Studies of reactions with polymers. II. The reaction of maleic anhydride with acrylonitrile onto PVA and the properties of the resultant

Graft terpolymers were prepared by graft polymerization of a mixture of acrylonitrile (AN) and maleic anhydride (MA) onto PVA in DMSO solution using KPS as an initiator. Structure and solubility of graft terpolymers varied with the concentrations of KPS and MA. Both lower and upper critical values of KPS concentration varied with MA concentration, and the resulting reaction could be divided into three regions—crosslinked, hydrophobic, and hydrophilic regions. Structures of graft terpolymers were considered to be composed of homopolymer side chain grafted onto PVA while gelation occurred from the surplus radicals in PVA backbone to carry on the coupling reaction. The mechanical properties and viscosities increased with the increase of the wt % of AN in graft terpolymers; however, to increase AN content in PVA by increasing KPS concentration would bring about the oxidation scission and do damage to mechanical properties. Thus it becomes obvious that KPS can only be used at a suitable amount.     

The reaction of polypropylene with maleic anhydride

An addition reaction of maleic anhydride with polypropylene takes place in the presence of radical reagents or sunlight. The initial rate of the reaction was proportional to the concentration of polypropylene and maleic anhydride, and one-half power of the concentration of the radical reagents. The increase in the temperature from 80 to 120°C increased the rate of the reaction and di-cumyl peroxide was effective as a radical reagent for this reaction. Ionic crosslinked rubber-like polymers were obtained from the reaction of maleic polypropylene with some alkali metal compounds. They showed the characteristic absorption band due to ? COO^? in their infrared spectra.     

Grafting of maleic anhydride onto polypropylene by reactive processing. I. Effect of maleic anhydride and peroxide concentrations on the reaction

Grafting reactions were performed in a Haake torque rheometer, according to a central composite experimental design, where the maleic anhydride and peroxide concentrations, rotor speed, and reaction time were varied. The 27 formulations were analyzed by Fourier transformed infrared spectroscopy and melt‐flow index measurements (MFI). An increase in peroxide concentration caused an increase in the percentage of reacted maleic anhydride and in MFI. The effect of initial maleic anhydride concentration presented different types of behavior, depending on the peroxide level. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 247–255, 1999     

The reaction of nonconjugated unsaturated fatty acid esters with maleic anhydride

Summary 1. The non-conjugated unsaturated fatty acid esters react with maleic anhydride at 200° C. or above. 2. At 200° C., methyl oleate reacts with almost 1 mole, methyl linoleate with 2 moles, and methyl linolenate with 2.5 moles of maleic anhydride, when an excess of anhydride is present. Methyl stearate reacts negligibly. 3. Methyl oleate reacts without affecting unsaturation. 4. The first molecule of anhydride reacting with methyl linoleate reacts mostly to saturate one double bond, while the second one adds on without affecting unsaturation. 5. The first two molecules of anhydride reacting with methyl linolenate react mostly to saturate one double bond each, while the third molecule adds on without affecting unsaturation. 6. The possible structures of the reaction products have been discussed. Presented before the American Oil Chemists’ Society at their meeting in Chicago, October 8–10, 1941. Now associated with the Southern Regional Research Laboratory, New Orleans, Louisiana. A cooperative organization participated in by the Bureaus of Agricultural Chemistry and Engineering and Plant Industry of the U. S. Department of Agriculture, and the Agricultural Experiment Stations of the North Central States of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin.     

Radical-induced ionic polymerization in the presence of maleic anhydride. I. Mechanism of polymerization of maleic anhydride by radical initiators

Three kinds of trapped radicals are observed in poly(maleic anhydride) (Poly-MAH) which were prepared by the use of radical initiators such as AIBN or BPO. It was found that these radicals were transformed to the active species so as to initiate the cationic polymerization. The structure of these radicals was studied by the ESR and the kinetic analysis of MAH polymerization in the presence of various additives.     

Study of the reaction of maleic anhydride with Illinois bituminous coal

Maleic anhydride reacted with Illinois No. 6 bituminous coal (mf) at 200 and 250 °C resulted in a 22.5 and 39.3% increase in weight, respectively, which was based on the benzene-insoluble residue. The carboxyl group content of this coal residue, after it had been refluxed with water and demineralized, was 2.01 meq g^?1 (459% increase) at 200 °C, and 2.74 meq g^?1 at 250 °C (626% increase). If one assumes an average molecular weight of 2000 for bituminous coal, these results correspond to approximately 2 mol dienophile reacting with each mol of coal. Carboxyl group content of the insoluble coal residue was determined by the barium acetate method.     

Controlled degradation reactions in EPDM bulk modification with maleic anhydride

Summary Two kinds of EPDM rubber were bulk functionalized with maleic anhydride, using dicumyl peroxide as radical source, in the presence of stabilizers and electron donor in order to minimize degradative oxidation. Different peroxide type initiators were tested aiming to control oxidation without deleteriously affecting grafting efficiency.     

马来酸酐改性纤维素衍生物的制备与性能

以1-烯丙基-3-甲基氯代咪唑〔AMIM〕Cl为离子液体,用4-二甲基氨基吡啶(DMAP)作催化剂,合成了马来酸酐改性纤维素衍生物新型纤维素材料。采用13C-NMR方法对衍生物进行了表征。将衍生物作为热塑弹性体添加在脲醛树脂胶中,在增强树脂胶性能方面表现出较好的效果。实验结果表明,催化剂DMAP的使用量为3%(催化剂与马来酸酐质量比),马来酸酐与微晶纤维素质量比为5∶1,100℃的条件下反应4h,合成了取代度为0.10的马来酸酐改性纤维素衍生物。将衍生物添加到脲醛树脂中,压制成的胶合板胶合强度达到1.28MPa,符合GB/T17657-1999中I类胶合板的强度要求。     

马来酸酐熔融接枝LDPE的性能

采用熔融接枝法制备了低密度聚乙烯(LDPE)与马来酸酐(MAH)接枝物,通过调整反应物的用量及反应条件控制接枝率。随着MAH及引发剂用量的增加,接枝率呈先增大后降低的趋势。低剪切速率时,接枝物的最大初始剪切黏度达4750 Pa·s,远高于纯LDPE;高剪切速率时,接枝物的剪切黏度与纯LDPE趋于相同,约500 Pa·s。接枝物的拉伸强度在8 MPa左右,同纯LDPE接近,断裂伸长率略有下降。     

Functionalization of Poly(organophosphazenes). VI. Substituent effect on the grafting reaction of maleic anhydride onto phenoxy-substituted phosphazene polymers

In this paper we describe the solution functionalization reaction of six phenoxysubstituted poly(organophosphazenes) with maleic anhydride and the effect of the phosphazene substituents on the overall grafting yield of anhydride moieties. It was found that the phosphazene polymer substituted with 4-ethylphenoxy groups is the most reactive of the whole series of exploited materials, while that bearing 4-t-butylphenoxy groups is the most inert one. This experimental reactivity trend observed in the grafting process is accounted for on the basis of both thermodynamic and steric factors.     

The dilute solution properties of maleic anhydride and maleic acid copolymers. II-unperturbed dimensions and persistence lengths of chains in solution

The light-scattering, osmotic pressure and viscosity data reported in the preceding paper are used to estimate the characteristic ratios and the persistence lengths of poly(maleic anhydride-co-ethyl vinyl ether) (MAn) and poly(maleic acid-co-ethyl vinyl ether) (H-MA) in organic solvents and sodium salt of H-MA (Na-MA) in NaCl aqueous solutions. The characteristics ratios obtained by Stockmayer-Fixman's extrapolation method are as follows: 6.5 for MAn in organic solvents, 9.6 for H-MA in organic solvents, and 10.8 for Na-MA in NaCl aqueous solutions. The persistence lengths of these copolymers were also calculated by applying the wormlike chain model to viscosity data; $\text{～9}\text{A}\text{?}$ for MAn in organic solvents and $\text{～12}\text{A}\text{?}$ for H-MA in organic solvents. For Na-MA in NaCl aqueous solutions, the persistence lengths vary in proportion to the inverse root of the ionic strength C_s (i.e., $\text{C}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{s}}$). The persistence length in the absence of electrostatic interaction (i.e., C_s←∞) is about 10 Å which corresponds to the values of H-MA in organic solvents.     

马来酐的安全生产

从马来酐生产过程中原料易燃易爆及成品易分解爆炸的特性，分析了马来酐生产过程中的不安全因素，详细阐述了操作过程及储存、运输、精制、水处理等环节安全生产，并通过事故个例教训提出消除安全隐患的办法。     

Controlled drug release by polymer dissolution. I. Partial esters of maleic anhydride copolymers—properties and theory

The kinetics of drug release from a series of partial esters of vinyl acetate–maleic anhydride has been investigated. These polymers in their un-ionized forms are hydrophobic and water insoluble, but in their ionized forms they are water soluble. Polymer dissolution is pH sensitive, and different half-esters have a characteristic pH range above which they are soluble and below which they are insoluble. When films are placed in buffered media, they erode at a constant rate that depends on the pH of dissolution of the polymer and on the pH of the buffered medium. Dissolution of the polymer is limited to the polymer–buffer medium interface, and drugs dissolved or uniformly dispersed in the polymer are released by zero-order kinetics. A detailed model has been developed that successfully correlates dissolution behavior and various experimental parameters.     

马来酸酐改性氯化聚乙烯的合成及粘接性能研究

研究了马来酸酐改性ＣＰＥ的合成反应条件,比较了纯ＣＰＥ和改性ＣＰＥ的粘接强度,用ＩＲ对 产物进行了表征。实验表明：马来酸酐能改善ＣＰＥ表面的粘接性;并探讨了己内酰胺作为电子给体添加剂对 接枝反应的影响。     

阳离子改性苯乙烯-马来酸酐共聚物的制备与表征及应用

以2,3-环氧丙基三甲基氯化铵(ETA)为阳离子化试剂,对苯乙烯-马来酸酐共聚物(SMA)进行阳离子化改性,制备出一种阳离子性高分子分散剂(SMG)。通过红外光谱、含氮量、表面张力以及溶解性等的测定,研究了SMG的结构与性质;通过对颜料黄14的分散性考察,研究了SMG的分散性能。结果表明,SMA在阳离子化过程中,酸酐基团全部开环,部分形成酯键,阳离子化度达到7.5%左右;SMG的表面活性较低,但对颜料黄14的分散稳定性较好,在pH=7.0条件下,可以使颜料的Zeta电位提高至 35.4 mV。     

Mechanical properties of blends of polycarbonate with unmodified and maleic anhydride grafted ABS

Blends of polycarbonate/acrylonitrile–butadiene–styrene terpolymer (PC/ABS) and polycarbonate/maleic anhydride grafted ABS (PC/MABS) were prepared over the whole range of compositions using a single-screw extruder. Tensile, flexural, notched Izod impact properties, and the heat deflection temperature of these blends were determined. Mechanical properties of PC/MABS blends are nearly equal to or higher than, those predicted by the rule of mixtures, whilst those of PC/ABS blends show nearly equal, or negative deviation, from the rule of mixtures. The notched impact strength of PC/MABS blends shows a positive blending effect and proportionate increase from 25wt% PC to 75wt% PC. Scanning electron micrographs were taken of etched surfaces of selective blends. © 1998 SCI.     

Polymer blends with modified coupling agent. I. Preparation and thermal properties of LICA 44 grafted styrene–maleic anhydride copolymer

Neopentyl(diallyl)oxy, tri(N-ethyleneamino)ethyl titanate (LICA 44) was grafted to the styrene/maleic anhydride (SMA) copolymer for the purpose of obtaining a new interfacial coupling agent for flame retardant ABS blends. The graft reaction was proceeded in DMSO under 80°C and reduced pressure. Samples were prepared under various amine/anhydride ratios (AAR) in feed and reaction time. The verification of reaction was based on FTIR spectra and the results of elemental analysis. The reaction percentages were high but decreased with the rising AAR. Both combination types, amide acid and imide, of SMA and LICA 44 were found, and the ratio of amide acid and imide is related to the AAR and reaction time. After the graft reaction, both the initial pyrolysis temperature (T_pi) and the char yield at 800°C of SMA increased significantly. LICA 44 is believed to cause the char promoting effect on SMA-g-L44. And the dealcohol phenomenon of trimethylolpropane diallyl ether (TMPDE) away from SMA-g-L44 was observed during the thermal analysis. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:37–44, 1998     

Functionalized polymers derived from the reaction of polymaleic anhydride with amines and alcohols

In the present study the application of polymaleic anhydride as a reactive polymer is illustrated in its reactions with didodecylamine, diphenylamine, and dodeecanol. These polymers consisting of lipophilic segments (originating from the long aliphatic chains) or of the mesomorphic diphenyl moiety coupled with the polar carboxylic or carboxylate group can in principle exhibit mesomorphism in the melt and aggregate in dispersion. Of these derivatives didodecyl derivative froms mesomorphic-like structure in the melt, dodecanol monoester derivative dissolves freely in water whereas the sodium salts of the polymers disperse in water due to the presence of distinct polar and lipophilic moieties in their molecules.     

Fabrication and characterization of maleic anhydride grafted polypropylene membranes with high antifouling properties

In this study, maleic anhydride grafted polypropylene microporous flat‐sheet membranes were prepared via a thermally induced phase separation method with a mixture of dibutyl phthalate and dioctyl phthalate as a diluent. The effects of the polymer composition and coagulation bath temperature on the morphology and performance of the fabricated membranes were investigated. The hydrophilicity results of the membranes demonstrated that membrane modification reduced the water contact angle by about 45°, whereas the pure water flux was enhanced about four times. The antifouling behavior of the fabricated membranes was also investigated in a membrane bioreactor. The results show that the pure water flux, membrane pore size, and porosity decreased, whereas the antifouling performance was improved with increasing polymer concentration and decreasing bath temperature. Finally, the results reveal that the removal efficiency of contaminates was independent on the membrane characterization and was done exclusively through biological removal. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43857.     

The dilute solution properties of maleic anhydride and maleic acid copolymers: 1. Light scattering, osmotic pressure and viscosity measurements

Dilute solution behaviour of poly(maleic anhydride-co-ethyl vinyl ether) and poly(maleic acid-co-ethyl vinyl ether) has been investigated by light scattering, osmotic pressure, and viscosity measurements. The molecular weights ($\text{M}\text{?}{}_{\mathrm{w}}$ and $\text{M}\text{?}{}_{\mathrm{n}}$), the second virial coefficients A₂, and the intrinsic viscosities [η] have been determined for three states of this copolymer: anhydride-form, H-form, and Na-salt independently. The constants in the Mark-Houwink relations were obtained for the above three states under different solvent conditions. The molecular weight of the anhydride-form is found to be higher than that of the acid-form or the Na-salt, suggesting the degradation in a process of hydrolysis. The second virial coefficient A₂ as well as the Mark-Houwink relation indicates that the anhydride-form and H-form behave as flexible polymer chains in good solvents. However, the polymer coil of Na-salt is highly expanded even at saturated NaCl concentration.