Graft copolymerization of hydrophilic monomers onto irradiated polypropylene fibers

A method of graft copolymerization of hydrophilic monomers, such as 1-vinyl-2-pyrrolidone, acrylonitrile, acrylic acid, and acrylamide, onto irradiated polypropylene fibers has been studied. γ ray as well as electron beam were employed for the irradiation processes. Graft-copolymerization kinetics and the properties of grafted fibers have been investigated. Moisture regain, dyes absorption, and melting point of the grafted fibers were found to increase with the increasing of the degree of grafting. Polypropylene for 1-vinyl-2-pyrrolidone grafted fibers showed excellent dye absorption for almost all kinds of dyes such as direct, basic, acid, reactive, disper, and naphthol dyes. However, for polypropylene acrylic acid grafted fibers, the colorfastness to washing was found to be unsatisfactory. The colorfastness to washing for polypropylene 1-vinyl-2-pyrrolidone grafted fibers was found to be fairly good for certain types of dyes such as vat and naphthol dyes.     

Radical grafting of polar monomers onto polypropylene by reactive extrusion

Polypropylene (PP) was functionalized in the melt by grafting polar monomers using an internal mixer and a corotating twin‐screw extruder. 2,5‐Bis(tertbutylperoxy)‐2,5‐dimethylhexane (Luperox 101) and dicumyl peroxide (DP) were the used radical initiators. The polar monomers were itaconic acid (IAc), 2‐octen‐1‐ylsuccinic anhydride (OY), 2‐hydroxyethyl methacrylate (HEMA), and 3‐allyloxy‐1,2‐propanediol (AP). Grafting was quantified by FTIR combined to Elemental Analysis. Grafting degree depends mainly on monomer and initiator natures and concentrations. Grafting degree maxima were 3.9, 2, 9.5, and 3.9 wt %, respectively, for IAc, OY, HEMA, and AP. Some properties of the modified PP were evaluated. Thermal analysis indicated that the polarity of PP increased by grafting reaction and size‐exclusion chromatography showed that the grafting was not accompanied by a significant M_w and viscosity decrease. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Grafting onto polyester fibers. IV. Synergism during graft copolymerization of binary mixtures of vinyl monomers onto polyester fibers

Graft-copolymerization reactions of binary mixtures of vinyl monomers (acrylamide–acrylic acid and acrylonitrile–acrylic acid) with polyester fibers have been studied by chemical initiation technique using benzoyl peroxide as an initiator. The total graft add-on was determined gravimetrically, while the modified Kjeldahl's method for N-estimation was employed to determine acrylamide and acrylonitrile grafts in their mixtures with acrylic acid grafts. Synergism of very high order was noticed during the graft-copolymerization reactions. In the case of the acrylamide–acrylic acid system a very high order of synergism (129.15%) was noticed at equimolar proportions of the monomers in the grafting bath. Both acrylamide and acrylic acid showed synergistic influence over each other during graft-copolymerization reactions. In the case of the acrylonitrile–acrylic acid system, however, the presence of acrylonitrile reduced the graft yield of the acrylic acid component showing a negative synergism; but acrylic acid enhanced the acrylonitrile graft yield to a considerable extent. The results have been explained in terms of reactivity ratios of the monomers. The conductivity results of the monomer mixtures also supported the experimental results.     

Radiation induced ionic polymerisation and grafting of vinyl monomers

Some special aspects of the radiation induced ionic polymerisation and grafting of vinyl monomers will be described. In particular the effects of solvents on the cationic polymerisation of the vinyl ethers will be discussed in detail. The unequivocal free ion nature of the polymerisation makes such information of considerable general interest. Estimates of the propagation rate constants with free cation polymerisation in solvents of different dietectric constants and solvation powers will be presented. Finally, some observations on the radiation induced graft polymerisation of ethyl vinyl ether to poly (vinyl chloride) and to polypropylene will be presented.     

Grafting onto polyester fibers. II. Kinetics of grafting of acrylic acid,acrylonitrile, and vinyl acetate onto polyester fibers

The kinetics of grafting of acrylonitrile, acrylic acid, and vinyl acetate onto polyester fiber by catalytic initiation and radiation were studied. The energy of activation determined for acrylic acid grafting by the catalytic method was 10.7 kcal/mole and that for vinyl acetate grafting by the radiation method, 11.7 kcal/mole. In the case of acrylonitrile grafting by the catalytic method, the rate of grafting decreased with increase in temperature of grafting, showing the differential behavior of the precipitating type of polymer from that of homogeneous polymerization.     

Radiation grafting of vinyl monomers onto wood pulp cellulose. II

The effect of radiation dose rate and beating time on the mutual radiation grafting of styrene to unbleached and bleached kraft wood pulp was studied. Companion studies on the effect of beating time, peroxidation grafting, and order of monomer addition on the preirradiation graft copolymerization of acrylamide and diethylaminoethyl methacrylate were conducted on bleached wood pulp. The grafting rate of styrene increased with dose rate, but the kinetics suggests a significant diffusional resistance to the observed grafting rate. The per cent graft measured at fixed grafting conditions decreased markedly as pulp beating (effected prior to grafting) was increased. It is suggested that the decrease in grafting with beating is due to an increase in the accessibility and swelling of the beaten fibers. Dimethylaminoethyl methacrylate appeared to inhibit the grafting of acrylamide, and double grafting had to be used to graft both hydrophilic polymers to the pulp. The mechanical properties of high-yield pulp and groundwood were improved by the addition of the grafted pulps. The double grafts appeared to show promise as fibrous beaten additives for dry strength improvement. The styrenegrafted pulps were found not to respond at all to the beating process.     

Radiation-induced grafting of functional acrylic monomers onto polyethylene and polypropylene films using acryloyl chloride

Summary Radiation-induced graft polymerization of acryloyl chloride onto films of polyolefins (polyethylene and polypropylene) using gamma radiation was investigated in order to establish a convenient method to obtain polymer films grafted with polyacrylic esters. Grafting was carried out by three different methods; (i) direct irradiation of film in monomer solution (ii) vapor phase irradiation method, and (iii) pre-irradiation in air. The effects of monomer concentration, radiation dose and methods of grafting, on the formation of grafted polyolefins are reported in this paper. Received: 5 April 2000/Revised version: 17 November 2000/Accepted: 20 November 2000     

Radiation grafting of vinyl monomers onto wood pulp cellulose. Part I

The effect of dose, dose rate, monomer type, and monomer concentration on the water transport behavior in grafted cellulose pulp and hand sheets was studied. At low dose rates, grafting rates of styrene onto wood pulp were less with hand sheets than with the pulp itself. Grafting was also found to be decreased by increasing the dose rate. Grafting mixtures of styrene and acrylonitrile gave better yields than styrene alone. Excellent grafting yields were obtained by treating the pulp or hand sheets with water before adding vinyl monomers. In this way, solvents such as dioxane could be eliminated from the grafting mixture. The hand sheets, grafted with mixtures of acrylonitrile and styrene, had good mechanical properties although less than the corresponding ungrafted sheets. Grafting decreased the moisture regain in pulp and hand sheets. Gamma irradiation of wood pulp under ambient conditions without additives reduced the water sorption considerably.     

Ultrasonic induced grafting of maleic anhydride onto polypropylene in melt state

This paper presented a model study on maleic anhydride (MAH) grafted polypropylene (PP) performed in melt state through ultrasonic initiation without any chemical initiator and solvent. The structures of PP-g-MAH were characterized by FTIR and ¹³C NMR and the mechanism were discussed. The graft degree (G) was determined by titration using a solution of organic base tetra-butyl ammonium hydroxide (TBAOH) in ethanol, and the effects of ultrasonic intensity, MAH concentration and styrene (St) on G and graft efficiency (G _E ) of MAH were investigated. Results showed that MAH was successfully grafted onto the PP chain and the optimum conditions for grafting were at an ultrasonic intensity of 300 W with a MAH concentration of 25 wt.%, and the maximum G of MAH of 3.34 wt.% was obtained when the molar ratio of St to MAH was 1:1. DSC and XRD were also employed to determine the thermodynamic performance and crystalline structures of the products.     

Grafting of polypropylene fibers. I. Radiation grafting of vinyl monomers,dyeing, and hydrophilic characteristics of the grafted polymer

Radiation-initiated grafting of methacrylic acid, acrylonitrile, and vinyl acetate on polypropylene fibers and the moisture content and dyeing characteristics of the grafted fibers have been reported. The extent of grafting with methacrylic acid is quite large when compared to acrylonitrile and vinyl acetate. The grafted fibers show an increase in moisture content with increase in the amount of graft. In general, the dyeability with disperse dyes increases due to grafting. In the case of cationic dyes, the polypropylene fibers grafted with methacrylic acid and acrylonitrile alone could be dyed.     

Grafting vinyl monomers onto polyester fibers. VI. Graft copolymerization of methyl methacrylate onto PET fibers using tetravalent cerium as initiator

The graft copolymerization of methyl methacrylate onto polyester fibers (PET) was investigated using tetravalent cerium as the initiator. The rate of grafting was found to increase progressively with the initiator and monomer concentrations up to 2.5 × 10^?2M and 70.41 × 10^?2M, respectively. The reaction was found to be catalysed by acid up to 15.0 × 10^?2M. The graft yield increased by increasing temperature. The effect of addition of some solvents and thiourea on the rate of grafting was also investigated. A suitable kinetic scheme has been pictured, and rate equations have been derived.     

Plasma-induced hydrogel grafting of vinyl monomers on polypropylene

Polypropylene (PP) film was plasma-treated using a 13.56 MHz direct plasma with argon, nitrogen, and oxygen as the plasma-forming gases. The three gases induced very different changes on the PP film surface, which were studied using contact angle measurements. Because of its degrading and oxidative effect, oxygen plasma pretreatment was not used for the homogeneous grafting of acrylic acid and acrylamide. Nitrogen plasma treatment did not lead to the formation of stable peroxides on the film surface and did not undergo grafting reactions. This may be due to the types of radicals and functional groups created on the surface during the plasma treatment. Finally, argon plasma pretreatment was found to be the most effective for the grafting of vinyl monomers. The amount of grafted poly(acrylic acid) was shown to be proportional to the concentration of peroxides created by argon plasma treatment.     

Solid-phase grafting of glycidyl methacrylate onto polypropylene

Free-radical grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) powder was studied in a batch mixer. The reaction temperature was below the melting point of PP so that PP was modified in the solid phase. The graft yield of GMA obtained under various experimental conditions allowed for a good appreciation of the effects of chemical parameters (the concentration of monomer, initiator, and interfacial agent) and those of processing parameters (reaction time and temperature). Toluene was used as an interfacial agent to etch the surface of PP powder to provide more sites for reaction. Quantitative determination of the graft level was performed by wet chemical methods. The results showed that the solid-phase grafting could take place over a temperature range of 100–140°C in the initiation of benzoyl peroxide (BPO). The ultimate GMA grafting level achieved was higher than that obtained in the melt state with dicumyl peroxide (DCPO) as a radical initiator. The grafting of GMA affected the crystalline morphology of PP and speeded up the crystallization process. The energy of activation and initial decomposition temperature of grafted samples were higher than those of ungrafted PP. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1905–1912, 1997     

Melt free-radical grafting of glycidyl methacrylate onto polypropylene

This paper concerns free-radical grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) in the molten state carried out in a batch mixer. This free-radical grafting proceeds very rapidly as it goes to completion within two to three minutes at 200°C. The grafting yield of GMA alone is low and it is greatly enhanced upon addition of styrene as a second monomer with a reduced chain degradation of PP. Homopolymer and copolymer of GMA formed during grafting were quantified. It is suggested that in the presence of styrene, the dominating grafting mechanism is that styrene reacts with the PP macroradicals to form more stable styryl macroradicals which then react with GMA to form GMA-grafted PP. The rate of this reaction is much greater than that between the PP macroradicals and GMA. Unlike grafting of mixtures of maleic anhydride and styrene, which is dictated primarily by formation of a charge transfer complex, free-radical grafting of GMA in the presence of styrene follows a random copolymerization process.     

Reactivity ratios during radiation‐induced grafting of comonomer mixtures onto polyester fabrics

Radiation‐induced grafting of binary mixtures of acrylonitrile (AN)/styrene (S) and acrylamide (AAm)/styrene (S) onto polyester fabric (PET) has been investigated. Synergism during radiation grafting was investigated by determining the graft yield fraction for each monomer in the final graft copolymer. Moreover, by knowing the mole fraction of each monomer in the grafting solution, the reactivity ratio of the individual monomers in the comonomer mixture during graft copolymerization could be determined: in the case of AN/S comonomer mixture, the calculated reactivity ratios for AN and S are 0.04 and 0.05, respectively; the calculated reactivity ratios of AAm and S in their comonomer mixture are 1.82 and 0.41, respectively. © 2001 Society of Chemical Industry     

马来酸二丁酯固相接枝聚丙烯

以马来酸二丁酯(DBM)为单体,在自制的固相反应器中,采用先降解、后固相接枝技术,制备了具有高流动性的马来酸二丁酯接枝聚丙烯(PP-g-DBM),并表征与分析了该接枝物结构,研究了反应时间、引发剂和单体用量对接枝率的影响,考察了相对分子质量、熔体流动速率(MFR)与反应时间的关系.结果表明:在混合引发剂质量分数为6%、w(DBM)为10%、反应温度为100～120℃的条件下,PP在降解3 h后,再接枝3 h,可以得到相对分子质量为5×104、MFR为650～750g/10min、接枝率为7%的PP-g-DBM.     

Radiation grafting of N,N-dimethylaminoethylmethacrylate and 4-vinylpyridine onto polypropylene by the one- and two-step methods

Summary Radiation grafting of N,N-dimethylaminoethylmethacrylate (DMAEMA) and 4-vinylpyridine (4-VP) from the 50% monomers solutions in toluene and dichloroethane onto polypropylene (PP) films was carried by their mutual γ-irradiation (one-step method). In the two-step method, the grafting of DMAEMA or 4-VP from their solutions in toluene was performed onto PP modified preliminary with the other polymer (poly4-VP or polyDMAEMA). It has been found that chemical structure of PP modified with the first grafted polymer affected the efficiency of the other monomer grafting by the second step. Received: 30 April 2001/Revised version: 21 October 2001/Accepted: 28 November 2001