高锰酸钾引发双水相中淀粉接枝丙烯酰胺共聚反应

在双水相中进行淀粉接枝丙烯酰胺共聚反应是一种新的聚合方法,对以聚乙二醇为分散介质、高锰酸钾为引发剂的双水相中淀粉接枝丙烯酰胺共聚反应进行了研究,考察了引发时间、引发剂浓度及配比对产品单体转化率、接枝率和接枝效率的影响。通过实验得到聚合反应的最佳工艺条件:引发时间为10 min,n(高锰酸钾)∶n(丙烯酰胺)=3.0×10-4∶1,n(高锰酸钾)∶n(H+)=1∶10,反应温度为50℃,反应时间7 h,此时得到的产品的单体转化率C为98.88%,接枝率G为144.53%,接枝效率GE为97.81%。最后通过红外光谱仪进行结构表征。     

Aqueous polymerization of acrylamide by electrolitically generated KMnO4 organic acid redox systems

Polymerization of acrylamide was carried out with potassium permanganate–malonic acid, potassium permanganate–tartaric acid, and potassium permanganate–citric acid redox initiator systems with and without electrolysis. The effect of potassium permanganate concentration, acrylamide concentration, and temperature on the polymerization yield was studied and molecular weights of polymers were determined and compared with electrolytic conditions. At low concentrations of potassium permanganate, continuously supplying Mn(III) has an advantage over the noneelectrolytic method for which polymerization did not occur under these conditions. © 1996 John Wiley & Sons, Inc.     

Synthesis and physicochemical properties of graft copolymer of corn starch and acrylamide

Graft copolymerization of corn starch with acrylamide using ceric ammonium sulphate/citric acid initiation system has been studied under nitrogen atmosphere in aqueous medium. The grafting parameters are favored by increasing monomer concentration and reaction time but are affected by higher concentration of initiator and high temperature. The optimum conditions established for grafting were as follows: the concentration of initiator, 0.003 mol/L; the concentration of citric acid, 0.03 mol/L; monomer/starch, 1:1 feed ratio (w/w); reaction time, 3.0 h; and temperature, 35°C. The extent of grafting was examined by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. Both swelling power and solubility increased with the increase in temperature. Graft copolymerization increased swelling power and reduced solubility. Rapid visco‐analyzer pasting profile was studied. Graft copolymerization of corn starch results in high pasting temperature, high peak viscosity, and setback as compared with native starch. Breakdown was retarded at low percentage grafting (6.60%) but increased at high percentage grafting (60.27%). POLYM. COMPOS. 28:47–56, 2007. © 2007 Society of Plastics Engineers     

Graft copolymerization of acrylonitrile onto starch using potassium permanganate as initiator

The ability of potassium permanganate to induce graft copolymerization of acrylonitrile (AN) onto starch was investigated. The graft yield depends on monomer and initiator concentrations as well as reaction time and temperature. Chemical analysis of the reaction product of starch and (AN) in presence of potassium permanganate revealed that the latter acted as initiator for polymerization of AN and as oxidizing agent for starch. Proof for grafting was provided through infrared analysis and solubility properties of the reaction product.     

淀粉接枝丙烯酸聚合型絮凝剂的合成及絮凝性能研究

以可溶性淀粉为主要原料,以丙烯酸为接枝单体,硝酸铈铵和过硫酸钾为复合引发剂,采用溶液聚合的方法对糊化处理后的淀粉进行接枝聚合,合成出环保型淀粉衍生物水处理絮凝剂。通过对接枝聚合反应温度、反应时间、引发剂用量以及丙烯酸单体用量等因素对接枝率影响的研究,确定较佳的接枝产物合成条件：淀粉10g,单体丙烯酸用量10mL,硝酸铈铵和过硫酸钾（摩尔比1：1）复合引发体系用量2mmol,接枝反应温度50℃,接枝反应时间3h,接枝率达到43．2％。利用选煤后的废水对其产品絮凝性能进行实验研究,确定较佳的废水絮凝处理条件。     

Improved synthesis of poly(MAA)–starch graft copolymers

Graft copolymerization of methacrylic acid (MAA) onto starch using a potassium persulfate/sodium thiosulfate redox initiation system was investigated. Emphasis was placed on the promotion of graft formation while minimizing homopolymerization. This could be achieved through a thorough investigation into the major factors affecting the polymerization reaction such as the state of the starch, redox ratio of the initiator, monomer and initiator concentrations, time and temperature of polymerization, and material-to-liquor ratio. The results obtained imply that the magnitude of the polymer yield including total conversion, graft yield, and homopolymer are determined by these factors. The yield is favored under the influence of higher temperature, longer time, short liquor, and increased monomer and initiator concentrations. A poly-(MAA)–starch graft copolymer is the main product of the polymerization reactions only when starch was preswelled (through cooking prior to grafting). Moreover, this grafted product could be precipitated by more dilution with water and easily separated by filtration. Hence, the results of the current work formed the basis of a novel method for the synthesis of poly(MAA)–starch graft copolymers. The mechanisms involved in the synthesis are reported. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1709–1715, 1998     

Synthesis of nanosized poly(ethyl acrylate) particles via differential emulsion polymerization

Nanoparticles of poly(ethyl acrylate) were synthesized via a semibatch differential emulsion polymerization method with potassium persulfate as the initiator and sodium dodecyl sulfate as the surfactant. The effects of the reaction temperature, aging time, and surfactant/initiator/monomer ratios on the polymer particle sizes were investigated. Poly(ethyl acrylate) with particle sizes of less than 20 nm was synthesized under mild conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1609–1614, 2006     

淀粉接枝丙烯酸异辛酯-醋酸乙烯共聚反应的研究

采用乳液聚合的方法,以硝酸铈铵为引发剂,十二烷基硫酸钠为乳化剂,重点考察了淀粉与醋酸乙烯／丙烯酸异辛酯的接枝共聚反应中引发剂浓度、单体浓度、反应温度、反应时间等条件对接枝率、接枝效率以及接枝反应速率的影响,得到了较为理想的产物。结果表明,接枝率最高可达248.9％,接枝效率可达72.1％,单体转化率可达94.3％。     

The use of amylose‐rich starch nanoparticles in emulsion polymerization

Regenerated starch nanoparticles (RSNPs) produced from dent corn, an amylose‐rich source of starch, are added to an emulsion polymerization. To reduce or eliminate the challenges of polymerizing in the presence of amylose‐rich starch, a seeded, semibatch, monomer‐starved approach is used. To prevent the accumulation of water soluble amylose in the aqueous phase, reaction with a hydrophobic compatibilizing monomer, butyl acrylate, is used prior to the primary butyl acrylate/methyl methacrylate/acrylic acid feed. In addition, an elevated initiator concentration is used in the seed stage to reduce the molecular weight of the soluble starch and promote grafting. The procedure yields a 100.0 cp latex with 40 wt % solids, 25 wt % RSNP loading, and 40 wt % incorporation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46485.     

焦磷酸锰络阴离子引发淀粉与苯乙烯及其二元单体接枝共聚的研究

采用廉价无毒的焦磷酸锰（Ｍｎ＾３＋）络离子作为引发剂，以十二烷基硫酸钠为乳化剂，对淀粉与苯乙烯及二元单体接枝共聚进行了初步探索，研究了单体浓度，引发剂浓度，反应温度及反应时间对接枝反应的影响趋势，发现Ｍｎ＾３＋具有良好的引发效果，接枝效率在６５％～９０％，接枝率可达２００％，对淀粉与Ｓｔ／ＡＮ，Ｓｔ／ＥＡ二元单体接枝共聚的研究表明接枝效率不高。     

Graft polymerization of different monomers onto carbamated starches derived from native and hydrolyzed starches

Rice starch was hydrolyzed with hydrochloric acid so that starches would be obtained with different molecular sizes. The derived hydrolyzed starches were carbamated at various reaction times and were grafted with different monomers with a potassium permanganate/citric acid system as an initiator. The newly tailored starch‐derived products were evaluated as sizing agents. The extent of carbamation increased with increasing hydrolysis and increasing reaction time. The graft yields of different monomers on carbamated starches and carbamated hydrolyzed starches increased with increasing carbamation and increasing hydrolysis in the following order: acrylamide > acrylonitrile > acrylic acid. Cotton fabrics sized with grafted carbamated hydrolyzed starches acquired higher mechanical properties (tensile strength, elongation at break, and abrasion resistance) than hydrolyzed starches, carbamated starches, and carbamated hydrolyzed starches. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 959–965, 2003     

Graft polymerization of acrylic acid onto starch using potassium permanganate acid (redox system)

Graft polymerization of acrylic acid (AA) onto rice starch using postassium permanganate/acid redox system as initiator was investigated. When starch was reacted with KMnO₄ solution, MnO₂ was deposited onto starch. The dependence of MnO₂ amount deposited was directly related to KMnO₄ concentration. Subjecting the MnO₂-containing starch to a solution consisting of monomer (AA) and acid (citric, tartaric, oxalic and hydrochloric acid) formed poly(AA)–starch graft copolymers. The graft yield, expressed as meq COOH/100 g starch, was measured by the amount of MnO₂ deposited, AA concentration, material-to-liquor ratio, kind and concentration of acid, as well as temperature and duration. Finally, the newly prepared poly(AA)–starch graft copolymers were applied to cotton textiles to determine their suitability as sizing agents. The highest graft yield was obtained with citric acid and the least with hydrochloric acid, with tartaric and oxalic acid in between. The graft yield increased by increasing the concentration of acid to a certain concentration beyond which grafting leveled off. A similar trend was observed when the magnitude of grafting was related to the amount of MnO₂ deposited. The graft yield increased by increasing the polymerization temperature from 30° to 50°C. Increasing the temperature to 60°C is accompanied by decreased grafting. On the other hand, fabric samples sized with poly(AA)–starch graft copolymers acquire higher tensile strength, elongation at break, and abrasion resistance than that sized with native rice starch, i.e., poly(AA)–starch graft copolymers serve as good sizing agents for cotton textiles. A tentative mechanism for grafting rice starch with AA using the KMnO₄/acid redox system was elucidated. © 1995 John Wiley & Sons, Inc.     

酶解淀粉-苯乙烯/丙烯酸丁酯接枝共聚物乳液的制备研究

采用无皂乳液聚合的方法,以过硫酸铵(APS)为引发剂,制备了酶解淀粉与苯乙烯(St)和丙烯酸丁酯(BA)的接枝共聚物。探讨了淀粉与单体配比、过硫酸铵用量、单体配比和反应温度对接枝反应的影响。结果表明,反应的优化条件为:m(淀粉)∶m(单体)=1∶3,(NH4)2S2O8的加入量为淀粉与单体总质量的0.5%,单体质量比为1∶1,反应温度为82℃,在此条件下,接枝率可达103.8%,接枝效率为37.4%,单体转化率为91.9%。红外光谱分析表明,苯乙烯和丙烯酸丁酯参与了接枝反应;SEM结果显示,接枝反应之后,淀粉形貌发生了变化,球状颗粒已经消失。     

PBT熔喷非织造布的接枝改性研究

研究了以高锰酸钾/硫酸为引发剂,丙烯酰胺与PBT熔喷非织造布的接枝共聚反应。考察了溶胀剂甲苯浓度、高锰酸钾浓度等因素对接枝共聚反应的影响规律。结果表明:当甲苯质量分数为2.0%、高锰酸钾浓度为0.001 5 moL/L、硫酸浓度为0.30 moL/L、预引发温度为60℃、预引发时间为60 min、丙烯酰胺浓度为0.35 moL/L、反应温度为60℃、反应时间为3.5 h时,接枝效果最佳。     

氧化还原引发淀粉与丙烯酸接枝共聚研究

研究了马铃薯淀粉与丙烯酸的接枝共聚反应,以过硫酸钾-亚硫酸氢钠为氧化还原引发体系,考察了不同引发剂浓度、单体浓度、反应温度、反应时间等对单体转化率、接枝率和接枝效率的影响;用红外光谱对共聚物进行了表征。结果表明,采用氧化还原引发体系可使聚合反应低温快速进行,并确定反应较佳条件。     

Kinetics and mechanism of free radical grafting of methyl acrylate onto sago starch

The graft copolymerization was carried out by methyl acrylate with sago starch in which ceric ammonium nitrate was used as an initiator. It has been found that the rates of graft polymerization and grafting efficiency were dependent upon the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU, anhydro glucose unit), mineral acid (H₂SO₄), and as well as reaction temperature and period. A rate equation of polymerization was established from the proposed reaction mechanism, and the rate of polymerization (R_p) was the first‐order dependence of the MA monomer concentration and square root of the CAN concentration. A new kinetic model of the grafting reaction has been proposed, and a normal kinetics of methyl acrylate polymerization was observed. An equation of a predicted model relating the graft fraction of poly(methyl acrylate) with the sago starch has been derived, and validity of the predicted model was verified by the experimental results. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 784–791, 2000     

微波辐射下淀粉-丙烯酰胺接枝共聚物的合成

以硝酸铈铵作为引发剂、丙烯酰胺为单体,用微波辐射法合成了淀粉接枝丙烯酰胺共聚物。探讨了反应时间、引发剂浓度、单体和淀粉质量比和反应温度等因素对接枝反应的影响。正交实验确定的最优工艺条件为:反应时间20 m in,引发剂浓度4 mmol/L,丙烯酰胺和淀粉质量比2.5∶1,反应温度55℃,最高接枝率和接枝效率分别达到211.6%和74.3%。     

Grafting onto wool,XVII. Graft copolymerization of methyl acrylate and ethyl acrylate by use of VO(acac)2 as initiator. Comparison of monomer reactivities

Graft copolymerization of acceptor monomers methyl acrylate and ethyl acrylate onto Himachali wool fiber has been studied in aqueous medium by using vanadium oxyacetyl acetonate as initiator at 40, 50, 60, and 70°C. Graft copolymerization was carried out for various reaction periods and nitric acid was found to catalyse the reaction. Percentage of grafting and percent efficiency have been determined as functions of concentration of nitric acid, concentration of initiator, concentration of monomer, time, and temperature. Under optimum conditions, methyl acrylate and ethyl acrylate afforded maximum grafting to the extent of 28.4 and 18.5%, respectively. Relative reactivities of methyl acrylate and ethyl acrylate towards grafting have been compared with those of methyl methacrylate, acrylic acid and vinyl acetate reported earlier from this laboratory. Different vinyl monomers showed the following reactivity order: MMA > MA > EA > AAc > VAc. Several grafting experiments were carried out in the presence of various additives which included tert-butylhydroperoxide (TBHP), dimethylsulfoxide, pyridine, and dimethylformamide. Only TBHP was found to enhance grafting to a considerable extent, other additives decrease percent grafting of both methyl acrylate and ethyl acrylate.     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

S-DMDAAC-AM阳离子型高分子絮凝剂的合成及性能研究

以淀粉(S)、二甲基二烯丙基氯化铵(DMDAAC)、丙烯酰胺(AM)为原料,采用氧化还原引发体系,合成r接枝共聚物S-DMDAAC-AM.考察了反应温度、反应时间、引发剂浓度、单体配比等因素对接枝共聚体系的接枝率、接枝效率和絮凝效果等因素的影响.试验结果表明,最优条件为淀粉(S):单体总量=3.5 g∶10.5 g,反...