Ionic Xanthate Method of Grafting. II

In the ionic xanthate method of grafting, the increase of sodium hydroxide concentration and liquor ratio increased the grafting parameters up to a limit. The limit varied from one monomer to another. The positive values of the standard degree of concentration of sodium hydroxide indicate that the graft polymerization reaction has happened. The extent of decrease in the grafting parameters with the increase of the liquor ratio may be due to the increase of the termination reactions as a result of increasing the number of HOH molecules and the consequent chain transfer reactions to solvent. Grafting parameters also increased with the increase of the concentration of monomers up to a limit. The reactivity of these monomers is in the order: methyl methacrylate > ethyl acrylate > allyl chloride > acrylonitrile > methyl acrylate > allyl alcohol, being dependent on both the radical stabilization and the strength of the electron acceptance of the monomers. The activation energy of the overall polymerization reaction (i.e., grafting and homopolymer) decreased with the increase of the crude grafting yield, and the reverse relation was achieved with the true grafting yield (i.e., grafting reaction only). This difference may be attributed to the difference in the conformation of the polymer chains to graft polymerize on the active sites of the cellulose chains.     

Peroxydiphosphate–metal ion–cellulose thiocarbonate redox system‐induced graft copolymerization of vinyl monomers onto cotton fabric

The grafting of methacrylic acid (MAA) and other vinyl monomers onto cotton cellulose in fabric form was investigated in an aqueous medium with a potassium peroxydiphosphate–metal ion–cellulose thiocarbonate redox initiation system. The graft copolymerization reaction was influenced by peroxydiphosphate (PP) concentration, the pH of the reaction medium, monomer concentration, the duration and temperature of polymerization, the nature of vinyl monomers, and the nature and concentration of metallic ions (activators). On the basis of a detailed investigation of these factors, the optimal conditions for the grafting of MAA onto cotton fabric with the said redox system were as follows: [Fe²⁺] = 0.1 mmol/L, [PP] = 2 mmol/L, [MAA] = 4%, pH‐2, grafting time = 2 h, grafting temperature = 70°C, and material/liquor ratio = 1 : 50. Under these optimal conditions, the graft yields of different monomers were in the following sequence: MAA ? acrylonitrile > acrylic acid > methyl acrylate > methyl methacrylate. The unmodified cellulosic fabric (the control) had no ability to be grafted with MAA with the PP–Fe²⁺ redox system. The percentage of grafting onto the thiocarbonated cellulosic fabric was more greatly enhanced in the presence of iron salts than in their absence. This held true when the lowest concentrations of these salts were used separately. A suitable mechanism for the grafting processes is suggested, in accordance with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1879–1889, 2003     

Pentavalent vanadium ion–cellulose thiocarbonate redox-system induced grafting of methyl methacrylate and other vinyl monomers onto cotton fabric

Cellulose thiocarbonate was prepared by reacting cotton cellulose fabric with carbon disulphide in the presence of sodium hydroxide. The treated fabric formed, with pentavalent vanadium ion, an effective redox system capable of initiating grafting of methyl methacrylate (MMA) and other monomers no+o the cotton fabric. The dependence of grafting on vanadium concentration, pH of the polymerization medium, temperature and duration of grafting, nature and concentration of monomer, and solvent/water ratio was studied. The results indicated that increasing the pentavalent vanadium (V^v) concentration up to 60 mmol/L was accompanied by enhancement in the rate of grafting; the latter was not affected by further increase in V^v concentration. Maximum grafting yield was achieved at pH 2; grafting fell greatly at higher pH. The rate of grafting followed the order: 70° > 60° > 50°C. The graft yield increased significantly by increasing the MMA concentration from 0.5 to 5%. Of the solvents studied, n-propanol and isopropanol enhanced the grafting rate provided that a solvent/water ratio of 5 : 95 was used; a higher solvent ratio decreased the magnitude of grafting. Other solvents, namely, methanol, ethanol, n-butanol, and acetone, in any proportion, decreased the rate of grafting. With the monomer used, the graft yield followed the order: methyl methacrylate > methyl acrylate > methacrylic acid > ethyl methacrylate > acrylic acid. Also reported was a tentative mechanism for vinyl-graft copolymerization onto cotton fabric using cellulose thiocarbonate-V^v. © 1993 John Wiley & Sons, Inc.     

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.     

Graft copolymerization of methyl methacrylate and other vinyl monomers onto cotton fabric using ferrous cellulose thiocarbonate–N-bromosuccinimide redox initiation system

The cellulose thiocarbonate, in the fabric from, was treated first with a freshly prepared ferrous ammonium sulphate (FAS) solution. The sotreated fabric formed, with N-bromosuccinimide (NBS), an effective redox system capable of initiating grafting of methyl methacrylate (MMA) and other vinyl monomers onto the cotton fabric. The effect of the polymerization conditions the polymer criteria, namely, graft yeild, homopolymer, total conversion, and grafting efficiency, was studied. These polymer criteria were found to depend extensively upon concentrations of the Fe²⁺ ion (activator), NBS (initiator), and MMA; pH of the polymerization medium, and duration and temperature of polymerization. Based on detailed investigation of these factors, the optimal conditions for grafting were as follows: Fe²⁺, 1 × 10⁻³ mol/L; NBS, 1 × 10⁻² mol/L; MMA, 4%; pH, 2: polymerization time, 150 min; polymerization temperature, 60°C; material/liquor ratio, 1: 100. Under these optimal conditions, the rates of grafting of different vinyl monomers were in the following sequence: methyl methacrylate ≫ methyl acrylate > acrylonitrile. Other vinyl monomers namely, acrylic acid, and methacrylic acid have no ability to be grafted to the cellulosic fabric using the said redox system. A tentative mechanism for the polymerization reaction is suggested. © 1996 John Wiley & Sons, Inc.     

Graft copolymerisation of vinyl monomers on modified cottons. VII. Grafting by chain transfer

Grafting of methyl methacrylate on cellulosic materials by chain transfer under the catalytic influence of azobisisobutyronitrile (AIBN) was extensively studied. The graft yield is influenced by reaction time, temperature, monomer and initiator concentration, reaction medium and nature of the substrate. In general, the grafting reaction shows an induction period after which the polymerisation proceeds rapidly. The graft yield increases and the induction period decreases by rising the reaction temperature from 50 to 70°C. This is also the case when the monomer concentration was increased from 2 to 6%. Increasing the AIBN concentration up to 0.01 M causes a significant enhancement in grafting while further increase brings about a marked fall in the graft yield. Among the reaction media studied, a water/solvent mixture containing 25% of either methanol, ethanol, propanol, butanol or acetone seems to constitute a reaction medium where the monomer and initiator are completely miscible and the swelling of cellulose by water is not hindered by the presence of these solvents. Increasing the solvent ratio in the water/solvent mixture causes a considerable decrease in the graft yield. The polymer content of the cellulosic materials, i. e. the graft yield, follows the order: partially carboxymethylated cotton > cotton treated with 12N sodium hydroxide > cyanoethylated cotton > cotton treated with 0.5 N sodium hydroxide > purified cotton. In addition, proof of grafting was provided by the fractional precipitation method.     

Grafting onto wool. VII. Ceric ion-initiated graft copolymerization of vinyl monomers. Comparison of monomer reactivities

In an attempt to compare relative reactivities of vinyl monomers toward grafting, methyl methacrylate (MMA) and acrylic acid (AAc) were grafted separately to Himachali wool in aqueous medium by using ceric ammonium nitrate (CAN) as redox initiator. Nitric acid was found to catalyze the reaction. Percent grafting was determined as a function of concentration of nitric acid, concentration of CAN, concentration of monomer, time, and temperature. Optimum conditions for maximum grafting were evaluated for each monomer and were found to depend upon the nature of the monomer. Reactivities of MMA and AAc toward grafting were compared with those of methyl acrylate (MA), ethyl acrylate (EA), and vinyl acetate (VAc) reported earlier from this laboratory and were found to follow the order MA > EA > MMA > VAc > AAc. An explanation for the observed order of reactivity of different vinyl monomers is presented.     

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     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

Graft polymerization of some vinyl monomers onto alkali-treated cellulose

Treatment of cellulose by different concentrations of alkali, namely, 5–30% NaOH, changed its fine structure and transferred cellulose I into cellulose II. The decreased crystallinity due to alkali treatment and the transformation of cellulose I into cellulose II lowered the reactivity of cellulose toward the grafting polymerization reactions. Compactness of the structure as a result of the treatment of cellulose with 5% sodium hydroxide concentration decreased the rate of the grafting reaction and the grafting yield. On the other hand, such treatment of cellulose with different concentrations of alkali increased the rate of ceric consumption, i.e., increased the rate of oxidation of cellulose. Thus, the termination reaction of the grafting polymerization process may occur as a result of such oxidation and because of the increase of the active sites onto cellulose, leading to a decrease of the grafting yields and rate of grafting polymerization reaction by using the free-radical grafting process. The use of the ionic-xanthate method of grafting polyvinyl- and polyallyl-on alkali-treated cellulose shows an increase of grafting efficiency and grafting yields. Maximum grafting efficiency and yields were achieved when cellulose was treated with sodium hydroxide concentration below 15%, and maximum crystallinity indices were obtained. Using 15–25% sodium hydroxide lowered the indices of crystallinity, and lower grafting yields and grafting efficiency were achieved. Thus, transformation of cellulose I into cellulose II decreased the reactivity of these treated celluloses toward graft polymerization reactions by the use of the ionic-xanthate method. In our opinion, termination reactions may also occur and affect the results.     

Graft copolymerization of wool using acrylate monomers. I. Optimum conditions of grafting and molecular weight of grafts

Wool fibres were grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate and methylmethacrylate to various percentages of grafting in nitrogen atmosphere using ceric ammonium nitrate in nitric acid as initiator. The effects of concentration of the initiator, acid, monomer, temperature and time on the grafting were investigated. A comparison of such results indicated the following reactivity order of monomers: methyl acrylate > ethyl acrylate > methylmethacrylate > n-butyl acrylate. The molecular weights of the grafts were investigated by isolating the grafts from the fibres.     

Azobisisobutyronitrile-induced vinyl graft polymerization onto nylon 66

The presence of nylon 66 during polymerization of methyl methacrylate (MMA) under the influence of azobisisobutyronitrile (AIBN) produces a nylon-PMMA graft copolymer. The copolymerization reaction is greatly influenced by the reaction medium, temperature and time of the reaction, concentration of MMA, and addition of metallic ions. Polymerization in pure organic solvents brings about little or no grafting. Incorporation of water into the polymerization system enhances grafting significantly. A reaction medium of a water/solvent mixture in a ratio of 75:25 constitutes the most favorable medium for the grafting reaction in question. Of the solvents examined, methanol, ethanol, propanol, isopropanol, and acetone work extremely well. Increase in reaction time is accompanied by an increase in the graft yield. The same holds true for the reaction temperature; the graft yield is much higher at 70 than at 50°C and follows the order 70°C > 60°C > 50°C. Increasing MMA concentration also causes considerable enhancement of the graft yield. The presence of 0.01M cupric sulfate in the polymerization system brings about an eightfold increase in the graft yield, whereas the presence of ferric sulfate at the same concentration causes a sixfold increase. The mode of initiation of grafting seems to be different in the presence of metallic ions than in their absence. A mechanism for the reactions involved in the both cases has been proposed.     

Radiation‐induced graft copolymerization of α‐methyl styrene and butyl acrylate mixture into polyetheretherketone films

Radiation‐induced graft copolymerization of α‐methyl styrene (AMS), butyl acrylate (BA) monomers, and their mixture was investigated on poly(etheretherketone) films. The graft polymerization was carried out using ethyl methyl ketone as the medium for the copolymerization and the maximum degree of grafting of 27% was achieved. It was observed that the grafting is significantly influenced by the reaction conditions, such as reaction time, preirrradiation dose, monomer concentration, monomer ratio, and the reaction temperature. The degree of grafting increases as the monomer concentration increases up to 30%, beyond which a decrease in the grafting was observed. The degree of grafting showed a maximum at 40% BA content in the monomer mixture. The temperature dependence of the grafting process shows decreasing grafting with the increase in the reaction temperature. The presence of AMS and BA grafts in the film was confirmed by FTIR spectra. The relative change in the PBA/PAMS fraction with respect to the reaction temperature has been found in this study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and photopolymerization kinetics of new flexible diacrylate and dimethacrylate crosslinkers based on C18 diacid

A series of new di(meth)acrylate monomers was synthesized from the reactions of methyl α-hydroxymethylacrylate (MHMA), ethyl α-hydroxymethylacrylate (EHMA), hydroxyethyl acrylate (HEA) and hydroxyethylmethacrylate (HEMA) with α,ω-C18 diacid chloride. The photopolymerization behavior and reaction kinetics of the synthesized monomers were investigated using photoinitiation with differential scanning calorimetry. The polymerization rates, conversions and kinetic constants for propagation and termination were determined for each of the monomers. The maximum rate of polymerizations of the diacrylate monomers was higher than that of the dimethacrylate monomers and followed the order: HDDA (1,6-hexanediol diacrylate)>HEA-C18>EHMA-C18∼HEMA-C18>MHMA-C18. The total conversions obtained were 78, 75, 72, 64 and 69% for MHMA-C18, EHMA-C18, HEMA-C18, HEA-C18 and HDDA, respectively, indicating comparable or higher conversions for methacrylates despite their lower rates of polymerization. Propagation and termination mechanisms of the monomers were investigated by plotting propagation and termination rate constants as a function of conversion.     

Redox-initiated vinyl graft polymerization onto wool with thiourea as the reductant. I. Grafting of methyl methacrylate with the hydrogen peroxide–thiourea catalyst system

The interaction of methyl methacrylate with wool under the catalytic influence of the hydrogen peroxide–thiourea redox system was studied under a variety of conditions. The degree of grafting depends upon the method empolyed; it is advantageous to first immerse wool in thiourea solution, monomer and hydrogen peroxide being then subsequently applied. Increasing the hydrogen peroxide concentration from 4 to 8 mmole/1. causes a significant enhancement in the graft yield. The latter remains practically unchanged upon further increment in hydrogen peroxide concentration within the range studied, i.e., up to 12 mmole/1. This was also observed with respect to thiourea concentration. On the other hand, increasing monomer concentration is accompanied by a significant increase in the graft yield. The polymerization reaction is temperature dependent; at the three temperatures examined, the graft yields follow the order 80° > 60° > 40°C. The rate of grafting is also dependent on the pH of the reaction medium over the range of 2 to 8, being decreased as the pH increased. Furthermore, the presence of traces of cupric ions in the polymerization system accentuates the graft formation. The alkali solubility as well as the urea bisulfite solubility of wool grafted with poly(methyl methacrylate) are much lower than those of physical mixtures of wool and poly(methyl methacrylate). This demonstrates that grafting of poly(methyl methacrylate) into wool has occurred.     

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

The feasibility of a cellulose thiocarbonate–azobisisobutyronitrile (AIBN) initiation system to induce graft copolymerization of methyl methacrylate (MMA) and other acrylic monomers onto cotton fabric was investigated. Other acrylic monomers were acrylic acid, acrylonitrile, and methyl acrylate. The initiation system under investigation was highly activated in the presence of a metal‐ion reductant or a metal‐ion oxidant in the polymerization medium. A number of variables in the grafting reaction were studied, including AIBN concentration, pH of the polymerization medium, nature of substrate, monomer concentration, duration and temperature of polymerization, and composition of the solvent/water polymerization medium. The solvents used were methanol, isopropanol, 1,4‐dioxane, cyclohexane, benzene, dimethyl formamide, and dimethyl sulfoxide. There were optimal concentrations of AIBN (5 mmol/L), MMA (8%), Fe²⁺ (0.1 mmol/L), Mn²⁺ (8 mmol/L), and Fe³⁺ (2 mmol/L). A polymerization medium of pH 2 and temperature of 70°C constituted the optimal conditions for grafting. The methanol/water mixture constituted the most favorable reaction medium for grafting MMA onto cotton fabric by using the Fe²⁺–cellulose thiocarbonate–AIBN redox system. MMA was superior to other monomers for grafting. The unmodified cotton cellulose showed very little tendency to be grafted with MMA compared with the chemically modified cellulosic substrate. A tentative mechanism for the grafting reaction was proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1261–1274, 2004     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000     

Wool graft copolymers initiated by azobisisobutyronitrile

Grafting of methyl methacrylate onto wool fibers using azobisisobutyronitrile as initiator has been investigated under a variety of conditions. Increasing the monomer concentration caused a significant increase in the graft yields. The same holds good for initiator concentration and reaction time, but to a lower degree. The grafting reaction was favorably influenced considerably by the nature of solvent used; it follows the order methanol > dimethylformamide > benzene. For practical significance, a mixture of water:methanol:DMF (75:24:1) was found to be the most effective medium for grafting. Presence of lithium chloride in the polymerization system favors grafting during the later stages of reaction, whereas presence of ceric sulfate was effective for higher grafting in the initial stages of reaction. Reduction of wool prior to grafting enhanced its ability to grafting; the latter increases in proportion to the thiol content. The opposite holds true for acetylation. Alkali solubility measurements reveal that an interaction between wool and methyl methacrylate in presence of AIBN took place.     

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。