以Fe~(2+)-H_2O_2氧化还原体系引发木薯淀粉与醋酸乙烯酯接枝共聚反应研究

研究了以Fe2+-H2O2为引发剂的木薯淀粉与醋酸乙烯酯的接枝共聚反应,并对重要的反应条件进行了讨论。结果表明:当单体与淀粉的质量配比为1.0~2.0,引发剂浓度为1.0 mmol/L,H2O2与Fe2+的摩尔比为2,反应温度为40°C,反应时间为3 h,采用Fe2+→单体→H2O2的加料顺序时,可以得到较高的转化率、接枝率、接枝效率,分别为86.47%、55.30%及31.98%,并探讨Fe2+-H2O2的引发机理。通过Srectrum One红外光谱及电镜对接枝物的结构进行了分析。     

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%。     

Modification of sago starch by graft copolymerization. Effect of reaction conditions on grafting parameters

Graft copolymerization of acrylonitrile onto sago starch was carried out by a free radical initiating process in which the ceric ion (Ce 4+ ) was used as an initiator. The reaction conditions significantly influence the graft copolymerization. The percentage of grafting, grafting efficiency and rate of grafting were all dependent on the concentration of ceric ammonium nitrate (CAN), acrylonitrile (AN), sago starch (AGU, anhydro glucose unit), mineral acid (H 2 SO 4 ) and the reaction temperature and period. The optimum yield was obtained when the concentrations of CAN, AN, AGU and H 2 SO 4 were used at 9.61×10 ?3 , 0.653, 0.152 and 0.187 mol L ?1 , respectively. The optimum temperature and reaction period were 50°C and 90 min, respectively. The rate of graft copolymerization was examined using the experimental results and the reaction mechanism. The polya1crylonitrile grafted sago starch was characterized by using FT-IR spectroscopy, DSC and SEM analysis.     

Optimization of synthesis and characterization of cassava starch‐graft‐poly(acrylonitrile) using response surface methodology

Graft copolymerization of poly(acrylonitrile) onto cassava starch was carried out with potassium persulphate (PPS) as the free radical initiator using a response surface Box–Behnken design. Different levels of monomer concentration, initiator concentration, and temperature were used, and regression models were generated in terms of these factors, which can be used to predict the grafting level and efficiency at a given level of the factors. The grafted starches were characterized by FTIR, XRD, and SEM analyses and determination of %grafting (%G), N‐content, thermal properties, water and saline solution retention, and rheological properties. Under the conditions used, %G was found to depend only on the temperature used for the reaction. The maximum %G of 120.1 was obtained for the sample synthesized under the following conditions: weight of AN = 0.753 mol/10 g starch, weight of PPS = 0.284 g and temperature = 55°C, and the grafting efficiency was 30.03%. The absorption bands at 2243 cm^?1 for the nitrile group (? CN) in the FTIR spectra of the products confirmed the grafting reaction. There was a decrease in crystallinity and disappearance of the granular structure after grafting of the starch. The melting temperatures of the graft copolymers determined by differential scanning calorimetry analysis were higher than that of the native starch. The grafted starches exhibited very high thermal stability as observed from the thermogravimetric analysis. The superabsorbent polymer prepared from the grafted starch by alkali saponification exhibited a maximum water absorbency of 636 g/g. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of biodegradable polyethylene by graft copolymerization of starch using glucose–Ce(IV) redox system

Graft copolymerization of low‐density polyethylene (LDPE) onto starch was carried out with glucose–cerium(IV) redox initiator in an aqueous sulfuric acid medium under nitrogen atmosphere. The graft yield was influenced by various parameters like reaction time, temperature, and concentrations of acid, glucose, polyethylene (PE), starch, and initiator. A maximum graft yield of 85.66% was obtained at a temperature of 50°C and at higher concentration of starch. Effect of grafting on crystallinity, morphology, and thermal properties of modified PE has been evaluated using X‐ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA/DTA). Biodegradability of starch‐grafted PE has been tested applying soil‐burial test. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3229–3239, 2006     

Synthesis and characterization of starch‐poly(methyl methacrylate) graft copolymers

The graft copolymerization was carried out by methyl methacrylate with starch in which azobisisobutyronitrile was used as an initiator. The grafting reactions were carried out within a 65–95°C temperature range, and the effect of the monomer, initiator concentrations, and the amount of starch on the graft yield were also investigated. The maximum graft yield was obtained at a azobisisobutyronitrile concentration of 2.0 × 10^?3 mol/L. The overall rate activation energy of the reaction was found to be 89.42 kJ/mol. The grafted starches were characterized with infrared spectroscopy, scanning electron microscopy, and thermogravimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 53–57, 2002     

Grafting onto wool

Summary In order to study the role of -SH group of wool in graft copolymerization, an attempt has been made to study grafting of acrylic acid (AAc) onto reduced wool in aqueous medium using ceric ammonium nitrate (CAN) as redox initiator. HNO₃ was found to catalyze the graft copolymerization. Reduction of wool was effected with thioglycolic acid (TGA) in aqueous medium. Percentage of grafting was determined as a function of concentration of (i) CAN, (ii) vinyl monomer (AAc), (iii) nitric acid, (iv) time and (v) temperature. Under optimum conditions, poly-(acrylic acid) was grafted to the reduced wool to the extent of 9.14%, the unreduced wool under optimum conditions afforded maximum grafting of poly(AAc) to the extent of 12.24%. Reduction of wool does not promote grafting of AAc in the presence of CAN.     

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。     

Graft polymerization of acrylonitrile onto paper and characterization of the grafted product

The chemical graft copolymerization reaction of acrylonitrile (AN) onto paper sheet was performed. The effect of initiator concentration, monomer concentration, and temperature on the reaction rate was studied. The reaction rate equation of the graft copolymerization reaction is found to be R_P = K₂ [initiator]^0.54[monomer]^1.13. The apparent activation energy (E_a) of the copolymerization reaction is found to be 35.99 KJ/mol. The infrared characteristic absorption bands for cellulosic paper structure and the paper gr‐AN are studied. Tensile break load, porosity, and burst strength were measured for the grafted and pure paper sheet. It was found that the mechanical properties are improved by grafting. The chemical resistance of the graft product against strong acid (HCl), strong alkali (NaOH), polar and nonpolar solvents was investigated. It was found that the resistance to these chemicals is enhanced by grafting. From the TGA and DTA data, it is clear that the grafted paper sheet is more thermally stable than pure paper sheet. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

黄原胶与丙烯酰胺接枝共聚反应的研究

以过硫酸铵为引发剂,在氮气保护下,研究了黄原胶与丙烯酰胺的接枝共聚反应。考察了单体浓度、引发剂浓度、反应温度和反应时间等因素对接枝率及接枝效率的影响,探讨了过硫酸铵引发黄原胶接枝丙烯酰胺共聚反应的基本规律。采用红外光谱、X射线粉末衍射对接枝共聚物的结构进行研究,用热重分析法表征了产物的热性能,并初步探讨了接枝机理。结果表明,过硫酸铵能有效地引发黄原胶与丙烯酰胺的接枝共聚反应,并且接枝率和接枝效率随单体浓度、引发剂浓度、反应温度的变化出现极大值,随反应时间的延长不断上升,直至基本不变。     

Graft copolymerization of methyl acrylate onto sago starch using ceric ammonium nitrate as an initiator

The graft copolymerization of methyl acrylate onto sago starch was carried out by a free radical initiating process. The free radicals were produced by the chemical initiation method in which ceric ammonium nitrate was used as an initiator. It was found that the percentages of grafting, grafting efficiency, and rate of grafting were all dependent on the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU), mineral acid (H₂SO₄), and reaction temperature and period. The variables affecting the graft copolymerization were thoroughly examined. The optimum yield of grafting was obtained when the concentration of CAN, MA, AGU, and H₂SO₄ were used at 8.77 × 10⁻³, 0.803, 0.135, and 0.175 mol L⁻¹, respectively. The optimum reaction temperature and period were 50°C and 60 min, respectively. The rate of graft polymerization was explored on the basis of experimental results and reaction mechanism. The evidence of grafted copolymers was investigated by using FTIR spectroscopy, TG, and DSC analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 516–523, 2000     

Optimized conditions for the grafting reaction of poly(methyl methacrylate) onto oil‐palm empty fruit bunch fibers

This article describes the graft copolymerization of poly(methyl methacrylate) (PMMA) onto oil‐palm empty fruit bunches (OPEFBs) with a fiber length of less than 75 μm. The graft copolymerization was carried out under a nitrogen atmosphere by a free‐radical initiation technique in an aqueous medium. Hydrogen peroxide and ferrous ions were used as a redox initiator/cocatalyst system. The PMMA homopolymer that formed during the reaction was removed from the grafted copolymers by Soxhlet extraction. Determining the effects of the reaction period, reaction temperature, and monomer concentration on the grafting percentage was the main objective, and they were investigated systematically. The optimum reaction period, reaction temperature, monomer concentration, and initiator concentration were 60 min, 50°C, 47.15 × 10^?3 mol, and 3.92 × 10^?3 mol, respectively. The maximum percentage of grafting achieved under these optimum conditions was 173%. The presence of PMMA functional groups on OPEFB and the enormous reduction of the hydroxyl‐group absorption band in PMMA‐g‐OPEFB spectra provided evidence of the successful grafting reaction. The improvement of the thermal stability of PMMA‐g‐OPEFB also showed the optimal achievement of the grafting reaction of PMMA onto OPEFB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Graft copolymerization of methyl methacrylate upon gelatin initiated by benzoyl peroxide in aqueous medium

The graft copolymerization of methyl methacrylate upon gelatin was studied using benzoyl peroxide as an organic initiator in aqueous medium. The grafting reactions were carried out within the 65–90°C temperature range, and the effect of monomer and initiator concentrations on the graft yield were also investigated. The maximum graft yield was obtained at a benzoyl peroxide concentration of 0.20 × 10⁻² mol/L and the optimum temperature was 80°C. Thermogravimetric analysis showed that the thermal stability of gelatin increased as a result of grafting. Further, such changes in the properties of methyl methacrylate‐grafted gelatin as density, moisture regain, and water uptake were also determined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1547–1556, 1999     

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...     

丙烯酰氧基螺噁嗪接枝羧甲基甲壳素反应条件的研究

采用接枝共聚法合成了一种具有螺噁嗪侧基的羧甲基甲壳素水溶性衍生物。讨论了反应温度、反应时间、引发剂用量、溶剂用量、单体用量对丙烯酰氧基螺噁嗪接枝羧甲基甲壳素反应的影响。接枝效率最高时反应条件为:羧甲基甲壳素0.4 g,溶剂水50.0 mL,引发剂0.35 mmol,单体3.0 mmol,反应温度70℃,反应时间4.0 h,接枝率为65.0%,接枝效率为25.2%。     

Grafting of vinyl monomers onto silk fibers: Trivalent-manganese-initiated graft copolymerization of acrylamide onto silk fibers

Graft copolymerization of acrylamide (AM) onto silk fibers, using Mn(III)–sulphate as initiator, has been investigated, in aqueous sulphuric acid in the temperature range of 30–55°C. Grafting reaction has been studied by varying the concentration of monomer, Mn(III), sulphuric acid, temperature, and also with the modified silk. The graft yield increases significantly with increase of monomer concentrations to the extent of 0.85M, after which the rate falls. With increase in Mn(III) concentration and H⁺ ion concentration the graft yield increases, but after an optimum concentration a depression in the graft yield is noticed. The rate of the reaction is temperature-dependent; with increase of temperature the graft-on increases. Among the solvent composition studied a solvent/water mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and a further increase of solvent composition decreases the graft yield. The effect of various additives such as transition metal salts, aromatic and heterocyclic amines on grafting reaction has been studied. A suitable mechanism for grafting has been proposed. Finally physical characterization such as thermal analysis (TGA) of the grafted samples has been carried out in order to ensure grafting and to study the change in the properties of the fibers.     

淀粉与苯乙烯/甲基丙烯酸甲酯乳液共聚合

研究了淀粉与苯乙烯 (St)、甲基丙烯酸甲酯 (MMA)的接枝聚合反应。以焦磷酸锰 [Mn(H2 P2 O7) 3 ]3 -为引发剂 ,以十二烷基苯磺酸钠为乳化剂 ,考察引发剂浓度、反应温度、单体浓度对原位聚合反应中单体的转化率(X % )、接枝率 (G % )、接枝效率 (GE % )的影响。实验结果表明最高接枝率可达到 5 2 .4 % ,接枝效率可达 77.2 %。     

线型低密度聚乙烯固相接枝丙烯酸丁酯的研究

利用固相接枝共聚的方法,制备了线型低密度聚乙烯接枝丙烯酸丁酯(LLDPE-g-BA)共聚物。讨论了反应温度、反应时间、引发剂用量、单体浓度对接枝率的影响,结果表明:随着反应温度的升高,反应时间的延长,引发剂用量以及单体/聚合物比例的增加,接枝率提高,最高接枝率达到10.12%。并用红外光谱表征产物的结构。LLDPE-g-BA可明显改善PET/LLDPE复合材料的界面相容性及力学性能。     

Graft copolymerization of n-vinyl-2-pyrrolidone on dimethyl sulfoxide pretreated poly(ethylene terephthalate) films using azobisisobutyronitrile initiator

Poly(ethylene terephthalate) (PET) films were grafted with n-vinyl-2-pyrrolidone (n-VP) using an azobisisobutyronitrile (AIBN) initiator. Films were pre-treated in dimethyl sulfoxide (DMSO) for 1 h at 140°C before the polymerization reaction was carried out. Variations of graft yield with time, temperature, initiator, and monomer concentrations were investigated. The optimum temperature and polymerization time was found to be 70°C and 4 h, respectively. Increasing monomer concentration from 0.28 to 1.22M and initiator concentration from 1.77 × 10⁻³ to 4.20 × 10⁻³M enhanced the percent grafting. The effects of monomer and initiator diffusion on PET films were also studied. The overall activation energy for grafting was calculated as 11.5 kcal/mol. Further changes in properties of PET films such as water-absorption capacity and intrinsic viscosity were determined. The grafted films were characterized with FTIR and scanning electron microscopy (SEM). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1437–1444, 1997     

氧化还原引发下的淀粉、丙烯酸反相乳液聚合

以环己烷为连续相,Span20为乳化剂,采用氧化还原引发体系,通过反相乳液聚合技术,合成淀粉、丙烯酸接枝共聚物。并用红外光谱对共聚物进行了表征。研究结果表明:采用氧化还原引发剂可使聚合反应低温快速进行,在过硫酸钾为3.1mmol/L,亚硫酸氢钠为3.1mmol/L,单体丙烯酸浓度为2.6mol/L,反应温度为30℃,反应时间为3h,乳化剂浓度为5%时,单体转化率为92.6%、淀粉接枝率为43.2%、淀粉接枝效率56.4%。