Self‐initiating performance of maleic anhydride on surface photografting polymerization

Maleic anhydride (MAH) was photografted onto low‐density polyethylene (LDPE) films with a grafting efficiency of about 70% in the absence of a photoinitiator. The self‐initiating performance was attributed to a mechanism of abstracting hydrogen atoms from LDPE chains by excited MAH dimers. The supporting experimental results were as follows: (1) the far‐UV radiation (200–300 nm) was indispensable for the graft polymerization and 2) the crosslinking reaction of LDPE inevitably accompanied the grafting of MAH. In addition, the initiation performance of MAH was further confirmed by surface photografting of acrylic acid in the presence of MAH, where MAH was used as the photoinitiator. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3246–3249, 2001     

热重法测定高马来酸酐含量苯乙烯-马来酸酐共聚物的组成

高马来酸酐含量苯乙烯-马来酸酐共聚物(SMA)是一种具有优良耐热性、刚性和尺寸稳定性的新型高分子材料.由于SMA分子中含有极性很强、反应活性很高的酸酐官能团,所以它被广泛应用于涂料、粘合剂的改性剂、地板抛光的乳化剂、复合材料和颜料的分散剂、水处理剂等领域[1-5].     

马来酸酐均聚反应机理的理论研究Ⅱ: α-羟基丁二酸酐碳阴离子和碱催化下的阴离子聚合机理

用AM1方法计算了马来酸酐、氢氧根阴离子及其加成物α-羟基丁二酸酐碳阴离子的电子结构、电荷分布和键级。应用前线轨道理论和成键三原则研究了碱(NaOH)催化条件下马来酸酐均聚过程中α-羟基丁二酸酐碳阴离子活性中间体参与反应的可能性及其阴离子聚合机理。计算结果能很好地阐明实验事实。     

Synthesis and characterization of poly(styrene‐maleic anhydride)‐montmorillonite nanocomposite

Poly(styrene‐maleic anhydride)‐montmorillonite nanocomposites were prepared by intercalation of layered montmorillonite with the polymer ions. Synthetic approaches including polymerization and phosphonium salt formation have been used for polymer intercalation and dispersion of the host layers in the polymer matrix. The ratio of the mineral in the composites ranged 30–50%. Wide‐angle X‐ray diffraction (WAXD) disclosed that the d₍₀₀₁₎ spacing between the internal lamellar surface were only expanding to about 13 and 15 Å according to the type of phosphonium salt suggesting packing of polymer molecules between the layers. Examination of these materials by scanning and transmission electron microscopy showed spherical nano size particles of average diameter, 350 nm. Copyright © 2002 John Wiley & Sons, Ltd.     

Theoretical study of initiated reaction mechanism of polymerization of maleic anhydride catalyzed by OH−1 anion

A theoretical study of the polymerization reaction mechanism of maleic anhydride (MA) initiated by hydrate is presented. The reaction pathway has been studied with the density functional theory (DFT) method at the B3LYP/6‐311G** level. The geometrical parameters of transition states (TS) are optimized; intrinsic reaction coordinate (IRC) calculations have also been performed to obtain further credible features. Frequency analyses of all the stationary points are calculated at the same basis sets. The total energies of all geometries are corrected at second‐order Møller–Plesset (MP2)/6‐311G**. Calculation results reveal that the reaction mechanism is attributable to anion polymerization. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Melt modification of poly(styrene‐co‐maleic anhydride) with alcohols in the presence of 1,3‐oxazolines

Various copolyesteramides were prepared by melt compounding at 220 °C involving reaction of poly(styrene‐co‐maleic anhydride), SMA, with 6, 17, and 28 wt % maleic anhydride content, and 1‐dodecanol, C12OH, in the presence of 2‐undecyl‐1,3‐oxazoline, C11OXA. Copolymer architectures were examined by means of ¹H NMR, FTIR, DSC, and TGA using model compounds prepared via solution reactions. While conversion of anhydride with alcohol was poor due to the thermodynamically favored anhydride ring formation, very high conversions were achieved when stoichiometric amounts of C11OXA were added. According to spectroscopic studies esteramide groups resulted from reaction of oxazoline with carboxylic acid intermediate. In the absence of alcohol, C11OXA reacted with anhydride to produce esterimides. Effective attachment of flexible n‐alkyl side chains via simultaneous reaction of C12OH and C11OXA resulted in lower glass‐transition temperatures of copolyesteramides. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1222–1231, 2000     

Neodymium oxide‐assisted melt free‐radical grafting of maleic anhydride on isotactic‐polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd₂O₃), ‐assisted melt free‐radical grafting of maleic anhydride (MAH) on isotactic‐polypropylene (i‐PP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd₂O₃ into reactive system leads to an enhancement of the grafting degree of MAH, along with an elevated degradation of i‐PP matrix. When Nd₂O₃ content is 4.5 mmol %, the increment of the grafting degree of MAH (maximally) is up to about 30% compared with that of the related system without adding Nd₂O₃, while the severest degradation of i‐PP matrix simultaneously occurs. On the basis of the reaction mechanism of PP‐g‐MAH proposed before, the sequence of β‐scission and grafting reaction is discussed in detail. It is found that, for the reactive system studied, most tertiary macroradicals first undergo β‐scission, and then, grafting reaction with MAH takes place at the new radical chain ends. The imported Nd₂O₃ has no effect on the aforementioned reaction mechanism, whereas it enhances the initiating efficiency of the initiator, dicumyl peroxide (DCP). We tentatively explain the experimental results by means of synergistic effect between DCP and Nd₂O₃. It is calculated that the synergistic effect is maximal when the molar ratio of DCP to Nd₂O₃ is approximately 1:6. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 134–142, 2006     

Acrylonitrile–maleic anhydride copolymer membrane (II): effects of post‐treatment1

The effects of post‐treatment (including thermal treatment and base treatment) on the structure and performance of acrylonitrile–maleic anhydride (AN‐MA) copolymer membrane were investigated. The water flux decreased gradually (except the deviations when the temperature of thermal treatment was 50 °C or the time of thermal treatment was 50 min but rejection of bovine serum albumin increased slowly with increasing temperature or prolonging the time of thermal treatment. “The swelling effect of water in network” was proposed to explain the deviations. AN‐MA copolymer membrane is not resistant to a base. However, the performance of the membrane can be adjusted by treatment with a dilute base solution. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and application of modified poly (styrene‐alt‐maleic anhydride) networks as a nano chelating resin for uptake of heavy metal ions

A chelating resin based on modified poly (styrene‐alt‐maleic anhydride) with 3‐aminobenzoic acid was synthesized. This modified resin was further reacted by 1,2‐diaminoethane or 1,3‐diaminopropane in the presence of ultrasonic irradiation to prepare tridimensional chelating resin for the removal of heavy metal ions from aqueous solutions. The adsorption behavior of Fe(II), Cu(II), Zn(II) and Pb(II) ions was investigated by synthesized chelating resins in various pH. Among the synthesized resins, CSMA‐AB1 and CSMA‐AB2 demonstrated a high affinity for the selected metal ions compared to SMA‐AB, and the order of removal percentage changes as follow: Fe(II) > Cu(II) > Zn(II) > Pb(II). The adsorption of all metal ions in acidic medium was moderate, and it was favored at the pH value of 6 and 7. Also, the prepared resins were examined for removal of metal ions from industrial wastewater and were shown to have a very efficient adsorption in the case of Cu(II), Fe(II) and Pb(II); however, the adsorption of Zn(II) was lower than others. The resin was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction analysis and thermogravimetric analysis/derivative thermogravimetry. Copyright © 2012 John Wiley & Sons, Ltd.     

Multifunctional,water‐soluble,C60‐pendant maleic anhydride copolymer

Starting from the synthesis of a new methanofullerene derivative bearing an alcohol group, we report on the preparation of a water‐soluble, fullerene‐pendant copolymer. This multifunctional, C₆₀‐pendant maleic anhydride copolymer was characterized by conductometric titration, Fourier transform infrared and ultraviolet spectroscopy, thermogravimetric analysis, and cyclic voltammetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5814–5822, 2005     

Synthesis of well‐defined copolymer of acrylonitrile and maleic anhydride via RAFT polymerization

Well‐defined copolymer of acrylonitrile (AN) and maleic anhydride (MAn) has been successfully synthesized via reversible addition‐fragmentation chain transfer polymerization. The polymerization kinetics and “living”/controlled features were thoroughly studied and confirmed. The thermal properties and spinnability of the prepared copolymers were investigated via differential scanning calorimetry, thermogravimetric analyzer, and electrospinning subsequently. When PAN‐co‐PMAn was used as precursors, nonwoven with “crosslinked” structures was obtained during electrospinning. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5263–5269     

Synthesis of divinylbenzene–maleic anhydride microspheres using precipitation polymerization

Narrow disperse micron-range divinylbenzene-maleic anhydride microspheres have been prepared in near quantitative yields using precipitation polymerization. A variety of solvents were investigated for use as the reaction medium with a 40:60 mixture of methyl ethyl ketone and heptane providing the best results. The effects of solvent composition on particle size and morphology and monomer loading effects were also investigated. Particle size decreased with increasing solvency (increasing MEK fraction) while increases in monomer loading caused larger particle sizes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2223–2227, 1998     

Peroxide initiated maleic anhydride grafting: Structural studies on an ester‐containing copolymer and related substrates

Maleic anhydride (MAn) was grafted onto the low molecular weight esters methyl decanoate (MD) and methyl 2‐ethylhexanoate (MEH) using the free‐radical initiators Lupersol‐101 and ‐130; the esters were used as model compounds for the copolymer poly(ethylene‐co‐methyl acrylate). The grafted products in both cases were isolated from the unreacted ester and were subjected to extensive analysis using spectroscopic and chromatographic techniques. Analysis of the grafted material indicated the presence of one or more succinic anhydride (SAn) residues grafted to the ester. In the case of the multiply grafted material it has been established conclusively by ¹³C‐NMR using 2,3‐¹³C₂ labeled MAn that the multiple grafts exist as single units. A limited number of grafting experiments was performed on the copolymer in the melt and the graft‐modified copolymer was characterized spectroscopically. Single graft units were observed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1609–1618, 1999     

Laser-Initiated copolymerization of N-vinylpyrrolidone with maleic anhydride and maleimide

This article describes the laser-initiated copolymerization of N-vinylpyrrolidone with maleic anhydride and maleimide via charge transfer complexes. The dependence of copolymer yield on the molar ratios of the monomers in the feed and on the irradiation time is described. Based on the ultraviolet and infrared spectroscopy, and chemical analysis results, a tentative mechanism of polymerization is suggested. The rates of polymerization of several monomer systems are compared. The N-vinylpyrrolidone and maleimide system shows the highest rate of polymerization.     

Preparation of polymer nanoparticles from renewable biobased furfuryl alcohol and maleic anhydride by stabilizer‐free dispersion polymerization

The spherical polymer nanoparticles of biobased renewable monomers, furfuryl alcohol (FA) and maleic anhydride (MAn), with diameters (D_n) in the range of 120 to 500 nm have been prepared by stabilizer‐free dispersion copolymerization. In acetate or its mixture, the conversion of the monomers greatly depended on the concentration of AIBN. When the molar ratio of AIBN/monomers was 3.6% (wt), the monomer conversion could be as high as 80%. The aggregations of the solvated polymer chains formed the nuclei of the polymer particles. After the nucleation stage, both the monomer conversions and particle sizes increased steadily, while the coefficient of variation of the particle size decreased. The almost linear relationship between the D_n³ and the weight of polymer suggested that there is no significant secondary nucleation. The copolymer of FA and MAn could not dissolve in common organic solvents. Elemental analyses, FTIR and ¹³CP‐MAS spectra showed that the copolymer was close to the alternative copolymer of FA and MAn irrespective to the molar ratios of FA/MAn in monomer feed. Furthermore, the two 2,5‐ and 3,4‐dihydrofuran ring configurations exist in the copolymer and the later is the major one. The reaction of copolymer particles with triethylenetetramine confirmed the reactivity of the succinic anhydride groups at the surface of copolymer particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ferrocene as an effective initiator for copolymerization of styrene with maleic anhydride

Ferrocene (Fc) was found to be an effective initiator for copolymerization of styrene (ST) with maleic anhydride (MAH). Copolymerization could be initiated by charge transfer complex formed between MAH as an electron acceptor and Fc as an electron donor. A good relationship between the formation of charge transfer complex and initiation activity was observed in the copolymerization of ST with MAH in various solvents. Overall energy of activation determined from an Arrhenius plot in dioxane was found to be 21.8 kJ/mol. © 1995 John Wiley & Sons, Inc.     

A kinetic study on grafting of maleic anhydride onto a thermoplastic elastomer

Maleation of a thermoplastic elastomer, styrene-[ethylene-butylene]-styrene (SEBS) triblock copolymer, was carried out by a solution grafting reaction with maleic anhydride initiated by dicumyl peroxide. The reaction products from the graft reaction in xylene, commonly chosen as the solvent for maleation graft reactions, were identified using liquid chromatograph (LC), IR, and ¹³C-NMR. Side products from the graft reaction were identified by the LC analysis and, it was concluded that xylene affected the graft reaction through its active methyl groups. Reaction mechanisms were investigated by performing free radical kinetics analysis. The reaction orders and the apparent rate constant were estimated. It was concluded that a proper choice of the solvent might favor better graft efficiency. © 1993 John Wiley & Sons, Inc.     

α-松油烯-马来酸酐加成物的气相色谱分析

气相色谱法直接测定α－松油佛－马来酸酐加成物，不但免去了容量滴定法测定时必先分离共存马来酸酐的繁琐手续，而且方法简便、快速，能满足合成过程中跟踪分析的需要。     

Bio‐based comb‐like copolymers derived from alkyl 10‐undecenoates and maleic anhydride

In this article, 10‐undecenoic acid, based on castor oil, was used a raw material for the synthesis of alternating copolymers. ω‐Unsaturated fatty esters as alkyl 10‐undecenoates were prepared by the esterification reaction of 10‐undecenoic acid with alkyl alcohol. A series of comb‐like copolymers were synthesized by free radical polymerization from maleic anhydride and alkyl 10‐undecenoates copolymers with different length of alkyl side chains in a toluene solution. These copolymers were investigated by ¹H and ¹³C nuclear magnetic resonance, Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry (DSC). The copolymers were obtained in a low molecular weight in a range 3370–12,240 g mol⁻¹ and their structural characterization indicated the formation of alternating copolymers. DSC characterization revealed that these comb‐like copolymers showed amorphous to semicrystalline behavior by increasing the length of side chains. The bio‐based comb‐like copolymers allow for the development of new polymeric materials for several applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1039–1045