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.     

Grafting onto wool. XIV. Graft copolymerization of vinyl monomers by use of Mn(AcAc)3 as an initiator

Ethyl acrylate (EA), butyl acrylate (BA), and vinyl acetate (VAc) have been graft copolymerized onto Himachali wool fiber in an aqueous medium by using Mn(AcAc)₃ as an initiator. Graft copolymerization was studied at 45°, 55°, 65° and 75°C for various reaction periods. Percentage of grafting and percent efficiency were determined as functions of concentration of monomer, concentation of initiator, concentration of nitric acid, time, and temperature. Several grafting experiments were carried out in the presence of various additives which included: (i) pyridine and (ii) Et₃ N. EA, BA, and VAc were found to differ in reactivity towards grafting and followed the order: EA > BA > VAc.     

Grafting onto wool. XVI. Graft copolymerization of vinyl monomers by use of TBHP–FAS as redox initiator

Methyl acrylate (MA), methyl methacrylate (MMA), and n-butyl vinyl ether (n-BVE) have been graft-copolymerized onto Himachali wool in an aqueous medium by using tertiary butyl hydroperoxide ferrous ammonium sulfate (TBHP-FAS) redox system at 40°C, 50°C, 60°C, and 70°C for various reaction periods. Percentage of grafting and percent efficiency have been determined as functions of concentration of monomers, molar ratios of [TBHP]/[FAS], time and temperture. Molar ratios of [TBHP]/[FAS] were found to influence grafting of different monomers studied. Chemical evidence indicates that a covalent bond formation occurs between grafted polymeric chain and backbone polymer. The rate of grafting (R_p) and induction period (I_p) of different monomers towards graft copolymerization were determined as function of total initial monomer concentrations. R_p and I_p of n-BVE are independent of total initial monomer concentrations while R_p and I_p of both MA and MMA were found to depend on the total initial monomer concentrations. MA, MMA, and n-BVE were found to differ in reactivity towards grafting onto wool in the presence of (TBHP-FAS) redox system; the following reactivity order was observed: MMA > MA > n-BVE.     

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.     

Graft polymerization of some vinyl monomers onto acrylic rubber. I. Chain transfer and grafting reaction

The grafting reactions of styrene (St), methyl methacrylate (MMA), and vinyl acetate (VAc) were investigated in the presence of n-butyl acrylate–acrylonitrile copolymer. Results showed that the nature of monomer and initiator were the major factors influencing the grafting activity. The grafting efficiency was 0.87 for St, 0.26 for MMA, and 0.18 for VAc under the most favorable conditions. Acrylic rubber reduced the rate of polymerization, and the retarding effect increased in the order St, MMA, VAc. The chain transfer constants for acrylic rubber were evaluated to be 4.8 × 10^?4 for St, 1.27 × 10^?3 for MMA, and 1.45 × 10^?3 for VAc. The rate of polymerization and the grafting efficiency decreased with increasing acrylonitrile content in acrylic rubber, while the chain transfer constant of St for acrylic rubber remained practically unchanged.     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Particle formation and growth in ab initio emulsifier-free emulsion polymerisation under monomer-starved conditions

Particle formation and growth in the monomer-starved emulsifier-free emulsion polymerisation of monomers with different water solubility including methyl acrylate (MA), methyl methacrylate (MMA), and vinyl acetate (VA) were studied. The rate of formation of precursor particles, via homogenous nucleation, is proportional to the monomer concentration in the water phase. One may think that the maximum number of particles will be obtained when the water phase is saturated with the monomer. The number of PMA particles showed a maximum when the water phase was starved with the monomer. The number of PVA particles did not show any sensitivity to the monomer concentration in the water phase. More unexpectedly the final number of PMMA particles showed a minimum when the water phase was just saturated with the monomer. The minimum in the final number of PMMA particles was correlated with the enhanced rate of particle growth due to the gel effect. Under monomer-starved conditions, the number of particles produced was in the order of water solubility of the monomers; MA > VA > MMA. A reverse order was produced under monomer-saturated conditions as particle coagulation became progressively more important for some of the monomers.     

Grafting onto wool. XX. Graft copolymerization of vinyl monomers by use of redox initiators. Comparison of monomer reactivities

Methyl methacrylate (MMA) and ethylacrylate (EA) have been graft copolymerized onto Himachali wool in aqueous medium by using a ferrous ammonium sulfate–hydrogen peroxide (FAS? H₂O₂) system as redox initiator. Percentage of grafting has been determined as functions of concentration of monomer, molar ratio of [FAS]/[H₂O₂], time and temperature. Percentage of grafting is found to depend upon the molar ratio of [FAS]/[H₂O₂]. An attempt has been made to compare the reactivities of the acceptor monomer (MMA and EA) with that of the donor monomer (VAc) toward grafting onto wool.     

Grafting onto wool. XI. Graft copolymerization of poly(vinyl acetate) and poly(methyl acrylate) onto reduced wool in presence of potassium persulfate–ferrous ammonium sulfate (KPS—FAS) system as redox initiator

In an attempt to ascertain the role of—SH groups of Himachali wool during graft copolymerization, poly(viny acetate) (PVAc) and poly(methyl acrylate) (PMA) were graft copolymerized onto reduced wool by using potassium persulfate—ferrous ammonium sulfate (KPS—FAS) redox pair in aqueous medium. Reduction of wool was carried out by sodium bisulfite solution of varying concentrations for different reaction periods. Concentration of reducing agent and the extent of reduction were found to influence grafting of vinyl monomers. Maximum grafting of methyl acrylate (MA) and vinyl acetate (VAc) occurred when wool was reduced by 1% and 0.5% NaHSO₃ solution, respectively, for 24 h. Increase in percent grafting of MA onto reduced wool compared to that of unreduced wool has been ascribed to the production of more—SH groups by reduction of—SS—groups of wool fiber.     

Photoinitiator‐free UV grafting of styrene,a weak donor,with various electron‐poor vinyl monomers to polypropylene film

This study investigated the possibility of using styrene, a weak donor forming donor(D)/acceptor(A) pairs with electron‐poor (EP) vinyl monomers, for initiating spontaneous photopolymerization and photografting of the copolymers onto polypropylene. Maleic anhydride (MA), methyl methacrylate (MMA), methyl acrylate (MAC), dimethyl maleate (DMMA), acrylonitrile (AN) and acrylic acid (AA) were the EP monomers used. Grafting yields together with FTIR analyses were used to confirm the presence of grafting. Styrene/MMA and styrene/AN systems achieved significant grafting, but such levels of grafting were not observed in the styrene/MAC and styrene/DMMA systems. No grafting was observed for styrene/AA or styrene/MA systems, but the latter system underwent photopolymerization. The effect of solvents on grafting was evaluated on styrene/MMA and styrene/AN systems and dimethylformamide (DMF) was found to retard grafting of both D/A systems. In contrast, chloroform and methanol enhanced grafting of the styrene/AN system although these two solvents had no significant effect on the grafting of the styrene/MMA system. Copyright © 2004 Society of Chemical Industry     

Study of thermal and dyeing behavior of isotactic polypropylene fiber graft copolymerized with acrylate monomers using preirradiation method

In an attempt to modify isotactic polypropylene (IPP) fiber, grafting of acrylate monomers such as methyl acrylate (MA) and ethyl acrylate (EA) onto IPP has been carried out by preirradiation method in aqueous medium. Percentage of grafting has been determined as a function of various reaction parameters. Rate of grafting (R_g) and induction period (I_p) have been evaluated as a function of total initial monomer concentration. Methyl acrylate was found to be more reactive than ethyl acrylate toward grafting. Thermogravimetric analysis (TGA) indicates that the thermal stability of polypropylene fiber is significantly improved upon grafting. While polypropylene fiber could not be dyed by crystal violet, the grafted fiber was dyed with crystal violet, and the dye uptake has been quantitatively determined by spectrometric method. © 1994 John Wiley & Sons, Inc.     

Surface modification of jute yarn by photografting of low‐glass transition temperature monomers

Jute yarns were grafted with three types of vinyl monomers of different functionalities such as methyl acrylate (MA), ethyl acrylate (EA), and 2‐hydroxyethyl acrylate (HEA) with ultraviolet radiation. The graft copolymerization reaction between the cellulose of the jute fibers and the monomer and the chemical environment of the treated fibers were confirmed by Fourier transform infrared spectroscopy. The reduction of OH groups and increment of >C?O groups in treated jute yarns were observed. DSC studies showed that the treated jute fibers were more thermally stable compared to the untreated one. The surface topography of the yarns was analyzed by an environmental scanning electron microscope. Different parameters, such as concentration of monomers and irradiation time, were optimized with the extent of mechanical properties such as tensile strength and elongation at break of the jute yarn. MA, EA, and HEA produced enhanced tensile strengths of 87, 78, and 85%, respectively. The monomers MA, EA, and HEA showed improved elongations at break of 118, 91, and 76%, respectively. The water uptake of treated and untreated jute yarns were studied. The maximum water uptake was observed of the grafted sample compared to the untreated jute yarn. The effects of additives such as urea on mechanical properties were also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 993–1000, 2003     

以聚乙烯醇为保护胶体的乳液与部分官能团的接枝反应研究

主要研究了在以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,乳液与环氧丙烯酸酯、聚氨酯、硅烷等官能团的接枝反应.在以过硫酸铵为引发剂、以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,乳液与上述各类官能团间发生的接枝反应直接影响乳液的黏度、固体含量、剪切强度等宏观性质.研究发现官能单体脂肪醇聚氧乙烯醚、丙烯酸异辛酯(2-EHA)等单体和丙烯酸(AA)与乙烯基三乙氧基硅烷共同作用时对乳液的宏观性质影响显著.     

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.     

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     

改性聚醋酸乙烯玻璃纤维网格布定型胶的研制

采用核/壳乳液聚合工艺,以醋酸乙烯(VAc)为主单体、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为改性单体、丙烯酸(AA)和N-羟甲基丙烯酰胺(NMA)为交联单体,合成出一种玻璃纤维定型用的改性聚醋酸乙烯(PVAc)粘合剂。研究结果表明:当聚合温度为75℃、m(AA)∶m(VAc)∶m(MMA)∶m(NMA)∶m(BA)=1∶35∶7∶1.5∶12时,改性PVAc乳液既具有优良的粘接性能,又具有很强的粘接性、耐水性、耐碱性和弹性,并可赋予玻璃纤维良好的定型防腐功效。     

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.     

食品包装材料用无毒干法覆膜胶乳液的研制

以醋酸乙烯酯(VAc)和甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸丁酯(BA)为软单体、交联单体(TM-200)/丙烯酸(AA)为复合交联剂、叔丁基过氧化氢(TBHP)/甲醛合次硫酸钠(吊白块)为氧化-还原型引发剂、可聚合型阴离子乳化剂(SVS-25)为环保型乳化剂和Gohsefimer Z-210为改性保护胶体,采用乳液聚合法制备出食品包装材料用无毒干法覆膜胶。研究结果表明:采用减压脱除及后添加氧化-还原型引发剂,可使覆膜胶中残余单体含量降至0.01%以下;当m(VAc)∶m(MMA)∶m(BA)=30∶10∶60、乳化剂中m(SVS-25)∶m(Gohsefimer Z-210)=1∶1、w(乳化剂)=2.0%和w(氧化-还原型引发剂)=0.20%时,覆膜胶的综合性能相对最好。     

溶剂型丙烯酸酯压敏胶的研制

以甲基丙烯酸甲酯(MMA)和醋酸乙烯酯(VAc)为硬单体、丙烯酸(AA)和丙烯酸羟乙酯(HEA)为交联单体、甲苯-2,4-二异氰酸酯(TDI)为交联剂和偶氮二异丁腈(AIBN)为引发剂,采用溶液聚合法制取溶剂型聚丙烯酸酯压敏胶(PSA),讨论了硬单体和交联单体的种类及用量、引发剂和交联剂的用量以及烘胶温度对PSA性能的影响。实验结果表明,当W(AA)=3%、W(VAc)=17%时,初粘力为13号球,剥离强度达到14.17N/15mm,PSA的综合性能最佳;当W(TDI)=1.2%时,剥离强度(17.26N/15mm)达到最大值;当W(AIBN)=0.5%时,胶液的黏度适中,综合性能最佳。     

Modification of polyvinyl chloride-vinyl acetate latex by seed emulsion polymerization of acrylic monomers

Fundamental studies were carried out to modify the thermal properties of polyvinyl chloride (PVC)-based latices. General features of composite PVC-vinyl acetate (VAc) copolymer latices synthesized from the seed emulsion polymerization of acrylic monomers are reported, in particular, the observation of particle morphology and the measurements of minimum film formation temperature (MFT) and DSC spectra. Acrylic monomers used as modifiers were methyl methacrylate (MMA), n-butyl methacrylate (BMA), methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (nBA), and MMA-nBA 75:25,50:50 and 25:75 wt%. Styrene whose polymer is incompatible with PVC-VAc was used as a counterpart of compatible PMMA. Compatibility between seed and modifier polymer and the mode of operation, either batch (flooded and pre-swollen) or semi-batch (starved and no swelling), induced morphology differences, and consequently variations of thermal properties.