategy for designing functional SF-based hydrogels for imaging applications in vivo.     

Preparation and swelling properties of semi‐IPN hydrogels based on chitosan‐g‐poly(acrylic acid) and phosphorylated polyvinyl alcohol

The phosphorylated poly(vinyl alcohol) (P‐PVA) samples with various substitution degrees were prepared through the esterification reaction of PVA and phosphoric acid. By using chitosan (CTS), acrylic acid (AA) and P‐PVA as raw materials, ammonium persulphate (APS) as an initiator and N,N‐methylenebisacrylamide as a crosslinker, the CTS‐g‐PAA/P‐PVA semi‐interpenetrated polymer network (IPN) ssuperabsorbent hydrogel was prepared in aqueous solution by the graft copolymerization of CTS and AA and followed by an interpenetrating and crosslinking of P‐PVA chains. The hydrogel was characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) techniques, and the influence of reaction variables, such as the substitution degree and content of P‐PVA on water absorbency were also investigated. FTIR and DSC results confirmed that PAA had been grafted onto CTS backbone and revealed the existence of phase separation and the formation of semi‐IPN network structure. SEM observations indicate that the incorporation of P‐PVA induced highly porous structure, and P‐PVA was uniformly dispersed in the polymeric network. Swelling results showed that CTS‐g‐PAA/P‐PVA semi‐IPN superabsorbent hydrogel exhibited improved swelling capability (421 g·g^?1 in distilled water and 55 g·g^?1 in 0.9 wt % NaCl solution) and swelling rate compared with CTS‐g‐PAA/PVA hydrogel (301 g·g^?1 in distilled water and 47 g·g^?1 in 0.9 wt % NaCl solution) due to the phosphorylation of PVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and evaluation of swelling kinetics of electric field responsive poly(vinyl alcohol)‐g‐polyacrylic acid/OMNT nanocomposite hydrogels

Novel electro‐responsive nanocomposite hydrogels were prepared by the radical graft polymerization reaction of partially neutralized acrylic acid on poly(vinyl alcohol) and organically modified MMT nanoclay (OMMT) using glutaraldehyde as a crosslinker and potassium initiator. The structures of the hydrogels were confirmed by using Fourier transform infrared, X‐ray diffraction, and scanning electron microscopy study. The nanocomposite hydrogels were characterized by evaluating such molecular weight between crosslinks, (Mc) crosslinking density (ρ), and mesh size (ξ). The effects of various parameters on the swelling behavior of the hydrogels were studied. The thermogravimetric analysis indicated that introduction of clay resulted in an increase in thermal stability. Finally, the electric stimuli responsive measurement indicates the bending of hydrogel toward the cathode in an aqueous solution of NaCl. POLYM. COMPOS., 36:34–41, 2015. © 2014 Society of Plastics Engineers     

Development of potentially biodegradable polyamide‐6 and polyvinyl alcohol blends: Physico‐mechanical properties,thermal properties,and soil test

Blends of polyamide‐6 with 5, 7.5, 10, 15, and 20 wt % of polyvinyl alcohol (PVA) were prepared by the extruding in a corotating twin‐screw extruder. The extrudate strands were cut into pellets and injection‐molded to make test specimens. These specimens were tested for physico‐mechanical properties such as tensile strength, impact strength, density, water absorption, hardness, and thermal characteristics by differential scanning calorimetry, heat distortion temperature (HDT), vicat softening point (VSP), and melt flow index. The prepared blends show enhanced biodegradation, water absorption, and density, but it is observed that the introduction of PVA into the polyamide–6 matrix shows considerable reduction in tensile strength, impact strength, HDT, VSP, and hardness initially, but subsequent addition does not show significant reduction because of the enhanced interaction between amide groups of polyamide‐6 and hydroxyl groups of PVA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2339–2346, 2005     

Interactions of active carbon with low‐ and high‐molecular weight polyethylene glycol and polyethylene oxide

Composites of active carbon in a polymeric matrix composed of polyethylene oxide (PEO) and polyethylene glycol (PEG) having different molecular weight distributions were obtained by melt mixing. Characterization of the amount of bound polymer in the whole range of composition for the polymeric matrix has been performed after dissolution of the matrix in water. Size exclusion chromatography of the solution has been used to determine the composition of the polymeric bound layer. It has been shown that in these conditions of mixing, the amount of bound polymer slightly decreases from a pure PEG to a pure PEO matrix. Furthermore, PEO is preferentially bound to the active carbon. A simple model is used to show that bonding occurs preferentially by monomeric units rather than by chain ends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3490–3497, 2006     

High molecular weight tail and long‐chain branching in low‐density polyethylenes

The composition of the high molecular weight tail in branched low‐density polyethylenes made by both tubular and autoclave reactors was studied in detail using size‐exclusion chromatography (SEC) coupled with a viscosity detector (VD) and a two‐angle light‐scattering detector (LSD). The detection of a second peak at very small elution volumes in the light‐scattering chromatogram but not in the refractive index chromatogram and viscosity chromatogram is due to high molecular weight species. It is also indicative of a change in the long‐chain branching distribution. It was found that the intrinsic viscosity contraction factor g′ scales with the radius of the gyration contraction factor, g, with the exponent, ε, having a value in the range 0.4–1.4. Furthermore, ε shows significant molar mass dependence. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2815–2822, 2001     

Double‐network hydrogel with high mechanical strength prepared from two biocompatible polymers

Novel double‐network (DN) hydrogels with high mechanical strength have been fabricated with two biocompatible polymers, poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG), through a simple freezing and thawing method. Some properties of the obtained hydrogels, such as the mechanical strength, rheological and thermodynamic behavior, drug release, and morphology, have been characterized. The results reveal that in sharp contrast to most common hydrogels made with simple natural or synthetic polymers, PVA/PEG hydrogels can sustain a compressive pressure as high as several megapascals, highlighting their potential application as biomedical materials. In addition, a model for describing the structural formation of PVA/PEG DN hydrogels is proposed: the condensed PVA‐rich phase forms microcrystals first, which bridge with one another to form a rigid and inhomogeneous net backbone to support the shape of the hydrogel, and then the dilute PEG‐rich phase partially crystallizes among the cavities or voids of the backbone; meanwhile, there are entanglements of molecular chains between the two polymers. Moreover, a mechanism is also proposed to explain the high mechanical strength of PVA/PEG DN hydrogels. It is suggested that the free motion of PEG clusters in the cavities of PVA networks can prevent the crack from growing to a macroscopic level because the linear PEG chains in the cavities effectively absorb the crack energy and relax the local stress either by viscous dissipation or by large deformation of the PEG chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phase behavior of N‐isopropylacrylamide/acrylic acid copolymer hydrogels prepared with ultrasound

N‐Isopropylacrylamide/acrylic acid copolymer hydrogels were synthesized with ultrasound. The thermoresponsive phase behaviors of gels synthesized with ultrasound (US gels) were investigated and compared with those of gels synthesized in the absence of ultrasound (FR gels). The US gels showed thermoresponsive swelling behavior with a large hysteresis over a wide range of temperatures around its phase‐transition temperature. The hysteresis became larger with an increasing copolymerized acrylic acid content. The US gels were also characterized from the viewpoint of chemical, hydration, and macroscopic physical structures. Little difference was observed in the chemical and hydration structures of the FR gels and US gels. The macroscopic physical structure of the US gels was, however, distinct from that of the FR gels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2449–2452, 2003     

Preparation,characterization, and water‐sorption study of polyvinyl alcohol based hydrogels with grafted hydrophilic and hydrophobic segments

The interpenetrating polymer network hydrogels based on poly(vinyl alcohol) were obtained by graft copolymerization of acrylamide and styrene onto polyvinyl alcohol in the presence of N,N′‐methylene bisacrylamide as a crosslinking agent. The hydrogels were characterized by optical microscopy, scanning electron microscopy, infrared spectral analysis, differential scanning calorimeter, and thermogravimetric analysis. The hydrogels showed enormous swelling in aqueous medium and displayed swelling characteristics, which were highly dependent on the chemical composition of the hydrogels and pH of the swelling medium. The kinetics of water uptake and the mechanisms of water transport were studied as a function of composition of the hydrogel and pH of the swelling medium. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1129–1142, 2005     

Preparation of high molecular weight poly(vinyl alcohol) with high yield using low‐temperature solution polymerization of vinyl acetate

Vinyl acetate (VAc) was solution‐polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) having low chain transfer constant at 30, 40, and 50°C, using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponification with sodium hydroxide. The polymerization rates of VAc in TBA and in DMSO were proportional to the 0.49 and 0.72 powers of ADMVN concentration, respectively. For the same polymerization conditions, TBA was absolutely superior to DMSO in increasing the molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VAc in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration calculated using initial rate method and by an activation energy difference of polymerization obtained from the Arrhenius plot. Low‐temperature solution polymerization of VAc in TBA or DMSO by adopting ADMVN proved successful in obtaining PVA of high molecular weight (number–average degree of polymerization (P_n): 4100–6100) and of high yield (ultimate conversion of VAc into PVAc: 55–80%) with diminishing heat generated during polymerization. In the case of bulk polymerization of VAc at the same conditions, maximum P_n and conversion of 5200–6200 and 20–30% was obtained, respectively. The P_n and lightness were higher, and the degree of branching was lower with PVA prepared from PVAc polymerized at lower temperatures in TBA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1003–1012, 2001     

Ultradrawing properties of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends prepared at various formation temperatures

The ultradrawing behavior of ultrahigh‐molecular‐weight polyethylene/low‐molecular‐weight polyethylene film specimens prepared at various concentrations and formation temperatures was studied. The critical draw ratio (D_rc) of UL_?0.7 film specimens was found to depend significantly on the formation temperature used to prepare the film specimens. At any fixed drawing temperature, the D_rc values of UL_?0.7 specimens prepared at various formation temperatures increased significantly as the formation temperatures were reduced. In fact, with an optimum drawing temperature of 95°C, the D_rc values of UL_?0.7 specimens prepared at a formation temperature of 0°C reached 488, about 50% higher than that of UL_?0.7 specimens prepared at a formation temperature of 95°C. These interesting phenomena were investigated in terms of the thermal, birefringence, and tensile properties of these undrawn and drawn UL_?0.7 specimens. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3728–3738, 2003     

Facile synthesis of extremely biocompatible double‐network hydrogels based on chitosan and poly(vinyl alcohol) with enhanced mechanical properties

An easy and ecofriendly method for designing double‐network (DN) hydrogels based on chitosan and poly(vinyl alcohol) (PVA) with high mechanical performance is described. When covalent bonds in the networks are used as crosslinking agents in the achievement of a higher mechanical strength, the irreversible deformation of these hydrogels after a large force is applied is still one of the most important obstacles. To overcome this problem, we used physical crosslinking for both networks. The mechanical strength, surface morphology, and cytotoxicity of the films were studied by tensile testing, scanning electron microscopy analysis, and an MTT assay. The synthesized chitosan–PVA DN hydrogels showed a large improvement in the tensile strength to 11.52 MPa with an elongation of 265.6%. The surface morphologies of the films demonstrated the effective interactions between the two networks and a suitable porosity. Also, because of the use of a natural polymer and honey as a plasticizer, the cell culture indicated that the synthesized DN hydrogels had good biocompatibility (with 327.49 ± 11.22% viability) and could be used as capable biomaterials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45752.     

Synthesis and characterization of low‐molecular‐weight polyacrolein

Acrolein was polymerized in a polar solvent in the presence of terc‐ and sec‐butyl lithium as initiators. Using a low monomer to initiator molar ratio and 1‐h reaction time, cyclic structures were shown to be formed in the main chain of the resulting oligomers. The influence of different monomer to initiator molar ratios on molecular weight and on molecular weight distribution was investigated. Chain‐transfer reactions toward the monomer resulted in lower molecular weights and narrower polydispersions as [M]/[I] increased. The influence of initiator type on the polymer molecular weight was also evaluated. FTIR analysis of the degradation products at different heating temperatures indicated that the oligomers structure is composed of aldehyde, ether, and vinyl functional groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of aluminoxane on molecular weight and molecular weight distribution of polyethylene prepared by an iron‐based catalyst

A series of aluminoxanes, tetraethylaluminoxane (TEAO), tetraalkylaluminoxane (TAAO), Et₂AlOB(4 ? F ? C₆H₄)OAlEt₂ (BTEAO) and ethyl‐iso‐butylaluminoxane modified with p‐fluorophenylboric acid (BEBAO), were prepared and their effects on molecular weight (MW) and molecular weight distribution (MWD) of polyethylene prepared by the iron‐based catalyst [(ArN?C(Me))₂C₅H₃N]FeCl₂ (Ar?2,6‐dimethylphenyl) ( 1 ) were investigated. It was found that TEAO and BTEAO were highly efficient activators for iron‐based catalysts and introducing the branched bulky group (eg iso‐Bu) into the aluminoxane activator could improve the MW of the resulting polyethylene. The MW of polyethylene produced by activators modified by p‐fluorophenylboric acid was higher than for other aluminoxane activators. The TEAO‐ and TAAO‐based polyethylene exhibited attractive bimodal MWD, and the lower MW fraction of bimodal MWD was shown to be produced in the early stage of polymerization due to chain transfer to the aluminium activator. Copyright © 2004 Society of Chemical Industry