Poly(vinyl alcohol) fiber radicals induced by photo-irradiation at room temperature

The decay behavior of radicals produced on poly(vinyl alcohol) (PVA) fiber by photo-irradiation at room temperature and the graft copolymerization of methyl methacrylate (MMA) on the irradiated PVA fiber were investigated. Two kinds of stable radicals showing singlet and triplet spectra were indicated for both unsensitized and ferric ion-sensitized samples, especially with the emphasis of triplet component radical. The decay of radicals was promoted by contact with various organic solvent-water solutions, which effects were in the order of dimethyl sulfoxide (DMSO)–water > acetone–water > water > dioxane–water > methanol–water. On the other hand, graft copolymerization of MMA on the preirradiated sample was effectively initiated with the aid of a little water or a mixed solution of organic solvent and water. Methanol and dioxane, which decay radicals milder than acetone and DMSO do, contributed to give a higher per cent grafting. As no initiation took place with the unirradiated sample, it is concluded that the ability of preirradiated samples to initiate graft copolymerization should be caused by the PVA fiber radicals, which are smoothly produced by photo-irradiation at room temperature and show a triplet spectrum.     

ESR study of reactions of cellulose with ·OH generated by Fe+2/H2O2

It was demonstrated by ESR spectroscopy that the Fe⁺²/H₂O₂ system gave a reactive species which generated an ESR triplet spectrum or sorbitol similar to that generated by hydroxyl radicals from the Ti⁺³/H₃O₂ system. An ESR spectrum was obtained for the hydroxyl radicals generated by the latter system. However, the lifetime of hydroxyl radicals, generated by the Fe⁺²/H₂O₂ system, was apparently very short, and an ESR spectrum for the hydroxyl radicals, generated by this system, was not observed. The Fe⁺²/H₂O₂ system also generated triplet spectra with cotton cellulose I, cotton cellulose II, and microcrystalline cellulose, suggesting that a hydrogen atom had been abstracted from the hydroxyl group on carbon C₆, or possibly the hydrogen atom on carbon C₅. The ESR spectrum generated on microcrystalline cellulose was less intense than those generated on cellulose I and II. On initiation of graft polymerization of the activated cellulose with acrylonitrile, the triplet spectrum disappeared and was replaced by two strong singlet spectra. One of the singlet spectra was likely generated on carbon C₁ or C₄ on depolymerization of the cellulose molecule, and the other was probably generated on the end of the growing polyacrylonitrile molecular chain. The absence of a triplet spectrum gave direct evidence for the order in which the acrylonitrile monomer was being grafted onto the cellulose molecule. The mechanisms proposed by Haber and Weiss for the reactions generated in the Fe⁺²/H₂O₂ system were generally supported.     

Photo-induced graft copolymerization of methyl methacrylate on poly(vinyl alcohol)

Photo-induced graft copolymerization of methyl methacrylate on poly(vinyl alcohol) (PVA) was examined in aqueous solutions. In unoxidized samples, only a few percent of PVA used took part in the formation of grafts, and the percent grafting was very low. However, if Fe²⁺, Fe³⁺, anthraquinone-2,7-disulfonate, or oxalic acid was used as sensitizer, the percent grafting was somewhat improved. Among them, the effect of Fe³⁺ was most remarkable. Oxidized PVA showed a higher initiating activity and was more susceptible to the sensitizing action of Fe³⁺ than unoxidized PVA. As Fe³⁺ has an ability to accelerate the photo-induced scission reaction of PVA chains for both oxidized and unoxidized PVA, it is thought to be very probable that the copolymer formed in the photo-induced systems has a block polymer-type structure like that in systems initiated by ceric ion or hydrogen peroxide.     

Synthesis of poly(acrylic acid)–Fe3+/gelatin/poly(vinyl alcohol) triple‐network supramolecular hydrogels with high toughness,high strength and self‐healing properties

Hydrogels with good mechanical and self‐healing properties are of great importance for various applications. Poly(acrylic acid)–Fe³⁺/gelatin/poly(vinyl alcohol) (PAA‐Fe³⁺/Gelatin/PVA) triple‐network supramolecular hydrogels were synthesized by a simple one‐pot method of copolymerization, cooling and freezing/thawing. The PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogels exhibit superior toughness, strength and recovery capacity compared to single‐ and double‐network hydrogels. The mechanical properties of the synthesized hydrogels could be tailored by adjusting the compositions. The PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogel with 0.20 mmol Fe³⁺, 3% gelatin and 15% PVA could achieve good mechanical properties, the tensile strength and elongation at break being 239.6 kPa and 12.8 mm mm^?1, respectively, and the compression strength reaching 16.7 MPa under a deformation of about 91.5%. The synthesized PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogels have good self‐healing properties owing to metal coordination between Fe³⁺ and carboxylic groups, hydrogen bonding between the gelatin chains and hydrogen bonding between the PVA chains. Healed PAA‐Fe³⁺(0.20)/Gelatin3%/PVA15% triple‐network hydrogels sustain a tensile strength of up to 231.4 kPa, which is around 96.6% of the tensile strength of the original samples. Therefore, the synthesized triple‐network supramolecular hydrogels would provide a new strategy for gel research and expand the potential for their application. © 2019 Society of Chemical Industry     

Photo-induced graft copolymerization of methyl methacrylate on oxidized poly(vinyl alcohol) fiber

Photo-induced graft copolymerization of methyl methacrylate on oxidized poly(vinyl alcohol) fiber was investigated. Oxidation of the fiber sample with sodium hypochlorite or periodic acid led the radical formation by photo-irradiation to intensify markedly. ESR spectra of the irradiated oxidized sample proved that a considerable amount of triplet component radical was contained in it, whereas the unoxidized sample mostly indicated a singlet. The spectra found in the irradiated unoxidized sample was assigned to two radicals, I and II, and for the oxidized sample, to III and IV. The spectrum for I must be a singlet, and a triplet for II, III, and IV. Among the last three, II was less stable toward heat. As the oxidized sample has a high activity for photoinitiation, the radicals of III and IV are presumed to be the sites of graft copolymerization:      

Radical formation and graft copolymerization on photo-irradiated aldehyde cellulose

The relationship between the activity to initiate graft copolymerization under photo-irradiation and the photo-induced radicals of periodic acid-oxidized cellulose (aldehyde cellulose) was investigated. Aldehyde cellulose proved to have a high activity to initiate graft copolymerization under photo-irradiation, and the effect was profound, especially for hydrophilic vinyl monomers such as acrylic acid and acrylamide. By studying the ESR spectrum of photo-irradiated aldehyde cellulose, the formation of a radical giving a singlet spectrum with linewidth of 14–15 G and a g value of 2.001 was observed. This was assigned to an acyl radical orginating in the aldehyde group of the sample. Employing low molecular weight aldehydes, it was confirmed that an acyl radical formed on aldehyde compounds by photo-irradiation has a function sufficient to initiate the graft copolymerization of vinyl monomers. It was concluded that the high activity needed to induce the graft copolymerization of aldehyde cellulose under photo-irradiation was based on an acyl radical which originated in the aldehyde group of the sample.     

Selective separation of some heavy metals by poly(vinyl alcohol)‐grafted membranes

A poly(vinyl alcohol) membrane (PVA) was modified by radiation graft copolymerization of acrylic acid/styrene (AAc/Sty) comonomers. The Cu and Fe ion‐transport properties of these membranes were investigated using a diaphragm dialysis cell. In the feed solution containing CuCl₂ or a mixture of CuCl₂ and FeCl₃, the PVA‐g‐P(AAc/Sty) membranes showed high degrees of permselectivity toward Cu²⁺ rather than toward Fe³⁺. The permeation of Cu²⁺ ions through the membranes was found to increase with decrease in the grafting yield. However, as the content of Cu²⁺ ions in the Cu/Fe binary mixture feed solutions decreased, the rate and the amount of transported Cu²⁺ through the grafted membrane decreased, with no appreciable permselectivity toward Fe³⁺. When Fe²⁺ ions were used instead of Fe³⁺ ions in the feed solution containing Cu²⁺, the transport of both Cu²⁺ and Fe²⁺ through the membrane was observed. The rate of transport of Fe²⁺ was higher than that of Cu²⁺. In addition, it was found that the selective transport of ions was significantly influenced by the pH difference between both sides of the membranes. As the pH of the feed or the received solution decreased, both Cu²⁺ and Fe³⁺ passed through the membrane and were transported to the received solution. The role of carboxylic acid and the hydroxyl groups of the grafted membranes in the transportation process of ions is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 125–132, 2000     

Radical annihilation of γ‐ray‐irradiated contact lens blanks made of a 2‐hydroxyethyl methacrylate copolymer at elevated temperatures

The annihilation of the radicals in irradiated 2‐hydroxyethyl methacrylate copolymer was analyzed by the use of electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra were deconvoluted into three radicals: a quartet (Ra), a triplet (Rb), and a broad singlet (Rc). Radical Ra was attributed to coupling with a methyl radical and/or a doublet or triplet with about the same hyperfine coupling due to a methylene radical. Radical Rb was due to a methylene radical produced by main‐chain scission. Radical Rc was attributed to various free radicals without coupling to protons. By comparing the EPR spectra of radicals Ra, Rb, and Rc with the spectrum of a 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) standard with a known spin number, we calculated the spin numbers of the radicals, which decreased with time in the temperature range 25–45°C, regardless of the irradiation dose. The annealing of Ra and Rb and the annealing of Rc at longer times followed second‐order kinetics; these were different from the kinetics for the color formation and defect‐controlled hardening of polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(vinyl alcohol)–Carbon Nanodots Fluorescent Hydrogel with Superior Mechanical Properties and Sensitive to Detection of Iron(III) Ions

A high‐strength fluorescent hydrogel is prepared by physical cross‐linking of carbon nanodots (CNDs) with poly(vinyl alcohol) (PVA). The stretching and compression of the PVA hydrogel are improved with CNDs by 176% and 64%, respectively. It still has excellent self‐healing behaviors without adding other healing agents. In addition, the search for rapid detection of heavy metals is still a huge challenge. The resulting hydrogel exhibits fluorescence quenching in the presence of Fe³⁺ by the fluorescence characteristics of CNDs, which has high selectivity and sensitivity. The PVA‐CNDs fluorescent hydrogel can be used as a solid detection platform for Fe³⁺, where the detection limit is found to be 10 µm for Fe³⁺ by fluorescence studies.     

Preparation of UV reactive montmorillonite and characterization of its nanocomposites with poly(vinyl alcohol)

A cation‐exchanged montmorillonite clay is prepared as filler material with high dispersibility, that should act as Fe³⁺‐donor for photochemical crosslinking of PVA/Fe³⁺‐MMT materials with filler contents of up to 50 wt % with regard to the polymer matrix. Hence, no organic photoinitiators and hazardous compounds are utilized. This material may be considered environmentally benign and could be applied in the field of food packaging or for biomedical applications. Upon UV exposure of liquid PVA/Fe³⁺‐MMT dispersion samples, a significant change of the refractive index is determined and the absorption at 360 nm decreased. This indicates the transition of Fe³⁺ to Fe²⁺, which initiates a radical crosslinking mechanism. A homogenous distribution and parallel orientation of the modified clay particles is revealed by SEM measurements. The solubility behavior of the PVA/Fe³⁺‐MMT composite materials in deionized water, changes considerably due to the high filler content and UV‐induced crosslinking, resulting in gel contents exceeding 90 wt %. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and swelling behaviors of semi‐IPNs superabsorbent resin based on chicken feather protein

A novel chicken feather protein‐g‐poly (potassium acrylate)/polyvinyl alcohol (CFP‐g‐PKA/PVA) semi‐IPNs superabsorbent resin (SAR) based on feather protein, acrylic acid (AA), and polyvinyl alcohol (PVA) was synthesized by graft copolymerization and semi‐interpenetrating technology. The results from FTIR, SEM, and TGA analysis showed that both CFP and PVA reacted with PKA during the polymerization process. The effects of AA, PVA, initiator and crosslinker content on water absorbency of semi‐IPNs SAR were studied. The swelling behavior in various pHs and saline solutions were also investigated. The water absorbency of SAR reached the maximum at pH = 6. The effect of the five cations on swelling had the following order: Al³⁺ > Ca²⁺ > Mg²⁺ > K⁺ > Na⁺. The highest water absorbency in distilled water and 0.9 wt % NaCl solutions were 714.22 and 70.08 g g^?1, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39748.     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatoargentate(III)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) using potassium diperiodatoargentate(III) [Ag(III)]–PVA redox system as initiator was studied in an alkaline medium. Some structural features and properties of the graft copolymer were confirmed by Fourier‐transfer infrared spectroscopy, scanning electron microscope, X‐ray diffraction and thermogravimetric analysis. The grafting parameters were determined as a function of concentrations of monomer, initiator, macromolecular backbone (X?_n = 1750, M? = 80 000 g mol^?1), reaction temperature and reaction time. A mechanism based on two single‐electron transfer steps is proposed to explain the formation of radicals and the initiation profile. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate and n‐butyl acrylate, were also used to produce graft copolymerizations. It has been confirmed that grafting occurred to some degree. Thermogravimetric analysis was performed in a study of the moisture resistance of the graft copolymer. Copyright © 2004 Society of Chemical Industry     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatonickelate(IV)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) with a potassium diperiodatonickelate(IV) [Ni(IV)]–PVA redox system as an initiator was investigated in an alkaline medium. The grafting parameters were determined as functions of the temperature and the concentrations of the monomer and initiator. The structures of the graft copolymers were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The Ni(IV)–PVA system was found to be an efficient redox initiator for this graft copolymerization. A single‐electron‐transfer mechanism was proposed for the formation of radicals and the initiation. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate, n‐butyl acrylate, and n‐butyl methacrylate, were used as reductants for graft copolymerization. These reactions definitely occurred to some degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 529–534, 2003     

异戊二烯和四氟乙烯—丙烯共聚物的光化学接枝反应

在紫外光作用下,二苯甲酮、蒽醌和安息香能通过夺氢反应使异戊二烯在四氟乙烯-丙烯共聚物中接枝,接枝反应按三重态自由基引发机理进行,接枝率随光照时间的增长而增加,但不会超过40％。和异戊二烯的自由基聚合反应不一样,接枝物中聚异戊二烯接枝链的微结构以3,4-和1,2-聚合为主,而前者以1,4-聚合为主。Ce~(+4)及Fe~(+2)-H_2O_2等氧化还原体系对该接枝反应不产生作用.极性溶剂四氢呋喃的加入,对接枝链微结构的影响很小。     

Virgin olive oil: Free radical production studied with spin-trapping electron paramagnetic resonance spectroscopy

Spin trapping using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) has been used to detect and distinguish free radicals in samples of Greek extra virgin olive oils. A number of the samples examined immediately after the addition of the spin trap showed a spontaneous complex electron paramagnetic resonance (EPR) signal. The majority of DMPO-radical adducts formed (80–90%) represented peroxyl and alkoxyl radical adducts. Similar spectra were recorded when DMPO was added in oxidized triolein and then treated with Fe²⁺, Fe³⁺, or Cu²⁺ or when EPR-silent olive oil samples were treated with these metallic ions. Metal ion-catalyzed decomposition of triolein hydroperoxides, as recorded by EPR signal intensity, increased with increasing metal ion concentration in the micromolar range. The relative concentration of alkoxyl-DMPO adducts increased with increasing Fe²⁺ or Fe³⁺ concentration, whereas that of peroxyl-DMPO species decreased. In contrast, the relative concentrations of alkoxyl and peroxyl species produced by Cu²⁺ were similar over the whole metal concentration range examined. Exposure of EPR-silent virgin olive oil or oxidized triolein to ultraviolet light in the presence of DMPO resulted in the detection of a three-line spectrum characterized by wide line widths.     

Grafting vinyl monomers onto nylon 6. VI. Graft copolymerization of methyl methacrylate onto nylon 6 using acetylacetonate complex of Mn(III), Co(III), and Fe(III)

The graft copolymerization of methyl methacrylate onto nylon 6 using metal complexes of Mn³⁺, Co³⁺, and Fe³⁺ as initiators was studied. The rate of polymerization, R_p, increased with increasing complex concentrations in the initial stages; but it decreased upon further increase of complex concentrations. With increasing monomer concentrations, the rate of polymerization increased progressively. The graft yield increased with increaing temperature within the range 60–75°C. A suitable kinetic scheme is presented and rate equations are derived.     

Photoconductivity of poly(vinyl alcohol) films with Fe3+ complexes and ESR study of their structures

We have studied whether photoconductivity is observed in polymer films containing the first transition metal complexes. Polymers investigated were poly(vinyl alcohol) (PVA), polyacrylamide, poly(acrylic acid), poly(vinyl pyrrolidone), and polyethylene glycol. Transition metal salts used were CrCl₃, MnCl₂, FeCl₃, CoCl₂, NiCl₂, FeBr₃, Fe(NO₃)₃, Fe₂(SO₄)₃, and Fe(ClO₄)₃. Only in the PVA–FeCl₃ film was relatively large photoconductivity due to the photoreduction of Fe³⁺ observed. ESR spectra indicate that an Fe³⁺ ion is chelated with two in-plane OH residues of PVA and coordinated with three Cl^?ions on the meridian. UV irradiation causes an electron transfer from Cl^? to Fe³⁺. The produced chlorine atom extracts an electron from the oxygen of a neighboring OH residue. The unpaired electron thus formed can move from one oxygen to another through hydrogen bonding. In other words, the photoconductivity is due to holes produced in the network of PVA hydrogen bonding by the reduction of Fe³⁺. Finally, we have tried to explain why the photoconductivity is observed only in the PVA–FeCl₃ film.     

Effect of metallic ions in photo-induced graft copolymerization onto cellulose

In photo-induced graft copolymerization of methyl methacrylate onto cellulose, the effect of metallic ions as sensitizer was investigated. Some metallic ions were effective in their adsorbed states and accelerated the formation of grafts in the order Fe²⁺ > Ag⁺ > Fe³⁺. However, Cu²⁺ acted negatively, and little effect was observed for Co²⁺, Ni²⁺, Mn²⁺, Zn²⁺, and Cr³⁺. In the systems in which aqueous metallic salt solutions were added, the formation of grafts was generally depressed, but Fe³⁺ was an exception. The effect of metallic ions on the scission reaction of cellulose main chains did not necessarily agree with the effect on the formation of grafts. This is attributed to the varied interaction between cellulose and the different active species produced by irradiation, depending on the type of metallic ions used.     

Ceric salt-initiated graft copolymerization of methyl methacrylate on preoxidized cellulose samples

The effects of preoxidation of cellulose samples on graft copolymerization in the presence of ceric salt (Ce⁴⁺) as an initiator were investigated. The use of Ce⁴⁺ as oxidizing agent inhibited the formation of grafts, and the number of grafts decreased as the concentration of Ce⁴⁺ in the pretreatment rose. In contrast, the samples oxidized with periodic acid (HIO)₄ or hydrogen peroxide (H₂O₂) tended to show improved initiation characteristics and gave a larger number of grafts than the unoxidized samples. The reactivity of oxidized samples toward Ce⁴⁺ was examined and the following results were obtained: The part of easy reactivity decreased in the Ce⁴⁺-oxidized samples but it increased in the HIO₄-oxidized samples; on the other hand, it did not vary greatly in the H₂O₂-oxidized samples. Cellulose is probably oxidized to different states by different oxidizing agents, and the reactivity of Ce⁴⁺ toward these oxidized samples, as one index, seems to be reflected in the graft copolymerization. It was consequently recognized that the graft copolymerization characteristics of cellulose samples could be improved significantly by proper selection of oxidiation conditions.     

Formation and behavior of mechanoradicals in pulp cellulose

The mechanical degradation of pulp cellulose fiber was studied at ambient temperature and at 77°K. ESR findings reveal that mechanical degradation occurs via free-radical routes. Three types of mechanoradicals contributing singlet, doublet, and triplet ESR signals are identified. The singlet signals are derived from the alkoxy radicals at C₄ positions as a consequence of the cleavage of glucosidic bonds, the radical pairs generated at C₁ positions contributing the doublet signals. Triplet signals are derived from the C₂ and C₃ positions due to the cleavage of C₂ and C₃ bonds. Of these radicals, alkoxy radicals are the most stable at ambient temperature. Carbon radicals are capable of interacting rapidly with oxygen molecules to produce peroxy radical intermediates, where alkoxy radicals are inert toward oxygen molecules. ESR study also reveals that cellulose mechanoradicals are capable of initiating vinyl polymerization. MMA propagating radicals are identified when the monomers are in contact with cellulose mechanoradicals. The ability of mechanoradicals to initiate graft copolymerization from cellulose fiber is discussed.