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

The 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     

Production of alkenyl succinic anhydrides from low‐erucic and low‐linolenic rapeseed oil methyl esters

Fatty acid methyl esters from low‐erucic and low‐linolenic rapeseed oil were used to produce alkenyl succinic anhydrides. A second‐order Doehlert uniform network design was used to investigate the influence of the reaction temperature and the molar ratio between the maleic anhydride and the main unsaturated rapeseed oil methyl esters on the yield of alkenyl succinic anhydride from methyl oleate. Further subjects of investigation were the conversion of methyl oleate, the formation of side reaction products, the Gardner color of the product and its viscosity, and finally the content of maleic anhydride remaining in the medium after the reaction. Alkenyl succinic anhydride from methyl oleate was isolated by column chromatography and analyzed by IR, ¹H‐ and ¹³C‐NMR and MS. The optimal reaction conditions for obtaining the maximum yield of alkenyl succinic anhydride from methyl oleate in the experimental domain (80%) were 210‐220 °C and a maleic anhydride/rapeseed oil methyl ester molar ratio of 1.5. However, the products synthesized in these conditions showed a high degree of viscosity (0.45 kg m^?1 s^?1), a very dark color (18 Gardner color) and a high content of undesirable side products (6%), which could hinder their industrial use. A molar ratio of less than 1.5 led to a clearer and less viscous product, although with a lower alkenyl succinic anhydride content.     

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

A polymer‐supported (PS) phase transfer catalyst, polyethylene‐g‐quaternary ammonium salt (PE‐g‐Q_N⁺), 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‐Q_N⁺. 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‐Q_N⁺ were characterized by FTIR Spectroscopy and thermogravimetric analysis (TGA). The ionic nature of quaternary ammonium salt, PE‐g‐Q_N⁺ has also been confirmed by conductance measurements. PE‐g‐Q_N⁺ 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     

Grafting copolymerization of maleic anhydride onto styrene‐butadiene‐styrene block copolymer through solvothermal process

The grafting copolymerization of maleic anhydride (MAH) onto styrene‐butadiene‐styrene terpolymer (SBS) was carried out through a new synthesis method––solvothermal synthesis. Infrared (IR) spectra and solid state ¹³C‐NMR confirmed that maleic anhydride was successfully grafted onto the SBS backbone. The effects of different solvents, different initiators and their concentration, the amount of MAH, SBS concentration, and reaction time on the graft degree were evaluated, and the optimal conditions were obtained. Results indicated that the grafting reaction of MAH onto SBS through solvothermal method can be carried out in both good solvents and poor solvents, which are much different from the traditional solution grafting method, and high grafting degree can be obtained in good solvents. Finally, we also compared the grafting degree (GD) prepared by the solvothermal method with that by the melt grafting method and solution grafting method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5274–5279, 2006     

Succinoylation of wheat straw hemicelluloses in N,N‐dimethylformamide/lithium chloride systems

The chemical modification of native wheat straw hemicelluloses with succinic anhydride using N,N‐dimethylformamide/lithium chloride system as solvent and pyridine and/or 4‐dimethyaminopyridine as catalyst has been examined. In particular, the progress of the succinoylation reaction is studied as a function of the molar ratio of succinic anhydride/anhydroxylose unit in native hemicelluloses from 1:1 to 5:1, DMAP concentration 0.025–0.20 g, reaction temperature 40–140 °C, and reaction time 2–12 h with succinic anhydride. The degree of substitution of succinylated hemicelluloses ranges between 0.4 and 1.5 depending on the experimental conditions. FTIR and ¹H NMR spectroscopic characterization of the esterified polymers indicates a monoester substitution. The thermal stability of the esterified polymer decreases slightly upon chemical modification, but no significant further decrease in thermal stability is observed for DS ≥ 0.7. © 2001 Society of Chemical Industry     

Phase‐transfer‐agent‐aided polymerization and graft copolymerization of acrylamide

The use of phase‐transfer catalysts, with water‐insoluble initiators, for polymerization and graft copolymerization reactions was explored. The polymerization of a water‐soluble vinyl monomer, acrylamide (AAm), and the graft copolymerization of AAm onto a water‐insoluble polymer backbone, isotactic polypropylene (IPP), with a water‐insoluble initiator, benzoyl peroxide (BPO), and a phase‐transfer catalyst, tetrabutyl ammonium bromide (Bu₄N⁺Br^?), were carried out in a water/xylene binary solvent system. The conversion percentage of AAm into polyacrylamide (PAAm) and the percentage of grafting of AAm onto IPP were determined as functions of various reaction parameters, such as the BPO, AAm, and phase‐transfer‐catalyst concentrations, the amounts of water and xylene in the water/xylene mixture, the time, and the temperature. The graft copolymer, IPP‐g‐PAAm, was characterized with IR spectroscopy and thermogravimetric analysis. By a comparison of the results of the phase‐transfer‐catalyzed graft copolymerization of AAm onto IPP and the preirradiation method, it was observed that the optimum reaction conditions were milder for the phase‐transfer‐catalyst‐aided graft copolymerization. Milder reaction conditions, including the temperature, the time of reaction, and a moderate initiator (BPO), in comparison with high‐energy γ‐rays, led to better quality products, and the reaction proceeded smoothly with high productivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2364–2375, 2004     

Synthesis of graft polyesters by ring-opening copolymerization of epoxy-terminated poly(ethylene glycol) with acid anhydrides

The copolymerization of epoxy-terminated poly(ethylene glycol methyl ether) (CH₃PEG–epoxide) with phthalic anhydride catalyzed by tertiary amines was performed in o-dichlorobenzene at 100°C to prepare the PEG graft polyester. 4-Dimethylaminopyridine was the most favorable catalyst to give the graft polyester with relatively high molecular weight. The acidity of the reaction solution decreased and M _n of the graft polyesters increased with reaction time. The CH₃PEG/phthalic acid ratio of the products was little affected by the kind of solvent and the reaction temperature above 100°C, but M _n increased with lowering the polarity of solvents and with raising the temperature. Other acid anhydrides, including maleic, succinic, tetrahydrophthalic, and pyromellitic anhydride, could be copolymerized with CH₃PEG–epoxide. The number of branched CH₃PEG chains was controlled by the mixing of low molecular weight epoxide such as n-butyl glycidyl ether. CH₃PEG component of the graft copolymers melted and crystallized at lower temperature than the raw CH₃PEG because of the restriction on the trunk polyester chain.     

Synthesis of wheat straw composite superabsorbent

A novel wheat straw composite superabsorbent was prepared by graft polymerization with acrylic acid (AA), acrylamide (AM), and maleic anhydride‐modified wheat straw in aqueous solution, using N,N‐methylene‐bis‐acrylamide (MBA) as a cross‐linker and ammonium persulfate (APS) and sodium bisulfite (SBS) as redox initiators. Factors influencing the degree of carboxylation, such as reaction time, reaction temperature, and the amount of maleic anhydride, were investigated. Morphologies and structure of the wheat straw composite superabsorbent were characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and X‐ray diffraction (XRD). Water absorption of wheat straw composite superabsorbent was rapid, requiring 13.1 min to reach 63% of equilibrium absorbency (781 g/g). FTIR spectra indicate that maleic anhydride has been reacted onto the wheat straw backbone and the structure of wheat straw graft copolymer is formed. SEM data show that the fibrous morphology of wheat straw disappears and gel aggregates with many large microporous holes are formed after wheat straw graft modification. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3404–3410, 2013     

Solid state grafting copolymerization of acrylamide onto poly(vinyl alcohol) initiated by redox system

A solid state grafting copolymerization of acrylamide (AM) onto poly(vinyl alcohol) (PVA) was conducted with ammonium persulfate and sodium bisulfite redox system as initiators. Before the reaction the PVA powder and required amount of AM were mixed evenly, and sprayed with water to swell the PVA powder and to dissolve AM. Then the swollen PVA powder was sprayed with the redox solution, and the reaction temperature was controlled at a temperature between 30°C and 80°C for 120 min. The grafting percentage and efficiency were determined as functions of monomer/PVA ratio, initiator concentration and reaction temperature. The structure and performance of the graft copolymers were confirmed by FTIR‐ATR, XRD, ¹³C NMR, and thermogravimetric analysis, together with mechanical property and apparent viscosity measurements. It has been confirmed that grafting copolymerization of AM onto PVA initiated by this redox system occurred with higher grafting percentage and efficiency in the solid state. The thermal stability and water‐solubility of grafted PVA were found to be better than those of unmodified PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39938.     

Comparison of succinylation methods for bacterial cellulose and adsorption capacities of bacterial cellulose derivatives for Cu<Superscript>2+</Superscript> ion

Bacterial cellulose (BC) was homogenously modified with succinic anhydride in N,N-dimethylacetamide/LiCl in the presence of triethylamine and heterogeneously in pyridine in the presence of 4-dimethylaminopyridine. FTIR, XRD, 13C CP MAS NMR, SEM were used to characterize BC and succinylated bacterial cellulose (SBC). For homogeneous modification, the degree of substitution (DS) of SBC differs from 0.21 to 1.45 with the variation of the adding amount of succinic anhydrate, temperature, reaction time, and the amount of triethylamine. DS and XRD profiles reveal that heterogenous reaction mainly happens on the surface of BC membrane. The adsorption capacity and mechanism of Cu²⁺ onto BC and SBC were investigated. The result shows the adsorption is affected by the morphology and the DS of adsorbents.     

Oleophilic modification of poly(vinyl alcohol) films by functionalized soybean oil triglycerides

In this study, maleinized (SOMAP) and isocyanated soybean oil (SONCO) triglycerides have been successfully grafted onto one surface of poly(vinyl alcohol)(PVA) films to give films that are hydrophilic on one side and hydrophobic on the other. The surface grafting was accomplished by the reaction of succinic anhydride or isocyanate functionalities of soybean oil derivatives and the hydroxyl groups of PVA films. The reaction was run in toluene, using PVA films on glass slides so that only one side of the film was accessible. After grafting, the films were rinsed with hot toluene to remove ungrafted triglycerides from the surface. The reaction on the surface was confirmed by ATR‐FTIR and ¹H‐NMR spectroscopic techniques. A series of films were prepared at different concentrations of SOMAP or SONCO in toluene. The increase in hydrophobicity with an increase in SOMAP or SONCO concentrations was observed by water contact angle measurements. The contact angles on the grafted side of the film reach their maximum value of 88° and 94° for 26 and 2.5% SOMAP and SONCO concentrations in toluene, respectively, while the ungrafted side gives contact angle of 48°. Surface morphologies of PVA‐g‐SOMAP and PVA‐g‐SONCO films were investigated by atomic force microscopy, whereas optical microscopy and staining was used to determine the homogeneity of the films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of a macromolecular surface modifier for polypropylene

A novel macromolecular surface modifier, a polypropylene‐graft‐poly(butyl methylacrylate) copolymer, was synthesized through the coupling of polypropylene containing maleic anhydride with monohydroxyl‐terminated poly(butyl methylacrylate). The effects of the raw ratio, reaction temperature, and molecular weight of the branches on the graft reaction were studied. The graft copolymers were characterized with IR, ¹H‐NMR, thermogravimetry, and differential scanning calorimetry. The results of attenuated total reflection/Fourier transform infrared and contact‐angle measurements indicated that polypropylene‐graft‐poly(butyl methylacrylate) could diffuse preferably onto the surface and be used as a surface modifier for polypropylene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3413–3419, 2006     

Polycondensation of lactic acid catalyzed by organic acid anhydrides

Poly(lactic acid) was prepared by the utilization of the acid anhydrides cis‐butenedoic anhydride, phthalic anhydride and pyromellitic dianhydride as catalysts. The effect of the amount of catalyst, temperature and reaction time on the polymerization was investigated in detail. The results show that the acid anhydride catalysts are very efficient in bulk polycondensation, giving poly(D ,L ‐lactic acid) with average molecular weights (M_w) of (1.7–2.3) × 10⁴ in high yield. Copyright © 2007 Society of Chemical Industry     

Preparation and characterization of ultra‐low molecular weight poly(vinyl alcohol) graft copolymer

Graft reaction of acrylamide (AM) and 4‐vinyl pyridine (4‐VP) onto ultra‐low molecular weight poly(vinyl alcohol) by ceric (IV) ion initiation had been systematically investigated; and the graft conditions were optimized by studying the effect of monomer/initiator concentration, solvents composition, reaction time and temperature. At optimized conditions, the maximum grafting efficiency and grafting ratio was ～ 50% and 51%, respectively with the presence of AM, whereas they decreased to 19% and 23%, respectively, without the presence of AM. Thermogravimetric analysis showed that as‐resulted graft copolymer had a lower thermal stability than homopolymer PVA. FTIR and ¹H‐NMR confirmed chemical structure of as‐synthesized graft copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

壳聚糖/聚己内酯接枝共聚物的均相合成与表征

以离子液体1-丁基-3-甲基咪唑醋酸盐（［BMIM］Ac）为反应介质,研究了壳聚糖与ε-己内酯的均相接枝共聚反应,考察了反应温度、时间、催化剂用量等对接枝率的影响,并利用红外光谱、核磁共振氢谱、热重分析、X射线衍射等对接枝共聚物进行了表征。结果表明,均相条件下壳聚糖与ε-己内酯的接枝共聚反应时间短、效率高,在反应温度为105℃,反应时间为8 h,催化剂Sn(OCt)₂的用量为ε-己内酯质量的0.1%,ε相似文献   

顺酐液相加氢制备丁二酸酐

一步法顺酐加氢生产丁二酸酐的最佳条件为:加氢压力1~1.6 MPa,反应温度50~100℃,反应时间1~2 h,骨架镍催化剂用量是顺酐用量的4%~6%,搅拌速度300 r/m in,在此条件,丁二酸酐的最高收率可达90%以上。     

Reaction kinetics of graft copolymerization and thermochemical studies of the degradation of poly(vinyl alcohol) graft copolymer

Poly(vinyl alcohol) (PVA) is a water‐soluble and biomedical polymer. 2‐Acrylamido‐2‐methyl‐1‐propanesulfonic acid was grafted onto PVA using ammonium persulfate as radical initiator. The influences of synthesis conditions such as temperature, concentrations of initiator, PVA and monomer were investigated. Both the initial rate of grafting and the final percentage of grafting were increased by an increase in reaction temperature. The reaction kinetics were studied to determine the rate constants of the first‐order reactions. An activation energy of 16.3 kJ mol^?1 was found for the grafting reaction. The graft copolymers were characterized by IR and intrinsic viscosity measurements. A proposed mechanism of the grafting reaction is discussed. Kinetics of the thermal degradation were studied using a thermogravimetric method and the order of thermal stabilities are given. The apparent activation thermodynamic parameters, E_a, ΔH*, ΔS* and ΔG* were determined and correlated to the thermal stabilities of the homo‐ and grafted polymers. © 2001 Society of Chemical Industry     

Crosslinking of poly(vinyl alcohol) using dianhydrides as hardeners

The crosslinking reaction of poly(vinyl alcohol) (PVA) with 3,3′,4,4′-tetracarboxybenzophenone dianhydride, pyromellitic carboxylic acid anhydride, and Epiclon B-4400 as hardeners was studied either in solution or by differential scanning calorimetry. A catalyst agent had to be used in all cases. Depending on the concentration of hardener and catalyst, differences are observed. T_g values increase with the ratio of hardener and catalyst, while activation energies decrease with the amount of catalyst but little changes can be seen when different dianhydride amounts are used. The thermal properties of the final products were unaltered by the hardener used. The decomposition temperature is initiated at a similar temperature in linear and crosslinked PVA, but while uncured PVA undergoes a complete degradation in one step, crosslinked PVA degrades in several steps. © 1996 John Wiley & Sons, Inc.     

单过氧丁二酸氧化环己酮合成ε-己内酯(英文)

In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid（PSA）. Then PSA was applied to synthesis of ε-caprolactone（ε-CL） by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR（infrared spectra） and1HNMR（1H nuclear magnetic resonance）. Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.     

Analysis of the solid phase copolymerization grafting process

Solid phase grafting, which is an emerging process for the production of graft copolymers, was analyzed and reviewed as an environmentally friendly and inexpensive graft copolymerization process. The effect of the process variables; amount of initiator, catalyst, interfacial agent, monomer, reaction temperature and reaction time were examined. Two graft copolymers, produced by solid phase grafting, were used to show differences in graft percentage by changing the process conditions. The two graft copolymers used were maleic anhydride graft onto polypropylene and acrylic acid graft onto polystyrene. A proposed mechanism was given for each example and characteristic bonds proposed in the PP-g-MA mechanism was positively identified by NMR spectroscopy. Graft levels of 4 wt% PS-g-AAc and 9.6 wt% PP-g-MA were obtained providing comparable or superior graft levels to other grafting processes. Successful scale-up of the solid phase technique proved that this process is efficient and marketable.