Graft Copolymerization Of Maleic Anhydride Research Articles

Study on Direct Grafting Maleic Anhydride onto Poly(D,L-lactide-co-glycolide) Chains

ABSTRACTDirect graft copolymerization of maleic anhydride (MAH) onto poly(D,L-lactide-co-glycolide) (PLGA) was performed by use of benzoyl peroxide (BPO) as initiator. Fourier transform infrared spectra, nuclear magnetic resonance, titration analysis of maleation extent and water contact angle were employed to characterize the obtained MPLGA. The effects of monomer concentration, initiator concentration and reaction temperature on the degree of maleation were investigated. The MPLGA scaffold was obtained by using NaCl as the porogen. The results showed that maleic anhydride was successfully grafted onto the PLGA chains. The monomer and initiator concentrations played an important role in the graft copolymerization; the extent of maleation first increased with increasing content of MAH and BPO and then declined. The extent of maleation continuously increased with increasing temperature to 100°C, and then the rate of increase decreased. The extent of maleation could be controlled in the range from 0.15 to 0.71% by adjusting the graft copolymerization conditions. The introduction of anhydride enhanced the water contact angle of PLGA. The MPLGA scaffold showed a network of interconnected pores ranging from 50 to 300 μm.

Study on Graft Copolymerization of Maleic Anhydride onto Ground Rubber Tire

The graft copolymerization of maleic anhydride (MAH) onto ground rubber tire (GRT) was investigated through solvothermal synthesis route using free radical initiator. The effects of solvents, initiators and their concentration, and GRT mesh size on the grafting yield (GY) were studied, and the optimal conditions were concluded. The results showed that the high GY was obtained by using toluene as solvent, 1% azobisisobutyronitrile as initiator, and GRT fine powder as raw material. Infrared spectra and X-ray photoelectron spectra confirmed that MAH was successfully grafted onto the GRT molecules. The thermogravimetric analysis revealed that the thermal stability of graft GRT (GRT-g-MAH) is better than that of GRT slightly. The blending experimental results suggest that the GRT-g-MAH can be used as a compatilizer for GRT/HDPE blends.

Synthesis, characterization and use of polymer‐supported phase transfer catalyst in organic reactions

AbstractA polymer‐supported (PS) phase transfer catalyst, polyethylene‐g‐quaternary ammonium salt (PE‐g‐QN+), is prepared through a three‐step graft copolymerization of maleic anhydride (MAn) onto polyethylene (PE) by photochemical method using 1% benzophenone (Bz) as photosensitizer. Post grafted acid hydrolysis of polyethylene‐g‐maleic anhydride (PE‐g‐MAn) results in the preparation of PE‐g‐succinic acid which on further treatment with tetrabutylammonium bromide (TBAB) under basic conditions in tetrahydrofuran (THF) gives PE‐g‐QN+. Optimum conditions pertaining to maximum percentage of grafting have been evaluated as a function of concentration of maleic anhydride, amount of photosensitizer, and time of reaction. Maximum percentage of grafting (25%) was obtained using 3.57 mol of MAn and 0.5 mL of 1% Bz in 120 min. The PE and graft copolymers, PE‐g‐MAn, and PE‐g‐QN+ were characterized by FTIR Spectroscopy and thermogravimetric analysis (TGA). The ionic nature of quaternary ammonium salt, PE‐g‐QN+ has also been confirmed by conductance measurements. PE‐g‐QN+ reagent have been used successfully for polymerization, amidation, and esterification reactions. The products obtained were characterized by FTIR and H1NMR spectral methods. The reagent was reused for the further reactions and it was observed that the polymeric reagent polymerize, amidate, and esterificate the compounds successfully but with little lower product yield. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Polyethylene‐supported N‐bromosuccinimide polymeric reagent for use in some oxidation reactions

AbstractWe report a three‐step preparation of a polymer‐supported oxidizing reagent, polyethylene‐g‐N‐bromosuccinimide (PE‐g‐NBS), through the graft copolymerization of maleic anhydride (MAn) onto polyethylene (PE) by a photochemical method with 1% benzophenone as a photosensitizer. The postgrafting treatment of polyethylene‐g‐maleic anhydride (PE‐g‐MAn) with urea on fusion gives polyethylene‐g‐succinimide (PE‐g‐succinimide), which, on further treatment with an aqueous solution of sodium hydroxide and bromine, gives the required reagent, PE‐g‐NBS. The maximum percentage grafting (25%) was obtained with 3.57 mol of MAn and 0.5 mL of 1% benzophenone in 120 min. Fourier transform infrared spectroscopy and thermogravimetric analysis methods were used to characterize the graft copolymer PE‐g‐MAn, PE‐g‐succinimide, and the polymeric support, that is, PE‐g‐NBS. The grafted PE and the polymeric support were found to be thermally stable. The polymer‐supported N‐bromosuccinimide was used successfully for the efficient oxidation of a series of alcohols, including 2‐propanol, n‐butanol, ethylene glycol, cyclohexanol, poly(vinyl alcohol), benzoin, benzyl alcohol, and chloromycetin, to their corresponding aldehydes and ketones. The selectivity of PE‐g‐NBS toward the oxidation of secondary alcoholic groups without the disturbance of the primary alcoholic groups was reflected during the oxidation of chloromycetin. The oxidized products were characterized by Fourier transform infrared and 1H‐NMR spectral methods. The reagent was reused for the oxidation of fresh alcohols, and it was found to oxidize them successfully, although with a little lower product yield. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Graft copolymerization of maleic anhydride onto low‐molecular‐weight polyisobutylene through solvothermal method

AbstractThe free‐radical graft copolymerization of maleic anhydride (MAH) onto highly reactive low molecular weight polyisobutylene was conducted by the use of benzoyl peroxide as an initiator through the solvothermal method. Fourier transform infrared spectra and 1H‐NMR spectra confirmed that maleic anhydride was successfully grafted onto highly reactive low molecular weight polyisobutylene backbone, and the grafting mechanism also was proposed. The effect of benzoyl peroxide content, MAH concentration, total reactant amount in the reaction vessels, reaction temperature and time, and different kinds and volumes of solvents on MAH's degree of grafting was investigated in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Effects of polypropylene-g-(maleic anhydride/styrene) compatibilizer on mechanical and rheological properties of polypropylene/clay nanocomposites

To enhance the dispersibility of clay in polypropylene (PP) matrix, PP-g-(maleic anhydride/styrene) (MA/ST) was prepared as a compatibilizer by graft copolymerization of maleic anhydride (MA) and styrene (ST) with PP. The addition of ST was known to be effective in improving the graft degree. PP/clay nanocomposites with the compatibilizer were prepared by melt intercalation. The X-ray diffraction (XRD) peaks of (0 0 1) plane of the organo-modified montmorillonite (O-MMT) were shifted to lower angles by an addition of PP-g-(MA/ST), indicating the intercalation capability of PP-g-(MA/ST) in the silicate layers. Transmission electron microscopy (TEM) photographs showed that the O-MMT in the presence of PP-g-(MA/ST) was intercalated and partly exfoliated during melt mixing. The addition of O-MMT and PP-g-(MA/ST) improved the thermal stability, tensile and rheological properties of the nanocomposites.

A Solvent Free Graft Copolymerization of Maleic Anhydride onto Cellulose Acetate Butyrate Bioplastic by Reactive Extrusion

AbstractSummary: Interfacial adhesion between fibers and matrix is a crucial factor for effective stress transfer from matrix to fiber; especially in short fiber reinforced composite systems. The use of a chemical compatibilizer is an efficient means to achieve such adhesion. Maleic anhydride‐grafted‐cellulose acetate butyrate (CAB‐g‐MA) is one such compatibilizer which can be used in biocomposite fabrication, and this has been synthesized in our laboratory by utilizing a twin‐screw reactive extrusion process in the presence of a free radical initiator (2,5‐dimethyl‐2,5‐di(tert‐butylperoxy)hexane). The unique feature of this process is its solvent‐free approach for grafting of maleic anhydride onto CAB, without hydroxyl group protection. CAB‐g‐MA was characterized using FTIR as well as by a non‐aqueous titration method. The effects of initiator and monomer concentrations and various processing conditions on the graft content were also investigated. The preliminary results show that by adding approximately 10 wt.‐% of CAB‐g‐MA into a plasticized cellulose acetate butyrate (TEB)‐industrial hemp fiber biocomposites system, an improvement in tensile strength (20%) and in tensile modulus (45%) were obtained. These results are promising in that they pave the way for future studies involving the use of CAB‐g‐MA as a suitable compatibilizer for cellulose ester‐natural fiber biocomposites. magnified image

Modification of acrylonitrile‐butadiene‐styrene terpolymer by graft copolymerization with maleic anhydride in the melt. II. Properties and phase behavior

AbstractThe graft copolymerization of maleic anhydride (MAH) onto acrylonitrile‐butadiene‐styrene terpolymer (ABS) using dicumyl peroxide and benzoyl peroxide as the binary initiator and styrene as the comonomer in the molten state was described. The properties and phase morphologies of the modified products (ABS‐g‐MAH) were studied. The results indicate that the melt flow index (MFI) of ABS‐g‐MAH increases with the increase of MAH content, the initiator concentration, and the screw speed, whereas the MFI decreases with the increase of temperature. The impact strength and the percentage elongation of ABS‐g‐MAH both decreased and the tensile strength of ABS‐g‐MAH increased slightly as the grafting degree increased. The phase inversion behavior of the modified product was observed by transmission electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2834–2839, 2004

Modification of acrylonitrile–butadiene–styrene terpolymer by grafting with maleic anhydride in the melt. I. Preparation and characterization

AbstractThe graft copolymerization of maleic anhydride (MAH) onto acrylonitrile–butadiene–styrene terpolymer (ABS) was carried out with dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as the binary initiators and with styrene as the comonomer in the molten state. IR spectra confirmed that MAH was successfully grafted onto the ABS backbone. A reaction mechanism was proposed: the grafting most likely took place through the addition of MAH radicals to the double bond of the butadiene region of ABS. Influences such as the MAH concentration, the initiators and their concentrations, the reaction temperature, the rotating speed, and the comonomer concentration were studied. The results indicated that using styrene as a comonomer and DCP/BPO as binary initiators was beneficial for the graft copolymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1249–1254, 2003

Styrene‐assisted free‐radical graft copolymerization of maleic anhydride onto polypropylene in supercritical carbon dioxide

AbstractThe free‐radical graft copolymerization of maleic anhydride (MAH) onto polypropylene (PP) with the assistance of styrene (St) in supercritical carbon dioxide (CO2) was studied. The effects of the St concentration and initiator concentration on the functionality degree of the grafted PP in supercritical CO2 were investigated. The addition of St drastically increased the MAH functionality degree, which reached a maximum when the molar ratio of MAH and St was 1:1. St, an electron‐donating monomer, could interact with MAH through charge‐transfer complexes to form the St–MAH copolymer (SMA), which could then react with PP macroradicals to produce branches by termination between radicals. There was SMA in the grafting reaction system characterized by Fourier transform infrared and differential scanning calorimetry. Furthermore, the highest MAH functionality degree was obtained when the concentration of 2,2′‐azobisisobutyronitrile (AIBN) was 0.6 wt % based on PP. The effects of the temperature and pressure of supercritical CO2 on the functionality degree of the grafted PP were analyzed. An increase in the temperature accelerated the decomposition rate constant of AIBN, thereby promoting the grafting reaction. In addition, an increase in the temperature increased the diffusion of monomers and radicals in the disperse reaction system of supercritical CO2. The highest degree of functionality was found at 80°C. Also, the functionality degree of grafted PP decreased with an increase in the pressure of supercritical CO2 within the experimental range. The morphologies of pure PP and grafted PP were significantly different under polarizing optical microscopy. The PP spherulites were about 38 μm in size, and the grafted PP spherulites were significantly reduced because of heterogeneous nucleation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 853–860, 2003

Effect of chemical crosslinking on swelling parameters of modified poly(vinyl alcohol) hydrogel

Graft copolymerization of maleic anhydride (MA) onto partially and fully hydrolyzed poly(vinyl alcohol), PVA, was carried out in presence and in absence of an initiator. The structural features of these grafts were confirmed by 1 HNMR analysis. 1 HNMR analysis was also used to determine the percentage of grafting. These grafts were crosslinked using different concentrations of either 1,1,1-trimethylolpropane trimethacrylate (TPT) or methylene bisacrylamide (MBA) as Hexa- or tetra-functional crosslinker, respectively. The crosslinkers concentrations ranged from 1% to 30% (wt.%) based on the total weight of grafts. The final water content, volume fraction of the polymer and swelling capacity were determined for all grafts. The effect of MBA and TPT crosslinkers structure on swelling properties of both partially and fully hydrolyzed PVA grafts were also determined.

Grafting of Maleic Anhydride onto Acrylonitrile-Butadiene-Styrene Terpolymer: Synthesis and Characterization

The graft copolymerization of maleic anhydride (MAH) onto a acryloni-trile-butadiene-styrene (ABS) terpolymer was carried out using benzoyl peroxide (BPO) as an initiator and toluene as a solvent. The effects of various parameters such as monomer concentration, initiator concentration, reaction time, and temperature on graft yield were studied. Addition occurs in the butadiene region of the polymer, either by the loss of vinylic hydrogen and subsequent radical formation and addition of monomer or by addition to the double bond. The graft copolymers were characterized by infrared, thermogravirnetric analysis, and differential scanning calorimetry. Thermal stability was improved and T g was increased.

X-Ray Photoelectron Spectroscopy of Lignocellulosic Materials Treated with Malea Ted Polypropylenes

The esterification reaction between lignocellulosic materials (ALCELL lignin and Bleached kraft cellulose) and maleated polypropylenes (graft copolymerization of maleic anhydride into polypropylene chains) was investigated. The reaction was conducted in a reactor in the presence of xylene used as a solvent and sodium hypophosphite as a catalyst. The reaction between lignocellulosic materials and pure maleic anhydride was also conducted to determine the effect of the long polypropylene chains on the formation of ester bonds. The XPS studies of maleated bleached kraft cellulose showed the emergence of C4 carbon type on high resolution spectra, which was related to ester carbonyl functionality formed by esterification reaction. No evidence of esterification was observed between ALCELL lignin and maleated polypropylenes. The XPS studies demonstrated that both ALCELL lignin and bleached kraft cellulose chemically react with maleic anhydride with the formation of ester bonds.

Studies of reactions with polymers. I. The reaction of maleic anhydride with PVA and the properties of the resultant

AbstractGraft copolymerization of maleic anhydride (MA) onto PVA was carried out both in the presence and absence of the initiator. In the former case, the resultant was a copolymer containing a carboxylic acid and a keto‐olefinic side chain. Therefore, the reaction product, viscosity, gel content, and mechanical properties differed from the resultant of the latter, which was obtained by esterification of PVA by MA. Both resultants showed polyelectrolytes characteristics. The dependence of the grafting percentage on the concentration of the initiator, the concentration of the monomer, the reaction temperature, and the reaction medium was studied. Grafted copolymers after heat treatment showed remarkable mechanical strength in the wet state when compared with original PVA.