Graft copolymerization of methyl acrylate onto nylon1010 initiated by potassium diperiodatonickelate(IV)

In this article, the graft copolymerization of methyl acrylate (MA) onto nylon1010 by using potassium diperiodatonickelate(IV) [Ni(IV)]–nylon1010 redox system as initiator was studied in alkaline medium. The effect of different factors on grafting parameters was investigated. The structure of the graft copolymer was determined by infrared (IR), X-ray diffraction, and scanning electron microscope (SEM). It was found that Ni(IV)–nylon1010 system is an efficient redox initiator for this graft copolymerization. A single-electron transfer mechanism is proposed to explain the formation of radicals and the initiation. The graft copolymer was used as the compatibilizer in blends of poly(methyl methacrylate) (PMMA) and nylon1010. The SEM photographs indicate that the graft copolymer greatly improved the compatibility of the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2636–2640, 2001     

Graft copolymerization of methyl acrylate onto chitosan initiated by potassium diperiodatoargentate (III)

A novel efficient redox system—potassium diperiodatoargentate [Ag(III)]‐chitosan—was employed to initiate the graft copolymerization of methyl acrylate (MA) onto chitosan in aqueous alkali solution. The effects of reaction variables such as monomer concentration, initiator concentration, reaction time, and temperature were investigated and the grafting conditions were optimized. The structures and the thermal stability of chitosan and chitosan‐g‐PMA were characterized by infrared spectroscopy (IR) and thermogravimetric analysis (TGA). The solubility of chitosan‐g‐PMA in some mixed solvent was tested. The graft copolymer was shown to be an effective compatibilizer in blends of poly(vinyl chloride) (PVC) and chitosan. Finally, a mechanism is proposed to explain the formation of radicals and the initiation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 799–804, 2006     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatoargentate(III)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) using potassium diperiodatoargentate(III) [Ag(III)]–PVA redox system as initiator was studied in an alkaline medium. Some structural features and properties of the graft copolymer were confirmed by Fourier‐transfer infrared spectroscopy, scanning electron microscope, X‐ray diffraction and thermogravimetric analysis. The grafting parameters were determined as a function of concentrations of monomer, initiator, macromolecular backbone (X?_n = 1750, M? = 80 000 g mol^?1), reaction temperature and reaction time. A mechanism based on two single‐electron transfer steps is proposed to explain the formation of radicals and the initiation profile. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate and n‐butyl acrylate, were also used to produce graft copolymerizations. It has been confirmed that grafting occurred to some degree. Thermogravimetric analysis was performed in a study of the moisture resistance of the graft copolymer. Copyright © 2004 Society of Chemical Industry     

Kinetics of graft copolymerization of poly(hexanedioic acid ethylene glycol) and methyl acrylate initiated by potassium diperiodatocuprate(III)

A redox system, potassium diperiodatocuprate(III) [DPC]/poly(hexanedioic acid ethylene glycol) (PEA) system, was employed to initiate graft copolymers of methyl acrylate (MA) and PEA in alkaline medium. The results indicate that the equation of the polymerization rate (R_p) is as follows: R_p = k [MA]^1.62[Cu(III)]^0.69, and that the overall activation energy of graft polymerization is 42.5 kJ/mol. The total conversion at different conditions (concentration of reactants, temperature, concentration of the DPC, and reaction time) was also investigated. The infrared spectra proved that the graft copolymers were synthesized successfully. Some basic properties of the graft copolymer were studied by instrumental analyses, including thermogravimetry and scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2376–2381, 2007     

Graft copolymerizaztion of methyl acrylate onto chitosan initiated by potassium diperiodatocuprate (III)

A novel redox system, potassium diperiodatocuprate [Cu (III)–chitosan], was employed to initiate the graft copolymerization of methyl acrylate (MA) onto chitosan in alkali aqueous solution. The effects of reaction variables such as monomer concentration, initiator concentration, pH and temperature were investigated. By means of a series of copolymerization reactions, the grafting conditions were optimized. Cu (III)–chitosan system was found to be an efficient redox initiator for this graft copolymerization. The structures and the thermal stability of chitosan and chitosan‐g‐poly(methyl acrylate) (PMA) were characterized by infrared spectroscopy (IR) and thermogravimetric analysis (TGA). In this article, a mechanism is proposed to explain the formation of radicals and the initiation. Finally, the graft copolymer was used as the compatibilizer in blends of poly(vinyl chloride) (PVC) and chitosan. The scanning electron microscope (SEM) photographs and differential scanning calorimetry (DSC) thermograms indicate that the graft copolymer improved the compatibility of the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2283–2289, 2003     

过硫酸钾引发羧甲基甲壳素和丙烯酸钾溶液接枝聚合

以过硫酸钾为引发剂,水为介质,制备了羧甲基甲壳素接枝丙烯酸钾共聚物,讨论了反应温度、反应时间、引发剂用量、单体用量对接枝率的影响,获得了最佳反应条件。结果表明：在含羧甲基甲壳素0．3g的30．0mL水溶液中,加入过硫酸钾50．0mg,丙烯酸钾水溶液8．0mL,于60℃反应120min时接枝率最高,达305．1％。接枝共聚物具有水溶性。接枝共聚改性反应可以扩展羧甲基甲壳素的应用价值。     

纤维素醚的乳接枝共聚合

在水溶性聚合物羟丙基甲基纤维素（ＨＰＭＣ０存在下进行丙烯酸酯的乳液支共聚合,研究了引发剂加料方式,用量和ＨＰＭＣ用量对接枝率的影响,结果表明,引发剂质量分数和引发与纤维素的预接触时间对接枝率有显著影响,增大ＨＰＭＣ质量分数导致表观接枝率和真实接枝率明显下降。     

Graft copolymerization of methyl methacrylate onto cellulosic biofibers

In this article, we have used the potassium persulfate to initiate the graft copolymerization of methyl methacrylate onto cellulosic biofibers in aqueous medium. Different reaction parameters, such as reaction time, initiator molar ratio, monomer concentration, amount of solvent, and reaction temperature, were optimized to get the maximum percentage of grafting (50.93%). The graft copolymers thus formed were characterized by Fourier transform infrared, scanning electron microscopy, X‐ray diffraction, and thermogravimetric, differential thermal analysis, and derivative thermogravimetric techniques. A mechanism is proposed to explain the generation of radicals and the initiation of graft copolymerization reactions. On grafting, percentage crystallinity decreases with reduction in its stiffness and hardness. The effect of grafting percentage on the physicochemical properties of raw as well as grafted fibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Graft copolymerization of methyl methacrylate onto jute fiber initiated by cerium(IV)–DMSO redox initiator system

The kinetics of graft copolymerization of methyl methacrylate (MMA) onto chemically modified jute fibers initiated by the Ce(IV)–DMSO redox system was studied in the temperature range of 40–60°C. By studying the effects of the concentration of the monomer, Ce(IV), and DMSO on the rate of grafting, the optimum conditions for grafting were determined. Also, the effect of temperature, time, concentration of the acid, the amount of jute fiber, and some inorganic salts and organic solvents on the rate was investigated. A kinetic scheme was proposed on the basis of the experimental findings. Infrared spectra of chemically modified jute and grafted jute was investigated. More than 120% of grafting could be achieved with the present system. The characterization of MMA-grafted chemically modified jute by TGA and DTA studies was made. The thermal stability of the jute fibers was improved by grafting. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2569–2576, 1998     

Graft copolymerization of 4-vinylpyridine and methyl acrylate onto polyethylene film by radiochemical method

Graft copolymerization of 4-vinyl pyridine (4-VP) and methyl acrylate (MA) onto polyethylene (PE) was studied in aqueous medium in air by the mutual irradiation method. The percentage of grafting was determined as a function of the (i) total dose, (ii) monomer concentration, and (iii) amount of water. The effect of different alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and pentanol on the percentage of grafting of 4-VP and MA was studied. The effects of different amines on the percentage of grafting of 4-VP were also studied. The graft copolymers were characterized by IR spectroscopy and thermal analysis and by identifying the isolated polymer from the grafted film. Grafted PE film was tested for permeability behavior and was found to be permeable to a 0.5% aqueous sodium chloride solution. A plausible mechanism is suggested to explain the grafting of 4-VP and MA onto PE film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 599–610, 1998     

Block copolymerization of poly(diethylene glycol phthalic anhydride) and methyl methacrylate initiated by potassium diperiodatonickelate(IV)

Block copolymers of methyl methacrylate (MMA) and poly(diethylene glycol Phthalic Anhydride) (PPAG) was synthesized using a novel redox system—potassium diperiodatonickelate(IV) [DPN]/PPAG system in an alkaline medium. Block copolymers with high percentage of blocking were obtained, which indicated that DPN/PPAG redox system was an efficient initiator for this blocking. Effects of different factors on the blocking parameters were examined. The overall activation energy of this blocking was calculated to be 55.12 kJ/mol. The structure of the block copolymer was determined by infrared, X‐ray diffraction, and scanning electron microscope (SEM). A mechanism is proposed to explain the generation of radicals and the initiation of block copolymerization. The block copolymer was used as the compatibilizer in blends of PMMA and Nylon6. The SEM photographs show that the block copolymer greatly improved the compatibility of the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1312–1317, 2006     

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     

羟乙基纤维素与丙烯酸-2-羟基丙酯的反应规律

以硝酸铈铵/乙二胺四乙酸(CAN/EDTA)为引发剂,研究了羟乙基纤维素(HEC)与丙烯酸-2-羟基丙酯(HPA)的接枝共聚反应,讨论了单体浓度、引发剂浓度、反应温度、反应时间等因素对接枝率的影响,试验结果表明:在引发剂CAN和EDTA为22mmol/L,单体HPA为0.31mol/L,反应温度为40℃,反应时间为4h时,接枝率和接枝效率值最佳,并用红外光谱对接枝共聚物结构进行了鉴定。     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatonickelate(IV)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) with a potassium diperiodatonickelate(IV) [Ni(IV)]–PVA redox system as an initiator was investigated in an alkaline medium. The grafting parameters were determined as functions of the temperature and the concentrations of the monomer and initiator. The structures of the graft copolymers were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The Ni(IV)–PVA system was found to be an efficient redox initiator for this graft copolymerization. A single‐electron‐transfer mechanism was proposed for the formation of radicals and the initiation. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate, n‐butyl acrylate, and n‐butyl methacrylate, were used as reductants for graft copolymerization. These reactions definitely occurred to some degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 529–534, 2003     

Grafting of methyl methacrylate onto sodium alginate initiated by potassium ditelluratoargentate(III)

Sodium alginate (SA) was graft‐copolymerized with methyl methacrylate in an alkali aqueous solution with potassium ditelluratoargentate(III) (DTA) as the initiator. Graft copolymers with both a high grafting efficiency (>90%) and a high percentage of grafting were obtained, which indicated that the DTA–SA redox pair was an efficient initiator for this grafting. The grafting parameters, including total conversion, grafting efficiency, and percentage grafting, were evaluated comparatively. The dependence of these parameters on temperature and time, monomer concentration, initiator concentration, and SA backbone concentration was also investigated. The overall activation energy of this grafting was calculated as 37.50 kJ/mol. Proof of grafting was obtained from gravimetric analysis and IR spectra. A tentative mechanism involving a two‐step, single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and the initiation of grafting. Some basic properties of the grafted copolymer were studied by instrumental analyses, including thermogravimetry, X‐ray diffraction, and scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1688–1694, 2005     

Block copolymerization of poly(ethylene glycol) and methyl acrylate using potassium diperiodatocuprate(III)

Block copolymers of methyl acrylate (MA) and poly(ethylene glycol) (PEG) have been obtained using a novel redox system—potassium diperiodatocuprate(III)[DPC]/PEG system in alkaline aqueous medium. Block copolymers with a high percentage of blocking were obtained, which indicated that the DPC/PEG redox system was an efficient initiator for this blocking. Effects of different conditions (concentration of reactants, temperature, concentration of the DPC, and reaction time) on the total conversion, percentage of blocking, and intrinsic viscosity were examined. The effects of different monomers and various PEGs with different molecular weight on the total conversion were also examined. A mechanism is proposed to explain the generation of radicals and the initiation of block compolymerization. Some basic properties of the block copolymers were also studied by thermogravimetry and scanning electron microscope. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2139–2145, 2005     

Optimized conditions for the grafting reaction of poly(methyl acrylate) onto rubberwood fiber

Graft copolymerization of poly(methyl acrylate) (PMA) onto rubberwood fiber (RWF) was carried out by free radical initiation. Hydrogen peroxide and ferrous ions were used as an initiator system. Effects of various parameters (reaction temperature and reaction time, as well as hydrogen peroxide, ferrous ammonium sulfate and monomer concentrations) on the grafting percentage were investigated. A high percentage of grafting was achieved when optimum reaction conditions were used. The optimum temperature of the reaction was determined to be about 55 °C and the reaction time was 120 min. The optimum concentration of H₂O₂ was 0.03 M and the amounts of Fe²⁺ and MA were 0.4 mmol and 0.05 mol, respectively. The PMA homopolymer was removed from the graft copolymer by Soxhlet extraction using acetone. The presence of PMA on the fiber was confirmed by FT-IR spectroscopy and gravimetry. The surface morphology of the poly(methyl acrylate)-graft-(rubberwood fiber) was studied by means of scanning electron microscopy. Copyright © 2004 Society of Chemical Industry     

Ceric(IV) ion‐induced graft copolymerization of acrylamide and ethyl acrylate onto cellulose

Graft copolymerization of acrylamide (AAm) and ethyl acrylate (EA) onto cellulose has been carried out from their binary mixtures using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 25 ± 1 °C. The extent of acrylamide grafting increased in the presence of the EA comonomer. The composition of the grafted chains (F_AAm = 0.52) was found to be constant during the feed molarity variation from 7.5 × 10^?2 to 60.0 × 10^?2 mol L^?1, whereas the composition of the grafted chains (F_AAm) was found to be dependent on feed composition (f_AAm) and reaction temperature. The effects of ceric(IV ) ion concentration, reaction time and temperature on the grafting parameters have been studied. The grafting parameters showed an increasing trend up to 6.0 × 10^?3 mol L^?1 concentration of CAN at a feed molarity of 30.0 × 10^?2 mol L^?1 and showed a decreasing trend on further increasing the concentration of CAN (>6.0 × 10^?3 mol L^?1) at a constant concentration of nitric acid (5.0 × 10^?2 mol L^?1). The composition of the grafted chains (F_AAm) was determined by IR spectroscopy and nitrogen content and the data obtained then used to determine the reactivity ratios of the acrylamide (r₁) and ethyl acrylate (r₂) comonomers by using a Mayo and Lewis plot. The reactivity ratios of acrylamide and ethyl acrylate were found to be r₁ = 0.54 and r₂ = 1.10, respectively, and hence the sequence lengths of acrylamide (m?M₁) and ethyl acrylate (m?M₂) in the grafted chains are arranged in an alternating form, as the product of the reactivity ratios of acrylamide and ethyl acrylate (r₁ × r₂) is less than unity. The rate of graft copolymerization of the comonomers onto cellulose was found to be dependant on the ‘squares’ of the concentrations of the comonomers and on the ‘square root’ of the concentration of ceric ammonium nitrate. The energy of activation (ΔE_a) of graft copolymerzation was found to be 5.57 kJ mol^?1 within the temperature range from 15 to 50 °C. On the basis of the results, suitable reaction steps have been proposed for the graft copolymerzation of acrylamide and ethyl acrylate comonomers from their mixtures. Copyright © 2005 Society of Chemical Industry     

木薯淀粉/VAc-MA接枝共聚物的合成研究

通过正交试验设计,研究醋酸乙烯酯和丙烯酸甲酯两种单体接枝改性木薯淀粉的影响因素。利用SAS统计分析得出适宜的工艺条件:引发剂浓度16mmol.L-1,总单体浓度1.45mol.L-1,两单体配比(VAc/MA)为30/70,反应温度65℃,反应时间5h。采用红外光谱对该接枝共聚物结构进行了分析。     

Graft copolymerization of sodium acrylate onto organophilic montmorillonites initiated by potassium diperiodatonickelate (IV) and application of graft copolymer in water‐superabsorbent

The graft copolymerization of sodium acrylate (SA) onto organophilic montmorillonites (OMMT) initiated by redox reaction of potassium diperiodatonickelate (IV) [Ni(IV)] with reactive groups on OMMT substrate was studied in alkaline medium. The grafting parameters have been investigated as a function of the ratio of monomer to OMMT, the concentration of initiator, temperature, and pH value. The structure of the graft copolymer (OMMT‐g‐PSA) was systematically characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscope (SEM). It was found that [Ni(IV)] belongs to a highly efficient initiator for graft copolymerization of SA onto OMMT via the redox iniation (grafting efficiency > 95%). Furthermore, the experimental results also showed that the graft copolymer gels synthesized under optimal condition exhibited a maximum water absorbency of 1104 g/g in distilled water and 111 g/g in 0.2 wt % NaCl solution, respectively, and its water retention ability is more than 91% after centrifugal separation for 2 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008