Graft Polymerization Of Methyl Methacrylate Research Articles

Graft polymerization of methyl methacrylate on the surface of poly(vinylidene fluoride) using tributylborane as an initiator

Graft polymerization of methyl methacrylate on the surface of poly(vinylidene fluoride) using tributylborane as an initiator

Graft polymerization of methyl methacrylate on the surface of poly(ethylene‐co‐tetrafluoroethylene) using benzoyl peroxide as initiator

AbstractThe surface of a poly(ethylene‐co‐tetrafluoroethylene) (ETFE) film was modified by benzoyl peroxide (BPO)‐initiated graft polymerization of methyl methacrylate (MMA). After graft polymerization, the appearance of the ETFE film changed considerably, and the Fourier transform infrared (FT‐IR) spectra showed absorption peaks attributed to carbonyl functionalities. The efficiency of graft polymerization was strongly influenced by several factors such as the reaction temperature, reaction time, and concentration of BPO. The highest graft yield (69%) was obtained at 0.1 mol% BPO concentration and at a reaction temperature of 75°C for 24 h. The properties of the ETFE film surface were altered by the graft polymerization of MMA, which facilitated dyeing of the surface.

Emulsion Graft Polymerization of Methyl Methacrylate onto Cellulose Nanofibers

Methyl methacrylate (MMA) was successfully grafted onto cellulose nanofibers (CNFs) at room temperature in an emulsion system using a diethyl(1,10-phenanthroline N1,N10)zinc(II) complex (Phen-DEZ) with oxygen as the radical initiator. The effects of reaction temperature, initiator concentration, and monomer content on the grafting reaction were investigated. The molecular weight of the non-grafted PMMA, which was produced during graft polymerization, was more than 1 million, as determined by size exclusion chromatography. The PMMA-grafted CNFs were analyzed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy, which confirmed the grafting of PMMA on the nanofiber surface. The study presents a strategy for the grafting of high-molecular weight PMMA onto CNFs in an emulsion system using Phen-DEZ and O2.

Self-assembly and nanostructure of poly(vinyl alcohol)-graft-poly(methyl methacrylate) amphiphilic nanoparticles

HypothesisPoly(vinyl alcohol)-g-poly(methyl methacrylate) (PVA-g-PMMA) amphiphilic copolymers self-assemble to form multi-micellar colloidal systems. ExperimentsA PVA-g-PMMA copolymer containing 16–17% w/w of PMMA was synthesized by the free radical graft polymerization of methyl methacrylate on a PVA backbone by utilizing cerium(IV) ammonium nitrate as initiator and tetramethylethylenediamine (TEMED) as initiation activator. The aggregation behavior of the copolymer in water was comprehensively characterized by dynamic light scattering (DLS) and static light scattering (SLS), small angle neutron scattering (SANS), asymmetrical flow field-flow fractionation (A4F) and transmission electron microscopy (TEM). The colloidal stability before and after non-covalent crosslinking of PVA domains with boric acid was assessed by DLS. Finally, nanoparticles were nano spray-dried. FindingsThis copolymer self-assembles in water to form a complex nanostructure of low aggregation number particles (ca. 12–15 nm in diameter) that aggregate into larger ones with size ca. 60–80 nm, as determined by SANS and TEM. In addition, boric acid-crosslinking preserves the nanoparticle size, while conferring full physical stability under extreme dilution conditions. Nano spray-drying consolidates the crosslnking and enables the production of a dry flowing powder that upon re-dispersion in water regenerates the nanoparticles without major size changes.

Effect of two different RAFT reactions on grafting MMA from pre-irradiated PP film

The graft polymerization of methyl methacrylate (MMA) from pre-irradiated polypropylene (PP) films mediated by two different addition-fragmentation chain transfer (RAFT) polymerization mechanisms—surface-initiated RAFT polymerization and interface-mediated RAFT polymerization was studied. In the first mechanism, electron beam irradiation technique was applied to produce the initial radical active sites and peroxides on PP films. 4-cyanopentanoic acid dithiobenzoate (CPADB) was added in the solution to mediate the graft polymerization. In the second mechanism, a new technique utilizing the decomposition and recombination of peroxides produced by electron beam and di(thiobenzoyl) disulfide (DBDS) to anchor CTA on PP films was applied. GPC, ATR-FTIR, XPS, SEM and water contact angle were used to characterize graft layer. Surface-initiated RAFT polymerization was found to be fast and facile with high degree of grafting (Dg) and large number-average molecular weight. But the samples after reaction were swelling and out of shape. Interface-mediated RAFT polymerization led to rather low Dg and low molecular weight. But the samples kept their pristine shapes and had better surface properties.

A Plasma-Initiated Graft Polymerization of Methyl Methacrylate in the Presence of a Reverse ATRP Catalyst

A plasma-initiated graft polymerization of methyl methacrylate (MMA) was carried out on the high-density polyethylene (HDPE) surface in the presence of the reverse atom transfer radical polymerization (RATRP) catalyst of CuCl2/2,2′-bipyridine (bpy). The polymerization kinetics presented a linear relation with polymerization time. A well-defined PMMA brush was fabricated on the surface, evidenced by the linear growth of molecular weights with conversions and narrow polymer dispersity (Ð = 1.31). Graft amounts were indicated to increase proportionally with the increase of conversions and molecular weights. Subsequently, a solvent-responsive surface was prepared by the block copolymerization of 2-hydroxyethyl methacrylate (HEMA) on the PMMA grafted surface. The polymerization is suggested to proceed via a RATRP mechanism, when plasma radicals could behave similarly as conventional radicals in forming dormant species.

Structural changes in HDPE produced by in-line plasma-pretreated reactive extrusion

Structure of high density poly ethylene (HDPE) was changed after Plasma-induced graft polymerization of methyl methacrylate (MMA) monomer onto HDPE. Continuous polymerization of monomer wetted HDPE pellets was carried out sequentially via in-line plasma pretreatment followed by reactive extrusion. It was influenced by plasma pretreatment times between 15 s and 120 s on degree of grafting and molecular structure of the extrudate. Maximum degree of grafting was limited to 6% after 30 s plasma pretreatment. The addition of dicumyl peroxide (DCP) increased the degree of grafting to 10% after 15 s of plasma treatment. Gel formation to levels in the range 3–5% was detected, increasing with plasma pretreatment time. The formation of long chain branched (LCB) architecture, of the extruded PMMA-g-HDPE, was confirmed by rheological test in oscillatory shear, which results in increases in low frequency storage and loss moduli and melt viscosity than that of neat HDPE, especially after DCP addition. Finally, formation of a fully crosslinked structure was observed after annealing at 210 °C for 1 h as evidenced by a change in rheological properties at lowest frequencies to solid-like behaviour. Such extensive crosslinking could be useful in producing high strength adhesive joints between HDPE and other materials.

Synthesis and Applications of Functional Polymers from Natural Okra Fibers for Removal of Cu(II) Ions from Aqueous Solution

Functional groups (−COOCH3 and −NH2) in natural okra fiber had been introduced by free radical graft polymerization of methyl methacrylate (MMA) and acrylamide (AAm) from their binary solution using ascorbic acid/H2O2 as a redox initiator at a temperature of 45°C for 90 min. Factors affecting the grafting of lignocellulosic fiber such as feed molarity and comonomer composition were investigated. The grafted copolymers were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM-EDX), and thermogravimetric analysis (TGA). Functional groups were tested for their potential application in the removal of copper ions from aqueous solutions. Batch experiments were performed to evaluate the adsorption capacity of the maximum grafted cellulosic fibers toward the Cu (II) ions. Pseudo-first-order and pseudo-second-order kinetic models were studied to analyze the Cu2+ adsorption process and results showed that the pseudo-second-order model was more suitable than the pseudo-first-order model. Further, Langmuir, Freundlich, and Tempkin models were also applied to describe the adsorption isotherm of Cu2+ by different fiber adsorbents. The results indicate that the Langmuir model fitted the adsorption equilibrium data better than other two models. The maximum monolayer capacity qm calculated using the Langmuir isotherm for raw and MMA+AAm grafted fiber were 4.89 and 33.05 mg/g, respectively.

Enhancement of compatibility based on vapor-phase-assisted surface polymerization (VASP) method for polymer composites with agricultural wastes

Cellulosic substances in polymer matrices are immiscible and non-dispersive because of mismatch between their surface properties. In order to fabricate a natural fiber-reinforced plastic, hydrophilic cellulosic substances should be modified to hydrophobicity to make it miscible and dispersible to polymer matrices. Herein, this work shows potential application of vapor-phase-assisted surface treatment as a new modification approach for cellulosic substances. Cellulosic substances were modified to improve the compatibility in the polymer matrix. The modified cellulose substrates were characterized by Fourier transform infrared spectrometer spectroscopy, thermogravimetric analysis, and scanning electron microscope, and the resulting shows the grafting polymer on cellulosic substances indeed. To more enhance compatibility in polymer matrix, grafting of the methacryloyl groups on cellulose substance was prepared through gaseous methacrylic anhydride on cellulose surface, and then higher modified cellulose substance was carried out with vapor-phase graft polymerization of methyl methacrylate finally. The vapor-phase-assisted surface treatments could highly modify the cellulose surface compared to conventional method in liquid process.

Review of methyl methacrylate (MMA)/tributylborane (TBB)-initiated resin adhesive to dentin.

This review, focusing mainly on research related to methyl methacrylate/tributylborane (MMA/TBB) resin, presents the early history of dentin bonding and MMA/TBB adhesive resin, followed by characteristics of resin bonding to dentin. Bond strengths of MMA/TBB adhesive resin to different adherends were discussed and compared with other bonding systems. Factors affecting bond strength (such as conditioners, primers, and medicaments used for dental treatment), bonding mechanism, and polymerization characteristics of MMA/TBB resin were also discussed. This review further reveals the unique adhesion features between MMA/TBB resin and dentin: in addition to monomer diffusion into the demineralized dentin surface, graft polymerization of MMA onto dentin collagen and interfacial initiation of polymerization at the resin-dentin interface provide the key bonding mechanisms.

Preparation and Characterization of Homogeneous Grafted Cellulose in DMAc/LiCl System

The homogeneous grafting of methyl methacrylate (MMA) onto cellulose was carried out by using ammonium persulfate as an initiator. DMAc/LiCl was used as the solvent for the dissolution of cellulose and the media for the homogeneous graft polymerization of MMA onto cellulose. The efficient reaction conditions of the grafting reaction were confirmed by weighing methods. The results showed that the efficient reaction conditions were as follows: reaction time, 2h; mass ratio of MMA/cellulose, 1/1(g/g); mass ratio of initiator/cellulose, 6/50 (g/g); and reaction temperature, 80°C. Under these conditions, the GP of homogeneous grafted cellulose can reach 76%. The grafted polymer was characterized by FTIR, SEM and TG-DTA.

Graft Polymerization of Methyl Methacrylate- Acrylonitrile onto Poly(ethene-co-1-butene) and Its Toughening Effect on SAN Resin

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN) was prepared by suspension grafting copolymerization of methyl methacrylate (MMA) and acrylonitrile(AN) onto PEB. PEB-g-MAN/SAN resin blends (ABMS) were prepared by blending PEB-g-MAN with styrene-acrylonitrile copolymer (SAN resin). The effects of AN/(MMA+AN) feed ratio (fAN), PEB/(PEB+MMA+AN) feed ratio (fPEB) and benzoyl peroxide (BPO) dosage on the monomer conversion ratio (CR), rubber's grafting ratio (GR), grafting efficiency (GE) of the copolymerization and the toughening effect of PEB-g-MAN on the SAN resin were investigated. FTIR quantitative analysis showed that when the weight percent of AN unit in the unextracted product was 21.5 wt% with fAN of 25 wt%, the toughening effect of unextracted PEB-g-MAN on SAN resin was the highest. Gel permeation chromatography (GPC) analysis showed that when fAN was 25 wt%, the grafted copolymer had the lowest molecular weight and ABMS had highest toughness. Transmission electron microscopy (TEM) analysis showed that the highest toughness occurred when the phase structure of ABMS was cocontinuous with fAN of 25 wt%. When fAN was 25 wt% PEB-g-MAN domains have numerous small SAN domains in them, which was occlusion structure. Scanning electron microscopy (SEM) analysis indicated that the ABMS fracture surfaces had plastic flow visible, which looked like a craze fibers morphology, for the sample with highest impact strength (fAN = 25 wt%). Dynamic mechanical thermal analysis (DMA) showed that the miscibility of the PEB phase and SAN phase improved after graft copolymerization of MMA and AN onto PEB.

Surface graft copolymerization of poly(methyl methacrylate) onto waste tire rubber powder through ozonization

AbstractGrinding of tires offers a promising opportunity for recycling waste rubber because fine waste tire rubber particle may be used as fillers and property modifiers in thermoplastic, elastomer, and thermoset blends. However, due to the lack of reactive sites on the WTR surface, the adhesion between WTR powder and matrix is poor. In this article, ozonization of waste tire rubber (WTR) powder was performed to produce some “immobile” reactive points (hydroperoxide groups) on the WTR surface. The free radical generated by the decomposition of hydroperoxide groups on WTR surface, was used to initiate graft polymerization of methyl methacrylate (MMA) onto the surface of WTR powder. The experimental results showed that MMA was successfully grafted onto the surface of WTR. The hydrophilicity of the MMA grafted WTR (MMA‐g‐WTR) was improved. The concentration of hydroperoxide groups and the graft degree were both increased with ozonization time. With increasing of polymerization time and polymerization temperature, the grafting degree increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Graft polymerization of methyl methacrylate on tin-weighted silk

Graft polymerization of methyl methacrylate on tin-weighted silk

The role of hydroperoxides as a precursor in the radiation-induced graft polymerization of methyl methacrylate to ultra-high molecular weight polyethylene

A graft polymerization of methyl methacrylate (MMA) to ultra-high molecular weight polyethylene (UHMWPE) with Co-60 γ-ray irradiation in air at room temperature has been carried out. The grafting yields were measured as a function of the storage time (elapsed time from the end of irradiation to the start of grafting), and it was found that the yields reach at the maximum values at around several days since the end of irradiation. In order to clarify the precursor of the graft polymerization, changes of the radical yields and the carbonyl groups were measured as a function of storage time with ESR and microscopic FT-IR, respectively. From the similarities between the depth profiles of the hydroperoxide formation and the grafting products, it was concluded that the hydroperoxides can be main precursors of the grafting of the radiation-induced polymerization of MMA to UHMWPE under the given conditions.

Preparation of a new micro-porous poly(methyl methacrylate)-grafted polyethylene separator for high performance Li secondary battery

In this study, micro-porous poly(methyl methacrylate)-grafted polyethylene separators (PE-g-PMMA) were prepared by a radiation-induced graft polymerization of methyl methacrylate onto a conventional PE separator followed by a phase inversion. After the phase inversion, the micro-pores were generated in the grafted PMMA layer. The prepared micro-porous PE-g-PMMA separators showed an improved electrolyte uptake and ionic conductivity due to their improved affinity with a liquid electrolyte and the presence of pores in the grafted PMMA layer. The PE-g-PMMA separators exhibited a lower thermal shrinkage compared to the original PE separator. The PE-g-PMMA separators showed a better oxidation stability up to 5.0 V when compared to the original PE separator (4.5 V).

Synthesis of poly(methyl methacrylate‐g‐glycidyl azide) graft copolymers using N, N‐dithiocarbamate‐mediated iniferters

AbstractA glycidyl azide polymer with pendent N, N‐diethyl dithiocarbamate groups (GAP‐DDC) was prepared by the reaction of poly(epichlorohydrin) (PECH) with pendent N, N‐diethyl dithiocarbamate groups (PECH‐DDC) and sodium azide (NaN3) in dimethylformamide (DMF). It was then used as a macro‐photoinitiator for the graft polymerization of methyl methacrylate (MMA). Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Conversion was determined gravimetrically and first‐order time conversion plot for the polymerization system showed linear increase with the polymerization time indicating that polymerization proceed in controlled fashion. The molecular weight distribution (Mw/Mn) was in the range of 1.4–1.6 during polymerization. The formation of poly(methyl methacrylate‐g‐glycidyl azide) (PMMA‐g‐GAP) graft copolymer was characterized by gel permeation chromatography, FT‐IR spectroscopy, Thermogravimetric analysis, and differential scanning calorimetry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Graft polymerization from pore wall of three-dimensionally ordered macroporous cross-linked polystyrene via atom transfer radical polymerization

The surface-initiated atom-transfer radical polymerization (ATRP) technique was applied to the graft polymerization of methyl methacrylate (MMA) and N-isopropylacrylamide (NIPAm) from three-dimensionally ordered macroporous cross-linked polystyrene (3DOM CLPS) on which the initiator, halogen atom was immobilized onto the pore wall of 3DOM CLPS by chloromethylation. FT-IR and TG-DWA analyses confirm that the graft polymerization of MMA and NIPAm via ATRP had been taken place at the pore wall of 3DOM CLPS. The initiating efficiency of chloromethyl groups was calculated according to the data of TGA-titration, revealed that the benzyl chloride is not only distributed on the surface of the pore walls but also must be present throughout the inner of the cross-linked polystyrene matrix. SEM analyses show that the grafted layers are smooth and homogeneous, and the ordered structure is well preserved after polymerization. By the adjustment of the graft polymerization time, the thickness of grafted polymer layers can be controlled. The max thickness of grafted PMMA layer is 85 nm and the max thickness of grafted PNIPAm layer is 35 nm.

Synthesis and kinetics of graft polymerization of methyl methacrylate from the RAFT coordinated surface of nano‐TiO2

AbstractPolymer chains of PMMA were grown from nano titania (n‐TiO2) by the reversible addition‐fragmentation chain transfer polymerization process. The mechanism and kinetics of MMA polymerization from both solution and “grafted from” n‐TiO2 were studied. The RAFT agent, 4‐cyano‐4‐(dodecylsulfanylthiocarbonyl) sulfanyl pentanoic acid, with an available carboxyl group was used to anchor onto the n‐TiO2 surface, with the SC(SC12H25) moiety used for subsequent RAFT polymerization of MMA to form n‐TiO2/PMMA nanocomposites. The functionalization of n‐TiO2 was determined by FTIR, XPS, partitioning studies, and thermal analysis. The livingness of the polymerization was verified using NMR and GPC, while the dispersion of the inorganic filler in the polymer was studied using electron microscopy, FTIR, and thermal analysis. The monomer conversion and molecular weight kinetics were explored for the living RAFT polymerization, both in solution and grafted from n‐TiO2, with first‐order kinetics being observed in both cases. Increased graft density on n‐TiO2 led to a lower rate of polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3926–3937, 2008

Organophilic Boehmite Nanoparticles by ATRP Methacrylates Polymerization: Synthesis, Characterization and Dispersion in Polypropylene

Boehmite nanoparticles covered with a polymer shell enhancing the organophilicity of the surface were prepared by physical adsorption of a polyelectrolyte atom transfer radical polymerization (ATRP) macroinitiator followed by graft-polymerization of methyl methacrylate or 2-hydroxyethyl methacrylate. The presence of polymer chains adsorbed/grafted on the Boehmite was confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy and by thermo-gravimetric analysis (TGA), which showed a significant amount of polymer covering the particles. The methodology of polymerization and the kinetics suggested the possibility to modulate the amount, type and thickness of grafted polymer shell. These organic-inorganic hybrid materials were melt compounded in a Brabender mixer with isotactic polypropylene in the presence of functionalized polypropylene. The dispersion degree of Boehmite nanoparticles in the polypropylene matrix as well as their reinforcing effect were studied by morphology characterization [scanning electron microscopy (SEM) and X-ray diffraction (XRD)], whereas thermal and thermo-mechanical properties were assessed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).