Spontaneous copolymerization of N-(2-hydroxyethyl)ethyleneimine with maleic anhydride

Summary The copolymerization of N-(2-hydroxyethyl)ethyleneimine, (HEEI) as nucleophilic monomer and maleic anhydride (MA) as electrophilic monomer in the absence of initiator in acetonitrile was investigated. Copolymers were characterized by IR, ¹H-NMR and ¹³C-NMR spectroscopy. The copolymer composition depends on the monomer ratio in the feed, determined by ¹H-NMR spectroscopy. The presence of MA bridges between copolymer chains was established by spectroscopic analysis. At lower temperature the yield and molecular weight of copolymers decrease as well as the MA unit content in the copolymer.     

Polymerization of ϵ‐caprolactone with maleic anhydride: Synthesis and characterization

High‐molecular‐weight polymers of ϵ‐caprolactone (CL) and maleic anhydride (MA) with anhydride group content of about 1% wt have been synthesized and studied. The polymerization reaction was carried out in bulk under nitrogen atmosphere. Stannous octoate (Sn(oct)₂), and 2,2'‐azobisisobutyronitrile (AIBN) were used as a catalyst and an initiator, respectively. A two‐level design of experiments was used to study the effect of various conditions on the characteristics of the copolymer. Reaction time, temperature, and concentration ratio of various reactants (two monomers, monomer to catalyst, and monomer to initiator) were the independent variables used, and the dependent variables included the molecular weight and the anhydride content in the polymer. Nuclear magnetic resonance (NMR) studies indicate that the succinic anhydride units were incorporated individually either to the polymer chain end or backbone. Anhydride content in the polymer and gel permeation chromatograph (GPC) studies indicate that the maleic anhydride acts as the true initiating species rather than as a comonomer in the system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3189–3194, 2000     

Synthesis and characterization of poly(methyl methacrylate‐co‐maleic anhydride) copolymers and its potential as a compatibilizer for amorphous polyamide blends

Poly(methyl methacrylate‐co‐maleic anhydride) copolymers (MMA‐MA) have been synthesized by solution method, using toluene as solvent and benzoyl peroxide as initiator. The MMA‐MA copolymers were characterized by size exclusion chromatography, Fourier transforms infrared spectroscopy (FTIR), and titration. It was found that the modified polymerization procedure used in this work was more effective in controlling the molecular weight when adding different amounts of maleic anhydride (MA) than procedures previously used. In spite of the significant difference in reactivity ratios between MMA and MA, up to 50% of the MA added to the reactor was incorporated into the copolymer. The evidences for reactions of the MA groups of the MMA‐MA copolymer with the amine end groups of the amorphous polyamide (aPA) during melt blending was obtained by rheological measurements. In this work, the molecular weight and the content of MA reactive functional groups in the MMA‐MA copolymer were varied independently and its effects on the interaction with aPA were studied. It was observed that a compromise between molecular weight and the level of reactive functional group of the compatibilizer should be sought to improve the compatibilization of the polymer systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

丙烯酰胺-马来酸酐共聚合物膜及其对CO2、CH4吸附性能研究

通过自由基聚合制备了丙烯酰胺(AM)和马来酸酐(MA)共聚合物.粘度法测定了聚合物的相对分子量,元素分析法和FTIR等分析表征了共聚物的化学结构,此外研究了共聚合物对CO2和CH4的溶胀吸附性能.在本实验条件下,共聚物的相对分子量、共聚物中两种单体的摩尔数之比m/n、对CO2的平衡吸附量等随聚合过程中单体配比AM/MA的增加而增大;共聚合物的相对分子量在7～17万之间,共聚物中两种单体的摩尔数之比在5～30之间,对CO2的平衡吸附量在45～70mg(CO2)· (g(干膜)) -1之间;而共聚物对CH4的平衡吸附量仅为4mg(CH4)·( g(干膜))-1左右,且不随单体配比AM/MA的增加而变化,这表明丙烯酰胺和马来酸酐共聚合物作为CO2/CH4分离用膜材料,具有较好的CO2优先选择吸附性能.     

Antiscaling properties of novel maleic‐anhydride copolymers prepared via iron (II) – chloride mediated ATRP

A class of maleic anhydride copolymers (YMR‐A series) with a narrow molecular weight distribution between 500–1500 and a polydispersity of 1.0–1.11 was obtained from n‐alkylacrylamide and maleic anhydride monomers via atom transfer radical polymerization. The monomer conversion reached about 71% corresponding to 1:4 [FeCl₂] to [SA] molar ratios for (AAH/MA) copolymer initiated by CPN whereas for the polymerization initiated by MCPN the conversion reached 51.9% under similar condition showing better performance of CPN initiator. Resultant polymers were characterized by means of ¹H‐NMR and ¹³C‐NMR. The inhibition behavior of these YMR‐A polymers against CaCO₃ and CaSO₄ was evaluated using static scale inhibition method. The inhibition efficiency on the calcium carbonate scale is much higher and even with 5 ppm dosage level the efficiency is around 99.33 % at pH 10.45 and temperature 70°C, where as for calcium sulfate scales the inhibition efficiency, is lower and 99.9% inhibition is observed at 7–9 ppm level. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39827.     

低温合成苯乙烯-马来酸酐交替共聚物

苯乙烯(St)和马来酸酐(MA)自由基引发共聚反应,生成共聚物SMA,是典型的交替共聚。在过氧化苯甲酰(BPO)引发下,以丙酮为溶剂,采用溶液聚合法合成苯乙烯-马来酸酐共聚物,并用收率作为评价标准,对反应条件进行研究。结果表明,在温度为60℃,BPO的质量分数x(BPO)=0.3%,n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=30%,反应2 h的条件下,聚合物的收率可达到98.5%。利用化学滴定法测得聚合物中马来酸酐摩尔分数为49.91%,结合理论,证明了合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。一种低温合成苯乙烯-马来酸酐交替共聚物的工艺得到开发。     

离子液体中丙烯腈三元共聚的研究

采用离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)为溶剂,进行了丙烯腈(AN)、丙烯酸甲酯(MA)、衣康酸(ITA)的自由基三元共聚反应的研究。讨论了总单体浓度、引发剂含量、聚合时间、MA含量、ITA含量对共聚物相对分子质量和转化率的影响。结果表明:以离子液体[BMIM]BF4为溶剂,AN、MA和ITA可发生三元共聚,聚合物相对分子质量可达10万以上;且MA的含量可以很低直至为0,对聚合物相对分子质量影响不大;以离子液体为溶剂的共聚物的化学结构与以NaSCN水溶液为溶剂的聚合物的结构相似。     

Removal of ungrafted monomer from polypropylene‐graft‐maleic anhydride via supercritical carbon dioxide extraction

The removal of spent initiator, excess initiator and unbound monomer from newly synthesized polypropylene‐graft‐maleic anhydride (PP‐g‐MA) has typically been carried out using Soxhlet extraction. Standard solvents used in the Soxhlet process are xylene, toluene, acetone or methanol. These chemicals are not only hazardous to some degree, but also lead to undesirable maleic anhydride (MA) ring opening. This paper establishes that supercritical carbon dioxide (scCO₂) extraction of residuals prevents anhydride ring opening and eliminates the need for post‐extraction vacuum‐drying of the copolymer product. An added benefit of this innovative process is that environmentally friendly carbon dioxide (CO₂) is used in place of harmful solvents. The successful extraction of the residuals is established by thermogravimetric analysis (TGA), whereas FTIR spectroscopy is used to compare the anhydride content of Soxhlet‐extracted PP‐g‐MA to that of scCO₂‐extracted copolymer. Polym. Eng. Sci. 44:1636–1641, 2004. © 2004 Society of Plastics Engineers.     

Synthesis and characterization of new hydrogels on the basis of water‐soluble maleic anhydride copolymers with γ‐aminopropyltriethoxysilane

This work describes the synthesis and macromolecular reactions of maleic anhydride (MA)–acrylic acid (AA) binary reactive copolymers with γ‐aminopropyltriethoxysilane (APTS) as a polyfunctional crosslinker. Copolymers with a given composition of MA–AA (47.17–52.83 wt %) were synthesized by radical binary copolymerization with benzoyl peroxide as an initiator in p‐dioxane at 70°C in nitrogen atmosphere and initial monomer ratio of 1 : 1. It is shown that the network structure is formed in MA–AA/APTS in water by intermolecular reaction between the anhydride unit and the amine group, as well as between the etoxysilyl fragment and free carboxyl groups of the acrylic acid and maleic anhydride unit. Swelling parameters such as beginning time of hydrogel formation, initial rate of swelling, swelling rate constant, equilibrium swelling, and equilibrium water content were determined for copolymer/APTS/water systems with various copolymer/crosslinker ratios. Formation of a hyperbranched network structure through the fragmentation of side‐chain reactive groups in the studied systems was confirmed by FTIR, TGA, and DSC methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4009–4015, 2003     

Synthesis and application of 2‐acrylamido‐2‐methyl propane sulfonic acid/acrylamide/N,N‐dimethyl acrylamide/maleic anhydride as a fluid loss control additive in oil well cementing

Using 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS), acrylamide (AM), N,N‐dimethyl acrylamide (NNDMA), and maleic anhydride (MA), a new dispersive type fluid loss control additive (FLCA) AMPS/AM/NNDMA/MA (PANM) was synthesized by free radical aqueous solution copolymerization, and the new FLCA could be used without dispersant existing in the cement. The optimal PANM (OPANM) was obtained under the optimum reaction conditions: mole ratio of AMPS/AM/NNDMA/MA = 4/2.5/2.5/1, monomer concentration = 32.5%, amount of (by weight of monomer) ammonium persulfate/sodium bisulfate = 1.0%, pH value = 4, and temperature = 40°C. The synthesized copolymer OPANM was identified by FTIR analysis. The evaluation results show the OPANM has excellent dispersing power, fluid loss control ability, thermal resistant, and salt tolerant ability. The OPANM was even stable when the temperature was below 300°C proved by TG analysis. The thickening time of the slurry containing the synthesized additive reduces as the temperature increases. The copolymer OPANM is expected to be an excellent FLCA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

新型聚马来酸酐-丙烯酸类阻垢剂的研究

将顺酐(MA)与苯酚在室温下混合即得到一种电荷转移配合物(CTC),然后用此配合物与丙烯酸(AA)按摩尔比1:2进行聚合反应,采用偶氮二异丁腈(AIBN)为引发剂,在反应温度60℃,反应时间5 h,引发剂用量为0.3%较缓和的条件下,合成了马来酸酐-丙烯酸共聚物(MA/AA)阻垢剂,实验结果表明,该聚合物阻垢剂对碳酸钙和磷酸钙均具有良好的阻垢性能,阻垢剂浓度为50 mg/L时,对碳酸钙的阻垢率达到100%,对磷酸钙的阻垢率达到60%以上。     

Anionic ring‐opening polymerization of adipic anhydride initiated by potassium poly(ethylene glycol)ate

Poly(adipic anhydride) (PAA) was prepared by the ring‐opening polymerization of adipic anhydride (AA) initiated by potassium poly(ethylene glycol)ate. The effects of various factors, such as the amount of initiator, concentration of the monomer, reaction time and temperature, and polarity of the solvent on the polymerization were investigated. The crude polymerized product was a mixture of PAA homopolymer and poly(ethylene glycol)–poly(adipic anhydride) block copolymer, as confirmed by ¹H‐NMR and gel permeation chromatography. Chain‐transfer reactions occurred intensively for the AA polymerization in both the nonpolar solvent toluene and the polar solvents CHCl₃ and tetrahydrofuran, which predominantly determined the molecular weight and the monomer conversion for the polymerized product. The lower monomer conversion in toluene was ascribed to a lower livingness for the initiator in the nonpolar solvent when compared with other two, polar solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2194–2201, 2003     

新型阻垢剂IA-SSS-MA聚合物的合成与表征

以衣康酸(IA)、苯乙烯磺酸钠(SSS)和马来酸酐(MA)为单体,以水为溶剂,过硫酸铵作引发剂,合成了衣康酸-苯乙烯磺酸钠-马来酸酐(IA-SSS-MA)三元聚合物阻垢剂,考察了单体配比、反应温度、引发剂量、滴加时间等对聚合物阻碳酸钙垢效果的影响,结果表明:当单体配比为IA∶SSS∶MA=5∶1∶0.25(摩尔比),反应温度100℃,引发剂量占单体总量13%,滴加时间为5 h,阻碳酸钙垢效果最好,阻垢率达到98.11%。     

A novel copolymer of N-[(tert-butylperoxy)methyl]acrylamide and maleic anhydride for use as a reactive surfactant in emulsion polymerization

A new copolymer of N-[(tert-butylperoxy)methyl]acrylamide (tBPMAAm), containing a primary–tertiary peroxide group and maleic anhydride (MA), was synthesized and employed as a reactive surfactant (inisurf) for the emulsion polymerization of styrene to yield surface-functionalized (peroxidized) reactive latex particles. The copolymerization characteristics were analyzed to determine the monomer reactivity ratios and to provide a way to control the copolymer composition. The ability of tBPMAAm–MA to act as a reactive surfactant during emulsion polymerization was confirmed by the synthesis of monodisperse polystyrene latexes of varying particle size. In addition, peroxide groups were localized on the surface of the particles in a controllable amount (depending on the copolymer concentration), thus, providing the opportunity for further modification of the surface of the particles. This novel copolymer is expected to be a promising and efficient material in the synthesis of functional polymer nanoparticles with well-defined core–shell morphologies.     

Synthesis and characterization of alkali‐modified styrene‐maleic anhydride copolymer for dispersion of TiO2

A copolymer of styrene and maleic anhydride was synthesized by free radical polymerization at 80°C using N,N‐dimethylformamide (DMF) as solvent and benzoylperoxide as initiator. The monomer feed ratio of styrene to maleic anhydride was varied in the range of 1 : 1 : to 3 : 1. The polymer yield was found to decrease with increase in styrene in the feed. The molecular weight of copolymers which were formed by taking styrene to maleic anhydride ratio of 1 : 1, 2 : 1, and 3 : 1, as determined by Ostwald Viscometery were about 1862, 2015, and 2276 respectively. The acid values of abovementioned three copolymers were found to be 480, 357, and 295, respectively. The typical viscosity values of 20% solids in ammonical solution of copolymers formed by taking feed ratios of Sty : MAn as 1 : 1 and 2 : 1 were 26 and 136 cp, respectively. For the feed ratio 3 : 1, a gel was formed. The synthesized copolymers were hydrolyzed by alkalis, namely, NaOH, KOH, and NH₄OH. The dispersing ability of hydrolyzed styrene‐maleic anhydride (SMA) copolymers for dispersion of titanium dioxide was studied. The modified SMA copolymers were found to be effective dispersants for TiO₂. Among the three alkalis studied, the Sodium salts of SMA were found to give better dispersion. The copolymer having a 1 : 1 feed ratio showed the best dispersing ability for TiO₂ particles among the three ratios studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3194–3205, 2007     

Syntheses and characterization of starch-poly(methacrylic acid) graft copolymers

Methacrylic acid (MA) was graft polymerized onto starch using Ce⁴⁺ initiator in aqueous medium. The dependence of grafting on the reaction variables, such as monomer and initiator concentration and time and temperature, was studied in detail. Acid hydrolysis and infrared (IR) spectroscopy were used for the confirmation of graft copolymer formation. Further, a representative graft copolymer was characterized by x-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The solubility/swellability and the gelatinization characteristics of the copolymers are also reported. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1399–1403, 1997     

新型三元聚合物阻垢剂的合成及性能评价

在水溶液中,以过硫酸钾为引发剂,马来酸酐(MA)、丙烯酸甲酯(MAC)、甲基丙烯磺酸钠(SMAS)为反应单体,合成无磷聚合物(MA/MAC/SMAS)。探讨了阻垢剂投加量、阻垢实验温度对聚合物阻垢率的影响,在静态试验条件下评价了其对氧化铁的分散性能,用正交实验法确定了最佳合成条件:单体配比n(马来酸酐)∶n(丙烯酸甲酯)∶n(甲基丙烯磺酸钠)=1.5∶0.5∶0.1,引发剂用量为单体的10%(wt),反应温度为80℃,反应时间为3 h。结果表明:引发剂用量是影响聚合物阻垢率的主要因素,该聚合物具有良好的阻垢分散性,阻垢率高达90.1%,     

Spontaneous copolymerization of N-(2-hydroxyethyl)ethyleneimine with isatoic anhydride

The polymerization of isatoic anhydride (electrophilic monomer) with N-(2-hydroxyethyl)ethyleneimine (nucleophilic monomer) was studied in the absence of added initiator at different feed monomer concentrations, temperature, and time of copolymerization. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopy, and TGA. Based on spectroscopic data and copolymer composition, a copolymer structure was suggested. Received: 25 April 1997/Revised: 11 August 1997/Accepted: 14 August 1997     

溶液聚合法合成苯乙烯-马来酸酐交替共聚物

在过氧化苯甲酰(BPO)引发下,以丁酮为溶剂,采用溶液聚合法合成了苯乙烯-马来酸酐共聚物,并详细研究了温度、引发剂用量、苯乙烯与马来酸酐配比、单体(苯乙烯与马来酸酐)质量分数及聚合时间对聚合反应的影响。研究表明,在温度80℃,x(BPO)=0.6%(相对于苯乙烯与马来酸酐),n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=15%(相对于混合溶液),反应时间4 h的条件下,聚合物收率可达99%。采用13CNMR、IR、GPC、元素分析对共聚物结构进行了表征。利用TG测定了其热稳定性。结合共聚物的元素分析与13CNMR的分析结果,表明合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。     

A new simple procedure to calculate monomer reactivity ratios by using on-line 1H NMR kinetic experiments: Copolymerization system with greater difference between the monomer reactivity ratios

Free radical copolymerization reaction of vinyl acetate (VA) and methyl acrylate (MA) in solution of benzene-d₆ using benzoyl peroxide (BPO) as the initiator was studied with on-line ¹H NMR kinetic experiments at 60 °C. It was observed that composition drifts in the comonomer mixture with reaction progress is significant. Hence, the monomer reactivity ratios of VA/MA system could be calculated by the data collected only from one sample via on-line following the comonomer mixture and copolymer compositions at different reaction time intervals up to medium overall monomer conversions. The results were in good agreement with the literature data reported for this system. The good fitting between theoretical and experimental changes in the comonomer mixture compositions as a function of reaction progress was observed, indicating the accuracy of the monomer reactivity ratios calculated by the new procedure presented here.