Investigations on vinylene carbonate. V. Immobilization of alkaline phosphatase onto LDPE films cografted with vinylene carbonate and N-vinyl-N-methylacetamide

Low-density polyethylene (LDPE) films cografted with vinylene carbonate (VCA) and N-vinyl-N-methylacetamide (VIMA) were studied as a matrix for the immobilization of the enzyme alkaline phosphatase (ALP) either by direct fixation or by inserting spacers. When water-soluble alkyldiamines such as diaminoethylene, diaminobutane, diethylenetriamine, and diaminohexane were used as spacers between the matrix and the enzyme, the surface concentration (SC) of the active ALP coupled on the matrix was increased, whereas the effect of the spacer on the SC was dependent on the length of the spacer. Bovine serum albumin (BSA) was preimmobilized onto the LDPE films to provide a better simulation of the biological environment for the enzyme, and the SC of ALP on the matrix was significantly increased by coupling ALP onto the BSA preimmobilized surfaces. Compared to native ALP, some physicochemical properties of ALP could be improved by the covalent immobilization. © 1993 John Wiley & Sons, Inc.     

Radiation-initiated graft copolymerization of individual monomer and comonomer onto polyethylene and polytetrafluoroethylene films

Preparation and some properties of the graft copolymers obtained by radiation-induced graft polymerization of methacrylic acid (MAA) and (acrylonitrile/MAA) comonomer onto polyethylene and polytetrafluoroethylene films, were investigated. The effect of reaction conditions, solvent, monomer, and inhibitor concentration, comonomer composition, and comonomer concentration, on the graft copolymerization process was studied. The grafting process was enhanced in the presence of comonomer (AN/MAA) as compared with individual grafting of MAA or acrylonitrile (AN). The optimum comonomer composition, at which the highest grafting yield was obtained, was found to be (80/20) wt % of (AN/MAA) comonomer. The graft copolymerization of (AN/MAA) comonomer was enhanced in presence of AN due to its higher polarity strength. The electrical and swelling properties of the graft copolymers were greatly affected by the contents of PAN and PMAA graft chains. Mechanical properties of the graft copolymers were significantly changed with the grafting yield.     

Photosensitive poly(vinylene carbonate)s based on reaction development patterning with dilute aqueous alkaline solution

We examined positive‐tone pattern formation based on reaction development patterning (RDP) using hydrolysis of carbonate groups on the side chains of vinyl polymers. Homopolymers and copolymers with carbonate groups were prepared by radical polymerization using vinylene carbonate (VCA) as a monomer. Application of RDP to the VCA homopolymer resulted in unclear positive‐tone pattern because the high reactivity of the carbonate group led to insufficient difference in solubility between the exposed and unexposed areas. When we applied RDP using 5.0 wt% NaOH_aq as developer to the copolymers between VCA and vinyl acetate (P(VCA–VAc)s), clear positive‐tone patterns were successfully obtained. The effect of the ratio of carbonate groups in the copolymers on the development property of the RDP process was examined, and the use of a copolymer in which the ratio between VCA and VAc was 1:0.6 was found to yield positive‐tone pattern with the highest contrast. Pattern formation using more dilute developer (1.0 wt% NaOH_aq) was also achieved. Though conventional photosensitive polymers are required to have acidic or protected acidic groups for alkaline development, we succeeded in addition of photosensitivity to P(VCA–VAc)s, which do not have such functional groups, by using dilute aqueous alkaline solutions as developers. © 2015 Society of Chemical Industry     

Cation exchange membranes by radiation-induced graft copolymerization of styrene onto PFA copolymer films. I. Preparation and characterization of the graft copolymer

PFA-g-polystyrene graft copolymers were prepared by simultaneous radiation-induced graft copolymerization of styrene onto poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) films. The effects of grafting conditions such as monomer concentration, dose, and dose rate were investigated. Three solvents, i.e., methanol, benzene, and dichloromethane, were used as diluents in this grafting system. Of the three solvents employed, dichloromethane was found to greatly enhance the grafting process, and the degree of grafting increased with the increase of monomer concentration until it reached its highest value at a styrene concentration of 60 (vol %). The dependence of the initial rate of grafting on the monomer concentration was found to be of the order of 1.2. The degree of grafting was found to increase with the increase in irradiation dose, while it considerably decreased with the increase in dose rate. The formation of graft copolymers was confirmed by FTIR analysis. The structural investigation by X-ray diffraction (XRD) shows that the degree of crystallinity content of such graft copolymers decreases with the increase in grafting, and consequently, the mechanical properties of the graft copolymers were influenced to some extent. Both tensile strength and elongation percent decreased with the increase in the degree of grafting. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2095–2102, 1999     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. V. Charge‐transfer complex (1)

In previous studies, the photografting polymerization of vinyl acetate (VAC) and maleic anhydride (MAH) was investigated systematically. After that, to increase the grafting rate and efficiency and make the project more practicable, a VAC–MAH binary monomer system was employed for simultaneous photografting onto the surface of low‐density polyethylene film. The effects of several crucial factors, including the composition and total concentration of the monomer solution and different types of photoinitiators and solvents, on the grafting polymerization were investigated in detail. The conversion percentage (CP), grafting efficiency (GE), and grafting percentage were measured by gravimetry. The results showed that the monomer composition played a big part in this binary system; appropriately increasing the content of MAH in the monomer feed was suited for grafting polymerization. The growth of the total monomer concentration, however, made the copolymerization faster and was unfavorable for grafting polymerization. The three photoinitiators—2,2‐dimethoxy‐2‐phenylacetophenone (Irgacure 651), benzoyl peroxide, and benzophenone (BP)—led to only slight differences in CP, but for GE, BP was the most suitable. As for the different solvents—acetone, ethyl acetate, tetrahydrofuran (THF), and chloroform—using those able to donate electrons (acetone and THF) resulted in relatively higher CPs; on the contrary, the use of the other solvents made GE obviously higher, and this should be attributed to the charge‐transfer complex (CTC) that formed in this system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 903–909, 2005     

Chemically Induced Graft Copolymerization of Methacrylic Acid onto Low Density Polyethylene Films Using Sodium Bisulfite

Abstract

A simple and inexpensive technique for preparation of membranes by chemically induced graft copolymerization of methacrylic acid (MAA) onto low-density polyethylene (PE) films using sodium bisulfite (SBS) initiator was developed. Several parameters affecting the grafting rate and yield, such as the concentration of aqueous monomer solutions (4–20%) and initiator (0.025–0.2 M/L), reaction temperature (50–70°C), and within reaction times ranging from 1 to 6 h were studied. The results show that grafted films with 20% up to 500% graft were obtained under the synthesis conditions mentioned. Some selective properties of the grafted films (membranes), such as swelling behavior and mechanical properties were investigated. Also, the films were characterized by infrared (IR) spectroscopy, thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM). Such prepared graft copolymers may be of great interest in some practical uses such as dialysis and ultrafiltration membranes and also for wastewater treatment from heavy and toxic metals.     

Graft copolymerization of acrylonitrile and its binary mixture with 4-vinyl pyridine onto isotactic polypropylene powder by preirradiation method

Graft copolymerization of acrylonitrile (AN) and its binary mixture with 4-vinyl pyridine (4-VP) onto isotactic polypropylene powder in aqueous medium, using γ-rays as an initiator, was studied. Optimum conditions for affording maximum percentage of grafting were evaluated. Rate of grafting (Rg) of AN and binary mixture (4-VP + AN) was determined as a function of total initial monomer concentrations. The graft copolymers were characterized by IR spectroscopy and thermogravimetric analysis. © 1995 John Wiley & Sons, Inc.     

Graft copolymerization of 4-vinylpyridine and methyl acrylate onto polyethylene film by radiochemical method

Graft copolymerization of 4-vinyl pyridine (4-VP) and methyl acrylate (MA) onto polyethylene (PE) was studied in aqueous medium in air by the mutual irradiation method. The percentage of grafting was determined as a function of the (i) total dose, (ii) monomer concentration, and (iii) amount of water. The effect of different alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and pentanol on the percentage of grafting of 4-VP and MA was studied. The effects of different amines on the percentage of grafting of 4-VP were also studied. The graft copolymers were characterized by IR spectroscopy and thermal analysis and by identifying the isolated polymer from the grafted film. Grafted PE film was tested for permeability behavior and was found to be permeable to a 0.5% aqueous sodium chloride solution. A plausible mechanism is suggested to explain the grafting of 4-VP and MA onto PE film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 599–610, 1998     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. VIII. Charge‐transfer complex (4)

In view of the complexity of surface photografting polymerization of vinyl acetate/maleic anhydride (VAC/MAH) binary monomer systems, a novel method was adopted in the present article to obtain insight into the relevant grafting copolymerization mechanism. This method includes two steps: semibenzopinacol dormant groups were first introduced onto LDPE film by UV‐irradiation and then thermally reactivated to produce LDPE macromolecular free radicals, which initiated the grafting copolymerization of VAC and MAH. It was demonstrated that, in the first step, the solvent used to introduce benzophenone (BP) to LDPE film largely affected the subsequent grafting copolymerization, which was closely related to the affinity of the solvent toward the substrate. The monomer feed composition had considerable influence on both the grafting and nongrafting copolymerization; however, the maximum copolymerization rates did not appear in the polymerization system with [VAC]/[MAH] being 1 : 1, but, in the system with a bit more VAC than MAH, as the total monomer concentration was raised, the maximum copolymerization rates tended to appear in the system with [VAC] equal to [MAH]. The relationship between the total copolymerization rate (RP) and monomer concentration was determined to be LnRP ∝ [VAC + MAH]^1.83. All of these results indicated that both charge transfer (CT) complex formed by VAC and MAH and free monomers took part in grafting copolymerization. This feature differentiated the surface grafting copolymerization of VAC/MAH from the well‐studied thermally induced alternating copolymerization of VAC/MAH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Process of grafting styrene onto LLDPE by swelling and suspension copolymerization

A technology of swelling and suspension copolymerization was conducted to graft styrene onto linear low‐density polyethylene (LLDPE). The graft mechanism of styrene with LLDPE had been described by ¹H NMR and IR. The mean particle diameter and size distribution of the products with different proportions of LLDPE to styrene monomer were calculated. The morphology and thermal behavior of copolymers were characterized by scanning electron microscopy and differential scanning calorimetry. The glass transition temperature of copolymers increased with the addition of LLDPE, which proved the existence of the polyethylene‐g‐polystyrene copolymer. The grafting efficiency and granulation rate of suspension copolymerization were investigated. It was found that the grafting efficiency increased and the granulation rate decreased with the addition of LLDPE. POLYM. ENG. SCI., 50:1713–1720, 2010. © 2010 Society of Plastics Engineers     

焦磷酸锰络阴离子引发淀粉与苯乙烯及其二元单体接枝共聚的研究

采用廉价无毒的焦磷酸锰（Ｍｎ＾３＋）络离子作为引发剂，以十二烷基硫酸钠为乳化剂，对淀粉与苯乙烯及二元单体接枝共聚进行了初步探索，研究了单体浓度，引发剂浓度，反应温度及反应时间对接枝反应的影响趋势，发现Ｍｎ＾３＋具有良好的引发效果，接枝效率在６５％～９０％，接枝率可达２００％，对淀粉与Ｓｔ／ＡＮ，Ｓｔ／ＥＡ二元单体接枝共聚的研究表明接枝效率不高。     

Functionalizing of polyurethane surfaces by photografting with hydrophilic monomers

Poly(ester urethane) (PU) with functional groups (amide, hydroxyl, carboxyl) on surfaces were prepared by grafting monomers such as acrylamide (AAm), hydroxyethyl acrylate (HEA), and methacrylic acid (MAA) onto the PU membranes. Grafting copolymerization was carried out by the combined use of photooxidization and UV irradiation grafting. The PU membrane was photooxidized in hydrogen peroxide solution under UV light to yield hydroperoxide groups on the surface and then irradiation grafting with monomer in water. The ATR‐FTIR spectrum, X‐ray photoelectron spectroscopy characterized the grafted copolymers and verified the occurrence of grafting copolymerization. The results showed that the content of hydroperoxide groups yielded was dependent on the photooxidization time and reached maximum at about 8 h. Grafting copolymerization was enhanced when irradiating by UV light. The degree of grafting was increased with the increase of content of hydroperoxide groups, irradiation time, and monomer concentration. The grafting copolymerization was enhanced when an appropriate amount of ferrous ions was added. After grafting, the wettability of PU and the water absorption percentage increased with the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2505–2512, 2000     

Homogeneous Photoinouced Graft Copolymerization of Acrylamide onto Abs Copolymers in the Presence of 4-Acetyldiphenyl as Photosensitizer.: 1. Influence of Butadiene Content in Abs Copolymers

Photoinduced graft copolymerization of acrylamide (AM) onto two types of acrylonitrile-butadiene-styrene (ABS) copolymers was extensively investigated in homogeneous media. The grafting process was conducted in chloroform in presence of 4-acetyldi-phenyl (4-AD). Ultraviolet (UV) irradiation was used in the range of 310 to 460 nm. The UV spectrum of 4-AD has sλ_max at 285 nm and shows n-π^? transitions. The grafting parameters, such as weight conversion, grafting percentage, and grafting efficiency, were determined as a function of the irradiation time and the concentrations of monomer, initiator, and substrate. A reverse effect was observed between the grafting percentage and the butadiene content in ABS copolymers. The rates of graft copolymerization of AM onto the two types of ABS copolymers were determined. A Trommsdorf effect was observed in certain systems. The IR spectrum of ABS-g-AM graft copolymer shows the appearance of a new peak at 1685 cm^-1 that declares the presence of poly-acrylamide-grafted chains onto the ABS copolymer backbone. A probable copolymerization mechanism was proposed.     

Surface modification of polyethylene terephthalate film by CO2 laser‐induced graft copolymerization of acrylamide

Graft copolymerization of acrylamide onto polyethylene terephthalate (PET) using a CO₂ pulsed laser was performed to improve water wettability. After laser irradiation in air, the films were placed in the aqueous solution of monomer and then heated to decompose peroxides formed onto the irradiated PET film. Peroxide density was determined spectrophotometrically by means of the iodide method. The grafted PET surfaces were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, and contact angle measurements. The electron micrographs showed that the grafting changed the surface morphology of the PET film, which is consistent with the infrared spectra of the grafted films. To evaluate the surface hydrophilicity, water drop contact angle was determined. The contact angle decreased as a result of graft polymerization. It was also found that the hydrophilicity is related to the surface morphology and grafting level. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 401–407, 2000     

Radiochemical graft copolymerization of methacrylonitrile and binary mixture of methacrylonitrile with 4-vinylpyridine onto isotactic polypropylene fiber

Graft copolymerization of methacrylonitrile (MAN) and its binary mixture with 4-vinylpyridine (4-VP) onto isotactic polypropylene (IPP) fiber has been studied in aqueous medium by the preirradiation method. Optimum conditions for obtaining the maximum percentage of grafting have been evaluated. Rate of grafting (Rg) has been determined as a function of total initial monomer concentration. The graft copolymers are characterized by IR spectroscopy, by thermogravimetric analysis, and by isolating the polymer from the graft copolymer. The effect of MAN, an acceptor monomer, on percentage of grafting of 4-VP, a donor monomer, has been discussed in the light of the mechanism proposed for grafting by the radiochemical method. © 1994 John Wiley & Sons, Inc.     

Surface modification of polyvinyl chloride with biodegradable monomers

Graft copolymerization of sucrose acrylate (SA) onto 55 μm films of poly(vinyl chloride) (PVC) was investigated with benzophenone or 2,2′-azoisobutironitrile as the initiator. The grafting reactions were carried out in a closed cell containing the films to be treated with a solution of the sensitizer and the monomer. In this system, ultraviolet light through a quartz window initiated the reaction by exciting the initiator used. The grafting took place on a PVC surface layer, from the solution. The homopolymer formed during copolymerization was removed by washing. The percentage of grafting was determined by gravimetric measurements and by dye adsorption (crystal violet), and the characterization of PVC(g)SA was carried out by the use of infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis. The weathering behavior of PVC(g)SA was studied with microorganisms in a growing medium, and the degradation was monitored by the weight loss of the films, FTIR, and SEM. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1195–1201, 1997     

Distribution of acrylic acid grafted chains introduced into polyethylene film by simultaneous radiation grafting with water and ethanol as solvents

The graft copolymerization of acrylic acid onto low‐density polyethylene films by simultaneous γ‐ray irradiation was carried out. The effect of water and ethanol as grafting solvents on the distribution of grafted poly (acrylic acid) in the low‐density polyethylene films was studied with optical microscopy observations of dyed and sliced samples and attenuated total reflection/Fourier infrared spectroscopy analysis. When no vigorous homopolymerization occurred, both polyethylene and poly(acrylic acid) existed in the grafted layer, and the thickness of the grafted layer and the poly(acrylic acid) concentration in the grafted layer increased with an increasing degree of grafting, regardless of the grafting conditions, the former increasing faster than the latter. In comparison with water as the solvent, in the absence of the inhibitor, homopolymerization could be suppressed to a certain degree in the ethanol solvent system, whereas in the presence of the inhibitor, obvious homopolymerization occurred at a lower monomer concentration, and both the degree of grafting and the thickness of the grafted layer were lower. Such differences could be explained by the chain transfer and the relatively low solubility of poly(acrylic acid) in ethanol. In addition, an experimental scheme using optical microscopy to observe the dyed and sliced polymers was optimized. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1570–1577, 2007     

Preparation of membranes based on high-density polyethylene graft copolymers for phosphate anion removal

This work was undertaken to synthesize graft copolymers that possess functional groups via the radiation-induced grafting of acrylamide onto a high-density polyethylene (HDPE) substrate. The optimum conditions suitable for radiation graft copolymerization were determined. In this regard, the effects of the solvent, the inhibitor concentration, the monomer concentration and the irradiation dose on the grafting yield were investigated. Selected properties of the prepared graft copolymers were investigated to elucidate the possibility of their practical use in the removal of metals and phosphate anions. The effects of different parameters that may affect the metal chelation process, such as pH, metal feed concentration and time of contact, were also studied. A chemically modified membrane loaded with Cu(II) was used for the removal of phosphate ions from aqueous solutions.     

Synthesis of graft copolymers from natural rubber using cumene hydroperoxide redox initiator

The graft copolymerization of 50/50 (w/w) styrene/methyl methacrylate mixtures onto natural rubber seed latex were carried out by using cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA‐chelated Fe²⁺ as a redox initiator. The effects of the process factors such as the amount of initiator, emulsifier, and chain‐transfer agent; monomer‐to‐rubber ratio; and temperature on the grafting efficiency (GE) and grafting level (GL) are reported. The mechanism of graft copolymerization was investigated. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis. Transmission electron microscopy (TEM) was used to study the morphology of the graft copolymers. It appears that the formation of graft copolymers occurs on the surface of the latex particles through a chain‐transfer process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2993–3001, 2002; DOI 10.1002/app.2328     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Influence of synthesis conditions

SYNOPSIS: The graft copolymerization of acrylamide monomer into polyethylene films was carried out by the preirradiation method. The influence of synthesis conditions, such as monomer concentration, preirradiation dose, reaction temperature, Mohr's salt, and pregrafting storage was investigated. The order of dependence of the rate of grafting on preirradiation dose and monomer concentration was found to be 0.87 and 1.86, respectively. An activation energy of 22.9 kJ/mol for the grafting reaction was obtained. The storage of preirradiated polyethylene film at −4°C prior to the reaction showed a decrease in the degree of grafting up to 10 days, beyond which the degree of grafting remained constant. The addition of FeSO₄ in the grafting medium not only inhibits the homopolymerization of the monomer but also decreases the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1331–1337, 2000