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     

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     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. IV. Maleic anhydride

In general, it has been accepted that maleic anhydride (MAH) cannot be homopolymerized under normal conditions. However, MAH can be grafted onto substrates under UV irradiation rather easily. In this study, the photografting polymerization of MAH was examined with low‐density polyethylene (LDPE) film as a substrate. The initiating performances of different photoinitiators, including benzophenone (BP), Irgacure 651, and benzoyl peroxide (BPO), were examined. The effects of some principal factors, such as the temperature, solvent, and UV intensity, on the grafting polymerization of MAH were also investigated. The results show that MAH can be smoothly grafted onto LDPE film by UV radiation. Enhancing the intensity of UV radiation and elevating the irradiation temperature facilitate the grafting polymerization of MAH. Among BP, Irgacure 651, and BPO, Irgacure 651 can initiate the polymerization of more MAH, but BP is more effective for the initiation of surface grafting polymerization. Solvents of MAH also have a great influence on the grafting polymerization; some of them even seem to take part in the reaction. The occurrence of photografting polymerization was verified with Fourier transform infrared and electron spectroscopy for chemical analysis spectra. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2318–2325, 2003     

Surface photografting polymerization of vinyl acetate (VAc), maleic anhydride,and their charge transfer complex. I. VAc(1)

Photografting of vinyl acetate (VAc) onto LDPE films was carried out with lamination technology and simultaneous method, using BP as photoinitiator. Some principal factors affecting the grafting polymerization were investigated in detail. The experimental results showed that oxygen dissolved in monomer solution had great influence on grafting polymerization. Compared with other routine monomers (St, MMA, AN, AA, and AAm), VAc exhibited higher photografting reactivity. It was observed that the reaction temperature affected the graft polymerization markedly. To film samples with a given diameter, there exists optimum thickness of monomer solution. Adding a pertinent amount of water to the photografting polymerization system could accelerate the polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1513–1521, 2000     

Surface photografting polymerization of vinyl acetate (VAc), maleic anhydride (MAH), and their charge transfer complex (CTC). III. VAc(3)

Vinyl acetate (VAc) was grafted onto low‐density polyethylene (LDPE) substrates by UV irradiation with benzophenone (BP) as the photoinitiator. BP preabsorbed film samples and BP precoated film samples were prepared in advance and applied as the substrates onto which VAc was photografted, together with the method in which BP was dissolved in VAc directly. In addition, the efficiency of the polymerizations applying the preirradiation technology was examined. The conversion percent, grafting percent, and grafting efficiency were determined by a gravimetric method. The contact angles of the grafted films against water were also measured. The results show that BP preabsorbing and precoating were favorable to grafting polymerization, especially the BP precoating method, which was due to its simple operation and the ease of controlling the amount of BP. The diffusion of BP and VAc through the substrates proved to be an important factor for grafting polymerization. Through UV irradiation, dormant groups can be introduced onto LDPE film, which may be activated again by UV irradiation or by heating, leading to the formation of free radicals. Grafting polymerization can be initiated during the activation process in the presence of monomer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1426–1433, 2001     

Melt grafting of poly(ethylene‐vinyl acetate) copolymer with maleic anhydride

Poly(ethylene‐vinyl acetate) (EVA) copolymer was melt grafted with maleic anhydride (MAH) in a twin screw extruder in the presence of peroxide. It is confirmed that MAH has been melt grafted on the backbone of EVA by FTIR using the method of hydrolysis. The NMR analysis suggests that the grafting reaction occurs on the tertiary carbon of main chain of EVA other than the methyl moiety of vinyl acetate (VA) group. The incorporation of VA groups onto the matrix shows a competitive effect on the grafting. The existence of VA groups promotes the extent of MAH graft onto EVA; nevertheless, it also weakens the crystallizability of main chain. When the content of peroxide initiator is 0.1 wt % based on the polymer matrix, the grafting degree increases with increasing the concentration of monomer. When the peroxide content is higher than 0.1 wt %, side reactions such as crosslinking or disproportionation will be introduced into this system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 841–846, 2006     

Surface photografting polymerization of trimethylolpropane triacrylate onto LDPE substrate in tetrahydrofuran/water mixtures

A surface photografting polymerization (λ > 300 nm) of a multifunctional monomer which was trimethylolpropane triacrylate (TMPTA), was conducted with benzophenone (BP) as photoinitiator and LDPE as model substrate, in mixed solvents containing tetrahydrofuran (THF) and water. Proved by ATR‐IR, highly crosslinked grafted layer was generated rapidly under UV irradiation. Effects on percent conversion of grafting are detailed with, such as feed ratio of BP to TMPTA, mass percent of TMPTA in the reaction system, mass percent of water in the mixed solvents and addition of the second monomer, methyl methacrylate (MMA). As both verified by SEM and AFM, relatively planar grafted layer was produced when photografting was carried out merely in THF; adding water in the reaction system caused the formation of “craters” in the grafted layer. In addition, effects of mass percent of water in the mixed solvents, UV irradiation time, TMPTA concentration and addition of MMA on the size, shape and quantity of the “craters” were investigated by SEM. A plausible mechanism for the formation of “craters” is also proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Surface modification of poly‐L‐lactide by photografting of hydrophilic polymers towards improving its hydrophilicity

Poly‐L ‐lactide (PLLA) has been used to prepare scaffolds to guide tissue regeneration in tissue engineering research. However, one of the limitations to the use of PLLA as an ideal biomaterial is its high hydrophobicity. To improve the hydrophilicity of PLLA, hydrophilic polymers were grafted onto PLLA membrane surfaces through the combination of photooxidization in hydrogen peroxide and subsequent ultraviolet (UV)‐induced grafting copolymerization in the monomer solution. Three kinds of modified PLLA membranes (i.e., PLLA‐g‐polyhydroxyethyl methacrylate, PLLA‐g‐polyacrylamide, and PLLA‐g‐polymethacrylic acid) were obtained, resulting in the more wettable PLLA membranes. The occurrence of the grafting polymerization was confirmed by attenuated total reflectance infrared spectroscopy (ATR‐IR) and X‐ray photoelectron spectroscopy (XPS) analysis. Surface morphology of the modified PLLA membranes was studied by scan electronic microscopy (SEM). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2163–2171, 2002     

Thermoresponsive behaviour in aqueous solution of poly(maleic acid‐alt‐vinyl acetate) grafted with poly(N‐isopropylacrylamide)

The synthesis of a thermoresponsive graft copolymer consisting of a maleic acid/vinyl acetate alternating copolymer backbone (MAc‐alt‐VA) and poly(N‐isopropylacrylamide) (PNIPAM) side chains is reported. Turbidimetric measurements in dilute aqueous solutions showed that no macroscopic phase separation takes place when the temperature is raised above the lower critical solution temperature (LCST) of PNIPAM, even at pH = 2. Moreover, in semi‐dilute aqueous solutions, a pronounced thermally induced viscosity increase (thermothickening) was observed. This thermoresponsive behaviour has been attributed to the interconnection of the hydrophilic MAc‐alt‐VA graft copolymer backbones by means of the hydrophobic PNIPAM side chain aggregates formed as the temperature increases above the LCST of this polymer. Copyright © 2004 Society of Chemical Industry     

Synthesis of polyethylene‐graft‐poly(styrene‐co‐maleic anhydride) and its compatibilizing effects on polyethylene/starch blends

Low density polyethylene (LDPE) was reacted with benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐l‐piperidinyloxy (TEMPO) to prepare a latent macroinitiator, PE–TEMPO. Little polymer was synthesized when maleic anhydride (MAH) was bulk polymerized in the presence of the PE–TEMPO. However, addition of styrene accelerated the polymerization rate and PE‐grafted‐poly(styrene‐co‐maleic anhyride) [PE‐g‐P(ST‐co‐MAH)] was produced to a high yield. Chemical reaction between MAH units and hydroxyl groups of starch was nearly undetectable in the PE/PE‐g‐P(ST‐co‐MAH)/starch blend system, and the tensile properties of the blend were not enhanced significantly. However, addition of tetrabutyl titanate (TNBT) during the blending procedure improved the tensile properties significantly through an increased interfacial adhesion between the components in the blend system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2434–2438, 2003     

Atom transfer radical polymerization of methyl methacrylate initiated with a macroinitiator of poly(vinyl acetate)

Well‐defined poly(vinyl acetate‐b‐methyl methacrylate) block copolymers were successfully synthesized by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p‐xylene with CuBr as a catalyst, 2,2′‐bipyridine as a ligand, and trichloromethyl‐end‐grouped poly(vinyl acetate) (PVAc–CCl₃) as a macroinitiator that was prepared via the telomerization of vinyl acetate with chloroform as a telogen. The block copolymers were characterized with gel permeation chromatography, Fourier transform infrared, and ¹H‐NMR. The effects of the solvent and temperature on ATRP of MMA were studied. The control over a large range of molecular weights was investigated with a high [MMA]/[PVAc–CCl₃] ratio for potential industry applications. In addition, the mechanism of the polymerization was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1089–1094, 2006     

Bulk grafting of poly(styrene‐alt‐maleic anhydride) onto preirradiated polyolefin membranes in supercritical carbon dioxide

To take advantage of the property of supercritical carbon dioxide as both a solvent and swelling agent, the bulk grafting of poly(styrene‐alt‐maleic anhydride) [P(MAH‐alt‐St)] onto preirradiated polyolefin membranes was performed by a combination of γ‐ray‐preirradiation‐induced graft copolymerization and supercritical fluid‐swollen polymerization. The trapped radicals on the polyolefin backbones were uniformly distributed by γ‐ray irradiation under a nitrogen atmosphere. Subsequently, these polymeric trapped radicals initiated the alternating copolymerization of styrene (St) and maleic anhydride (MAH) infused into the swollen polymer matrix with the aid of supercritical CO₂. It was important that the graft copolymers were relatively pure without any contaminants, including homopolymers, monomers, and initiators. The experimental results show that the degree of grafting could be easily controlled. In addition, St/MAH could synergistically promote the bulk grafting process and strongly effect on the alternating trend; this was confirmed by element analysis and differential scanning calorimetry. Soxhlet extraction, X‐ray diffraction, and Fourier transform infrared spectroscopy indicated that the P(MAH‐alt‐St) was covalently bonded to the polymeric backbones. Scanning electron microscopy showed that the alternating graft chains were uniformly dispersed throughout the 5‐mm thickness of the polymer membranes on the nanometer scale. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Graft copolymerization of vinyl monomers onto silk fibers initiated by a semiconductor‐based photocatalyst

Graft copolymerization onto silk (Bombyx mori) was carried out with vinyl monomers (methyl methacrylate and acrylamide) and initiated by a semiconductor‐based photocatalyst (cadmium sulfide). The utility of a semiconductor as an initiator in free‐radical photografting and the effects of ethylene glycol and triethylamine with cadmium sulfide on graft copolymerization were explored. Depending on the reaction conditions, 10–48% grafting with methyl methacrylate and 4–26% grafting with acrylamide were achieved. The reaction conditions were optimized, and the grafted fibers were characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetry analysis, and tensile strength measurements. The chemical resistance and water absorption of the grafted fibers were compared with those ungrafted fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

N,N‐diethyl dithiocarbamato group induced photografting of methyl methacrylate onto polyurethane

The N,N‐diethyl dithiocarbamato group present in a variety of compounds acts as an initiator in the photopolymerization processes. The photolability of this group is due to the cleavage of the C S bond by UV irradiation. N,N‐Diethyl dithiocarbamato‐(1,2)‐propane diol with a pendent N,N‐diethyl dithiocarbamato group was prepared from 3‐chloro‐(1,2)‐propane diol and sodium diethyl dithiocarbamate. A polyurethane macrophotoinitiator was then synthesized by a two‐step process, where N,N‐diethyl dithiocarbamato‐(1,2)‐propane diol was used as the chain extender. Other components used included 4,4′‐diphenylmethane diisocyanate and poly(propylene glycol) (molecular weight = 1000). The polyurethane thus synthesized had pendent N,N‐diethyl dithiocarbamato groups. This polyurethane macrophotoinitiator was then used to polymerize methyl methacrylate in a photochemical reactor (Compact‐LP‐MP 88) at 254 nm. The resulting graft copolymer, polyurethane‐g‐poly(methyl methacrylate), was freed from the homopolymer by a standard procedure. The graft copolymer was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, solution viscometry, and scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modification of polysulfone membranes via surface‐initiated atom transfer radical polymerization and their antifouling properties

Surface‐initiated atom transfer radical polymerization (ATRP) was used to tailor the functionality of polysulfone (PSF) membranes. A simple one‐step method for the chloromethylation of PSF under mild conditions was used to introduce surface benzyl chloride groups as active ATRP initiators. Covalently tethered hydrophilic polymer brushes of poly(ethylene glycol)monomethacrylate and 2‐hydroxyethyl methacrylate and their block copolymer brushes were prepared via surface‐initiated ATRP from the chloromethylated PSF surfaces. A kinetic study revealed that the chain growth from the membranes was consistent with a controlled process. X‐ray photoelectron spectroscopy was used to characterize the surface‐modified membrane after each modification stage. Protein adsorption experiments revealed substantial antifouling properties of the grafted PSF membranes in comparison with the those of the pristine PSF surface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Solid‐state grafting of succinic anhydride onto poly(vinyl alcohol)

The graft reaction of succinic anhydride onto poly(vinyl alcohol) (PVA) was catalyzed by p‐toluenesulfonic acid monohydrate in solid state. The infrared spectra and ¹H‐NMR spectra confirmed that succinic anhydride was successfully grafted onto PVA backbone. The influences of reaction temperature, reaction time, the amount of succinic anhydride, and the amount of catalyst on the graft reaction were studied. Uncrosslinked PVA graft copolymer with grafting degree up to about 6.5% could be obtained under low reaction temperature, short reaction time, and low amount of catalyst, whereas crosslinked PVA with high gel content could be obtained under high reaction temperature, long reaction time, and high amount of catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 848–852, 2007     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Emulsion grafting of vinyl acetate onto preirradiated poly(3‐hydroxybutyrate) film

Vinyl acetate (VAc) was grafted onto poly(3‐hydroxybutyrate) film by a preirradiation method. Grafting reactions were carried out in VAc/water/surfactant emulsion, VAc/water, and VAc/methanol systems. For emulsion grafting, Nonion L‐4 was ascertained to be the optimum surfactant with respect to the stability of a single emulsion layer. The emulsion with a 10 : 1 (w/w) ratio of VAc to surfactant yielded the highest degree of grafting: 23%. The grafting efficiency in the emulsion and the water and methanol solvents were evaluated. The results indicated that the grafting efficiency of the emulsion was 100 times that of VAc/methanol when the same 2 wt % VAc was used in the grafting reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactivity ratios of free monomers and their charge‐transfer complex in the copolymerization of N‐butyl maleimide and styrene

As for the charge‐transfer complex (CTC) formed by N‐butyl maleimide (NMBI) and styrene in chloroform, the complex formation constant was determined by ¹H‐NMR of Hanna–Ashbaugh. The copolymerization of NBMI (NBMI, M₁) and styrene (St, M₂) in chloroform using AIBN as an initiator was investigated. On the basis of the kinetic model proposed by Shan, the reactivity ratios of free monomers and CTC in the copolymerization were calculated to be r₁₂ = 0.0440, r₂₁ = 0.0349, r_1C = 0.00688, r_2C = 0.00476, and the ratios of rate constants were obtained to be k_1C/k₁₂ = 6.40, k_2C/k₂₁ = 7.33. In addition, the copolymer was characterized by IR, ¹H‐NMR, DSC, and TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3007–3012, 2002; DOI 10.1002/app.2330     

Photografting polymerization of polyacrylamide on PHBV films (I)

Photografting polymerization of polyacrylamide (PAM) onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) films using benzophenone as photoinitiator was studied. The morphology and structure of the grafted PHBV film were characterized by Fourier transformed infrared spectroscopy (FTIR) with attenuated total reflectance (ATR) and scanning electron microscope (SEM) with energy dispersive X‐ray spectrometer (EDX). The grafting percentage and grafting efficiency of the grafted PHBV film went up with the increase of acrylamide concentration and irradiation time. It was observed that photografting polymerization of PAM was not only limited to the film surface, but also in situ occurred inside the film to form the pore microstructure. Sheep bone marrow stromal cell studies showed that MSCs cells attachment efficiency on the grafted PHBV films increased and cells grew well. These results demonstrated the potentiality of PAM‐photografting PHBV in medical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4088–4095, 2007