Photo-initiated vapor-phase grafting of acrylic monomers onto fibrous substrates in the presence of biacetyl

A novel vapor-phase process has been developed for grafting relatively volatile acrylic monomers onto various polymeric substrates, using photo-initiation by near ultraviolet irradiation in the presence of biacetyl vapors. With it, very even graft polymerizations on the substrates, with minimum amounts of homopolymerization, were found. Furthermore, there were essentially no changes in the tensile or aesthetic properties of the treated surfaces. The degree of photografting is dependent upon the chemical composition and porosity of the substrate, the volatility and reactivity of the monomers, prewetting of the substrate with a suitable wetting agent, and the conditions of irradiation used. The effects of various reaction parameters on the photo-induced grafting of methyl acrylate, methyl methacrylate, and acrylonitrile on wool keratin are studied in detail. Increasing biacetyl and monomer flow rates and flow times, irradiation times, and moisture content of the wool all caused progressive increases in the amount of polymer grafted to the wool, up to limiting values dependent on the reaction parameters involved and monomer used. In all instances, the amount of homopolymer found on the fiber was limited and remained essentially constant over the range of conditions studied. A series of acrylic monomers of different volatilities and reactivities including methyl acrylate, methyl methacrylate, butyl acrylate, acrylic acid, acrylamide, acrylonitrile, N,N-dimethylaminoethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate was successfully grafted onto several hydrophilic and hydrophobic textile fibers (wool, cotton, rayon, nylon, acrylics, polyester, and polypropylene) and other polymeric surfaces such as filter paper, cellophane, and acetate film by this process. The wetting agents used included water, methyl and n-propyl alcohol, N,N-dimethylformamide, dimethylsulfoxide, benzene, and chlorinated hydrocarbon solvents.     

丙烯酸甲酯与聚醋酸乙烯酯的核／壳乳液聚合反应

本文研究了丙烯酸甲酯在聚醋酸乙烯酯种子胶粒上的核/壳复合高分子乳液聚合反应。讨论了接枝聚合反应中引发剂的浓度、单体与聚合物的比例、乳化剂用量等工艺参数对该类接枝聚合反应的影响,提出了核/壳乳液聚合反应的一些反应规律。     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. II. Chemical Structure of Grafted Power Feed Polymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through a non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. With the increase of PVA, grafting was also increased. Feeding method did not affect grafting nor grafting efficiency to a great extent. However, the amount of initiator had a negative correlation against grafting or grafting efficiency. From NMR spectroscopy, it was known that n-butyl acrylate monomer grafted onto PVA rather than copolymerized with styrene monomer. In order to increase the cohesive strengths of each phase, grafting was introduced to the power feed polymerization. In these cases, the chemical structure of grafted power feed polymer was investigated.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. II. Chemical Structure of Grafted Power Feed Polymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through a non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. With the increase of PVA, grafting was also increased. Feeding method did not affect grafting nor grafting efficiency to a great extent. However, the amount of initiator had a negative correlation against grafting or grafting efficiency. From NMR spectroscopy, it was known that n-butyl acrylate monomer grafted onto PVA rather than copolymerized with styrene monomer. In order to increase the cohesive strengths of each phase, grafting was introduced to the power feed polymerization. In these cases, the chemical structure of grafted power feed polymer was investigated.     

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。     

Vapor-phase grafting of methyl acrylate on fiber surfaces treated with aqueous dispersions of metal oxides

Textile fabrics of cotton, wool, nylon, polyester, acrylic, and polyolefin pretreated with aqueous dispersions of photosensitive metal oxides (antimony, tin, titanium, and zinc oxide) were exposed to methyl acrylate vapors with simultaneous ultraviolet irradiation (>3100 Å) for up to 2hr. The metal oxides acted either as effective photosensitizers, causing increased polymer grafting on the fiber surface, or as photoabsorbers causing a net decrease in grafting compared to unsensitized photografting. Metal oxide-induced grafting occurred more readily on hydrophilic fibers and was accompanied by less homopolymer formation, in comparison to grafting on more hydrophobic fibers. Antimony and tin oxides were more effective on hydrophilic fibers, while zinc oxide was more effective on hydrophobic fibers. Titanium dioxide was essentially ineffective as a photosensitizer. The sensitized grafting process was studied in relationship to irradiation and monomer flow time, the degree of homopolymer formation accompanying grafting, the nature of the metal oxide and polymer graft on the fiber surface, and the reflectance characteristics of the metal oxide-treated fabrics.     

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 vinyl monomers on cellulosic materials

Graft copolymers of acrylonitrile, ethyl acrylate, methyl acrylate, ethyl methacrylate and methyl methacrylate and of acrylonitrile/ethyl methacrylate and acrylonitrile/methyl methacrylate monomer mixtures on carboxymethylcellulose (degree of substitution 0.4–0.5) were prepared by use of ceric ion initiator in aqueous medium. The extent of graft polymer formation was measured in terms of graft level, molecular weight of grafted polymer chains and frequency of grafting as function of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight and frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen content of the acrylonitrile/alkyl methacrylate copolymer samples showed that a relativity low amount of the acrylonitrile monomeric units were incorporated into the graft copolymer even at high acrylonitrile content of the feed.     

Graft Copolymerization of Acrylamide onto Oil Palm Empty Fruit Bunch (OPEFB) Fiber

Grafting of acrylamide (AAm) onto oil palm empty fruits bunch fiber using hydrogen peroxide as initiator and methyl acrylate as comonomer was investigated. The amount of comonomer needed to make grafting of acrylamide possible was determined. The percentage of poly(acrylamide) and the comonomer in the final graft copolymer was estimated by elemental analysis. Results obtained indicated that methyl acrylate facilitated the incorporation of acrylamide monomer onto OPEFB. The reactivity ratios for both monomers were determined by using Fineman–Ross plot. The effects of reaction temperature and period as well as amount of the initiator, solvent, monomer and comonomer on the percentage of grafting at fixed amount of comonomer (11 mmol) were studied. Maximum percentage of grafting was achieved when the amount of initiator and solvent 3.98×10⁻³ mol and 50 mL respectively. The optimum reaction temperature was 50 ^○C and the reaction period was 90 min. Highest percentage of grafting was 232% when 25.6 mmol of acrylamide was used under these optimum conditions. The presence of functional group in the grafted polymer is characterized by infrared spectroscopy and the surface morphology is observed by scanning electron microscopy. Thermoanalytic investigation on OPEFB and OPEFB-g-PAAM were carried out to evaluate the thermal stability and respective activation energy of the materials.     

Photo-induced polymerization of methyl acrylate vapors on prewetted polyamide and polyester fibers

Photo-induced polymerization of methyl acrylate vapors on polyamide and polyester fibers occurred when these fibers were wetted with the polar solvents methanol, N,N-dimethylformamide, or dimethyl sulfoxide (neat or in aqueous solution). Polymer grafting was accompanied by homopolymer formation, with the amount of grafting and ratio of grafting to homopolymerization being dependent on the fiber type, the solvent used to wet the fiber, and the amount of water present in the wetting solution. Overall deposition of polymer was higher on polyamide than on polyester under all wetting conditions. Water present in the wetting agent had a limited effect on polymerization of poly(methyl acrylate) on polyamide, whereas water caused a rapid decrease in polymerization on polyester. The nature of polymer grafting on the fibers under various wetting conditions was examined by scanning electron microscopy and tensile property measurements, and the mode of polymer deposition was outlined in light of our findings.     

反相微乳液法合成耐温抗盐聚合物驱油剂

以丙烯酰胺（AM）、2-丙烯酰胺-2-甲基丙磺酸（AMPS）和甲基丙烯酸十八酯为单体,过硫酸钾（K2S2O8）-亚硫酸氢钠（NaHSO3）为氧化还原引发体系,Span60为乳化剂、煤油为分散相进行反相微乳液聚合,合成了驱油用耐温抗盐聚合物。研究了单体的加量、单体的浓度、引发剂的浓度、反应温度、pH值等因素对聚合物粘度的影响,并对产品的耐温抗盐性进行评价。结果表明：在AMPS加量为20%、甲基丙烯酸十八酯加量为1%、单体的浓度为25%、反应温度为53℃、引发剂浓度为0.4%、pH值为10、反应7～8h时,聚合物的粘度最大,并表现出良好的耐温抗盐性能。     

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.     

Deposition of acrylate polymers in wool fibers

The factors influencing the kinetics of formation of acrylate polymers in wool fibers are described. Allyl methacrylate and N,N′-methylenebisacrylamide were found to copolymerize satisfactorily with methyl or ethyl acrylate to form crosslinked polymers. Conditions were found for almost complete conversion of the available monomer to polymer in a batch-type process.     

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     

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.     

Grafting mechanisms in hybrid miniemulsion polymerization

The ultimate objective of hybrid miniemulsion polymerization is to produce a water‐based crosslinkable coating through in situ grafting of a free radical growing acrylic polymer with an unsaturated resin. Certain authors have reported low grafting while others have reported higher. This article explores the factors that influence the grafting tendencies of these systems. Methacrylates such as methyl methacrylate (MMA) have a sterically hindered radical center that lowers its reactivity toward unsaturated resin. This steric hindrance from the methyl group forces grafting of this type of monomer to occur by abstraction of a hydrogen allylic to a resinous double bond. This chain transfer produces a relatively inactive radical on the resin that reduces the grafting efficiency. The transfer process also inherently produces some degree of terminated PMMA polymer within the particle. Grafting occurs in this type of system through termination of living PMMA chains with that radical produced on the resin. For relatively water‐soluble monomers such as MMA, grafting efficiency is further lessened by homogeneous nucleation resulting from the monomer hydrophilicity. These newly created particles cannot contain alkyd due to its hydrophobicity and thus inability to transport across the aqueous phase, and hence cannot produce grafted polymer. Nonetheless, degree of grafting of nearly 50% was observed in these systems. For hybrid systems involving an acrylate monomer such as butyl acrylate (BA), virtually complete grafting with alkyd was observed. This is due to the uninhibited BA radical center allowing the molecule to add directly through a resin double bond. This process offers the possibility for complete grafting. Homogeneous nucleation is not involved in this system due to the insolubility of BA in the aqueous phase. Resin double bond content and degree of conjugation also play an integral role in the grafting process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1825–1836, 2003     

聚丙烯酸类超强吸水剂的合成与性能研究

以丙烯酸烯丙酯作为交联剂、丙烯酸(AA)为单体、过硫酸钾(KPS)为引发剂,采用溶液聚合法合成了一种聚丙烯酸类超强吸水剂。研究了合成条件对吸水性能的影响:当ρ(丙烯酸烯丙酯)=0 594g/L,ρ(KPS)=0 178g/L,单体中和度x(丙烯酸钠)=90%,c(丙烯酸钠)=4 17mol/L,聚合温度为60℃时,制得的聚合物每克吸去离子水最高达到1360mL,吸盐水(生理盐水)162mL。所得的聚合物具有良好的吸水可逆性,30min的吸水量可以达到饱和吸水量的90%。制得聚合物的热重分析表明,未吸水的该聚合物在350℃开始分解。聚合物吸水前后XRD测试结果显示:吸水前聚合物结构基本无规整性,吸水后膨胀使主链展开,结构趋于规整。     

酶解淀粉-苯乙烯/丙烯酸丁酯接枝共聚物乳液的制备研究

采用无皂乳液聚合的方法,以过硫酸铵(APS)为引发剂,制备了酶解淀粉与苯乙烯(St)和丙烯酸丁酯(BA)的接枝共聚物。探讨了淀粉与单体配比、过硫酸铵用量、单体配比和反应温度对接枝反应的影响。结果表明,反应的优化条件为:m(淀粉)∶m(单体)=1∶3,(NH4)2S2O8的加入量为淀粉与单体总质量的0.5%,单体质量比为1∶1,反应温度为82℃,在此条件下,接枝率可达103.8%,接枝效率为37.4%,单体转化率为91.9%。红外光谱分析表明,苯乙烯和丙烯酸丁酯参与了接枝反应;SEM结果显示,接枝反应之后,淀粉形貌发生了变化,球状颗粒已经消失。     

Radiochemical grafting of methacrylonitrile and its binary mixture with methyl acrylate onto gelatin

Methacrylonitrile (MAN) has been graft copolymerized individually and as a binary mixture with methyl acrylate (MA) onto gelatin by a simultaneous irradiation method. Percentage grafting has been studied as a function of total radiation dose, monomer concentration, amount of water and water–methanol system. It was found that addition of MA increased the grafting efficiency of MAN. A plausible explanation has been suggested to account for the trends in the results © 1998 SCI.     

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。