Investigation of radiation grafting of vinyl acetate onto (tetrafluoroethylene–perfluorovinyl ether) copolymer films

A study has been made of radiation-induced grafting of vinyl acetate (VAc) on to (tetrafluoroethylene–perfluorovinyl ether) copolymer (PFA). Effects of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield were investigated. In this grafting system, ammonium ferrous sulphate (Mohr′s salt) was added to the monomer-solvent mixture to minimize the homopolymerization of VAc and the most suitable concentration was found to be 2.0 wt%. It was found that the dependence of the initial grafting rate on monomer concentration is of the order 1.5. The degree of grafting tends to level off at high irradiation doses due to the recombination of formed free radicals without initiating graft polymerization. Some properties of the prepared graft copolymer such as swelling behaviour, electrical conductivity, thermal and mechanical properties were also investigated. The electrical conductivity was improved by hydrolysis of poly(vinyl acetate) in the grafted chains to their respective vinyl alcohols. The tensile properties were improved by grafting; however, the elongation percent decreased. The DTA data showed thermal stability of such graft copolymers for temperatures up to 300°C, but stability decreased at higher temperatures.     

Radiation Grafting of N-Isopropylacrylamide onto Poly(vinyl chloride) tubes by Gamma Irradiation

Summary Grafted copolymer of poly(vinyl chloride) (PVC) with N-isopropylacrylamide (NIPAAm) was prepared by radiation-grafting method using γ-ray source. NIPAAm was graft polymerized from its aqueous solution onto PVC tubes by preirradiation method, all samples were exposed in the presence of air at room temperature to ⁶⁰Co. Conditions for achieving maximum grafting yield were observed between 0.5 and 1 moldm^-3 of monomer concentration, pre-irradiation dose of PVC from 5 to 110 kGy, and reaction temperature of 323 and 333 K. Characterization of the grafted copolymer was conducted by various methods: FTIR-ATR, TGA, and SEM. The temperature-responsive behavior of grafted copolymer was studied by swelling at various temperatures and pH 6.8.     

Synthesis and Characterization of Starch-Poly(vinyl Acetate) Graft Copolymers and their Saponified Form

A redox initiation system based on potassium persulfate/acetone sodium bisulphite (KPS/ASBS) was developed to initiate the graft copolymerization of vinyl acetate (VAc) monomer onto corn starch in aqueous solution. The grafting reaction was studied with respect to grafting yield (GY), grafting efficiency (GE) and total conversion (TC) and results obtained were compared with those a well-established redox initiation system namely potassium persulfate/sodium bisulphite (KPS/SBS). The effect of reaction variables such as redox initiator concentration, liquor ratio, reaction time and temperature as well as VAc concentration were investigated. The GY, GE and TC increased significantly with increase of the redox initiation concentration up to 8/16 mmol/l irrespective of the initiation system used. Moreover, optimal grafting was obtained at 60 ^○C for KPS/ASBS redox system and 70 ^○C for KPS/SBS redox system. Saponification of poly (vinyl acetate)-starch graft copolymers were effected using NaOH in three different bath media (n-hexane, acetone or methanol) to convert starch-g-poly(vinyl acetate) to starch-g-poly(vinyl alcohol). Higher extent of solubility in hot water of the saponified form was achieved by using a bath containing n-hexane/sodium hydroxide; however, increasing the graft yield higher than 26.3% decreases the solubility. The structures and thermal stability of starch, grafted starch copolymer and saponified grafted starch copolymer were characterized by infrared spectroscopy and thermogravimetric analysis. Moreover, the rheological behavior as well as sizing performance of the saponified grafted starch copolymers were evaluated and compared with the native starch and commercial polyvinyl alcohol.     

Effects of synthesis conditions on radiation-induced graft copolymerization of methacrylic acid on to poly(vinyl chloride) films

Poly(vinyl chloride) (PVC) films were grafted with methacrylic acid (MAA) using a simultaneous-irradiation technique. The effect of solvent ratio (methanol-water) on grafting was studied and maximum grafting was found for an equivolume mixture of methanol and water. The graft level increased with increase of the plasticizer (dioctylphthalate) content in PVC. Grafting was found to be higher at low dose rate and increased linearly up to 0.25 Mrad for all dose rates and then levelled off. Grafting also increased continuously with increasing monomer concentrations up to 5.4mol/litre, but a linear increase in grafting was observed only up to 2.5 mol/litre. The dependences of rate of grafting on dose rate and monomer concentration were found to be 0.62 and 1.20 respectively.     

Study of radiation-induced graft copolymerization of vinyl acetate onto ethylene-co-propylene rubber

The radiation-induced graft copolymerization of vinyl acetate (VAc) onto ethylene-copropylene rubber (EPR) has been studied in methanol with radiation of cobalt-60. The effects of irradiation dose, dose rate, concentration of monomer, Cu⁺⁺ concentration, and temperature on the degree of grafting were investigated. The dependence of the initial grafting rate on dose rate, monome, and Cu⁺⁺ concentration were found to be 1.0, 1.95, and 0.5 order, respectively. The apparent activation energy was calculated to be 49 kJ/mol. Mechanical properties of the grafted polymer were investigated as a function of the grafting percentage. The tensile strength increases and elongation of break decreases with the increase of the degree of grafting in the region of low grafting percentage (≅ 10%). © 1996 John Wiley & Sons, Inc.     

Preparation,characterization, and properties of poly(vinyl chloride)/organophilic‐montmorillonite nanocomposites

Poly(vinyl chloride) (PVC)/organophilic‐montmorillonite (OMMT) nanocomposites were prepared by direct melt intercalation. PVC/compatibilizer ((vinyl acetate) copolymer (VAc))/OMMT nanocomposites were also prepared by melt intercalation by a masterbatch process. The effect of OMMT content on the nanostructures and properties of nanocomposites was studied. The nanostructures were studied by wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM). The linear viscoelastic properties and dynamic mechanical properties of PVC/OMMT nanocomposites were also investigated by an advanced rheometric expansion system (ARES) rheometer. The results showed that partially exfoliated and partially intercalated structures coexisted in the PVC/OMMT and PVC/VAc/OMMT nanocomposites. The mechanical properties test results indicated that the notched Charpy impact strengths of nanocomposites were improved compared to that of pristine PVC and had a maximum value at 1 phr OMMT loadings. The compatibilizer could further improve the impact strengths. But the existence of OMMT decreased the thermal stability of PVC/OMMT and PVC/VAc/OMMT nanocomposites. The linear viscoelastic properties test results indicated the dependence of G′ and G″ on ω shows nonterminal behaviors, and they had better processibility compared with pristine PVC. However, the glass transition temperatures of PVC/OMMT nanocomposites almost had little change compared to that of pristine PVC. POLYM. COMPOS., 27:55–64, 2006. © 2005 Society of Plastics Engineers     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Ultrafiltration membranes obtained by grafting hydrophilic monomers onto poly(vinyl chloride)

The grafting of vinylacetate (VAc) or hydroxyethylmethacrylate (HEMA) onto poly(vinyl chloride) (PVC) has been performed by means of γ-rays or chemical initiators. The grafted polymer so obtained has been separated by selective extraction and submitted to IR spectroscopy in order to check the amount of grafting. The grafting percentage was measured as a function of the grafting conditions. Using the above-mentioned polymer, dissolved again in DMF, asymmetric ultrafiltration membranes have been prepared by the phase inversion technique. The membranes have been tested with Dextran solutions. Their performances have been studied as functions of the grafting amount. The values of rejection and permeating flux demonstrated the effectiveness of the treatment in enhancing the performances of PVC ultrafiltration membranes.     

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45074.     

ARGET ATRP法合成聚氯乙烯接枝丙烯酸丁酯共聚物

以不稳定氯含量高的聚氯乙烯（U-PVC）和氯乙烯-溴代异丁酸烯丙酯共聚物（PVC-co-ABrMP）为大分子引发剂,使用电子转移催化再生原子转移自由基聚合（ARGET ATRP）进行丙烯酸丁酯（BA）的溶液接枝共聚。在固定CuCl₂：三（2-吡啶甲基）胺：辛酸亚锡（摩尔比）时,当CuCl₂用量（相对于氯乙烯链节数）小于0.1%时,BA转化率随CuCl₂用量增加而明显增加;辛酸亚锡与CuCl₂摩尔比大于50时,辛酸亚锡用量对聚合速率的影响较小;相同催化体系用量下,采用PVC-co-ABrMP为引发剂,可获得更高的BA转化率。通过PVC-co-ABrMP酯基水解得到PBA支链,其分子量分布指数为1.29,符合“活性”自由基聚合的特征。接枝PBA对PVC有明显的内增塑效果,PBA摩尔分数为32.75%的PVC-g-BA的玻璃化温度为8.34℃。     

Improvement in physical properties of poly(vinyl chloride) by radiation-induced graft copolymerization with mixed monomers

Gamma-ray-induced graft copolymerization of butadiene with vinyl monomers onto PVC was attempted to improve the physical properties of PVC. The Izod impact strength was increased from 2 kg·cm/cm² to more than 100 kg·cm/cm² by grafting ca. 10% butadiene. But the tensile strength and melt flow were decreased by the grafting. The electron micrograph showed that the mass of polybutadiene in the graft copolymer had a convenient diameter (0.1–1 μ) for absorbing the impact energy. The weatherability of PVC grafted with butadiene was improved by cografting of butadiene with acrylates and methacrylates which had long side chains.     

Synthesis and properties of poly(vinyl chloride-g-2-methyl-2-oxazoline)

Summary Poly(vinyl chloride-g-2-methyl-2-oxazoline) copolymers were prepared by grafting from the allyl chloride sites of PVC with KI or AgOSO₃CF₃ as coinitiators. Use of AgOSO₃CF₃ led to higher grafting efficiencies and higher contents of poly(2-methyl-2-oxazoline) in the graft copolymers. DTA analyses of the P(VC-g-Me-Oxz) identified the thermal transitions of this copolymer; TGA analyses showed that the graft copolymers were less thermally stable than the constituent homopolymers. Unlike blends of P(Me-Oxz) and PVC, the graft copolymers could be molded easily; the graft materials exhibited greater flexural moduli but lower HDT's than PVC.     

氯乙烯/丙烯酸酯二元及多元共聚物的研究进展

介绍了氯乙烯/丙烯酸酯多元共聚物、聚氯乙烯树脂/丙烯酸酯/顺丁烯二酰亚胺接枝共聚物、聚氯乙烯树脂/N-取代马来酸胺/丙烯酸酯接枝共聚树脂、氯乙烯/乙酸乙烯/丙烯酸羟丙酯共聚物、氯乙烯/乙酸乙烯/丙烯酸丁酯共聚乳液、聚丙烯酸酯-氯乙烯接枝共聚物、氯乙烯/乙烯/丙烯酸羟乙酯共聚涂料树脂、氯乙烯/丙烯酸甲酯共聚乳液的特点、生产工艺及其性能和用途.     

Radiation crosslinking of poly(vinyl chloride) with trimethylolpropanetrimethacrylate. II. Dependence on radiation dose and blend composition

The radiation crosslinking of poly(vinyl chloride) (PVC) blended with trimethylolpropanetrimethacrylate (TMPTMA) has been examined. The polyfunctional TMPTMA undergoes polymerization incorporating the PVC into a 3-dimensional network. The kinetics and mechanisms of these crosslinking reactions were studied with particular reference to dependence on radiation dose and blend composition. The crosslinking rate was found to be proportional to the TMPTMA concentration. As the TMPTMA concentration decreased, soluble graft copolymers were produced in addition to insoluble networks. A gel permeation chromatography technique provided compositional information on the gel and sol fractions. The competition between polymerization, grafting, and degradation reactions was examined.     

Synthesis and properties of chitosan-modified poly(vinyl butyrate)

Modification of chitosan by grafting of vinyl butyrate was carried out in homogeneous phase using potassium persulfate as redox initator and 1.5% acetic acid as solvent. The percent grafting and grafting efficiency were analysed and the high grafting efficiency up to 94% was observed. The effects of reaction variables such as monomer concentration, initiator concentration, temperature and reaction time were investigated. It was observed that the solubility of chitosan was markedly reduced after grafting with vinyl butyrate. The grafted product is insoluble in common organic solvents as well in dilute organic and inorganic acids. Characterization of the graft copolymers were carried out by using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) technics. Characteristic signal of carbonyl group was observed at 1,731 cm⁻¹ which belongs to the poly vinyl butyrate segments in the graft copolymer. The melting transition of the chitosan main chain in the copolymer shifted to 124°C from its original value 101°C. In addition to these, we have also studied topology of the graft copolymer and the SEM micrograph showed continuous homogenous matrix which means there is no phase separation.     

Iodine reaction of vinyl acetate — vinyl propionate copolymers II. Dependence of iodine affinities of the copolymers on the sequence distribution of vinyl acetate-units

The reactions of iodine with vinyl acetate (VAc) — vinyl propionate (VPr) copolymers in aqueous solutions of potassium iodide were investigated photometrically. The iodine affinity (I/VAc) of VAc-units was defined as the number of bound iodine atoms per VAc-unit and determined from the absorbance of the formed colored complex. The dependence of the I/VAc values on the copolymer composition was discussed with respect to the sequence distribution of VAc-units in the copolymer chains. The dependence of the I/VAc value on the copolymer composition of block copolymers provided a useful information concerning the saponification of PVAc because the here used block copolymers were prepared by propionylation of partially saponified PVAc.     

聚乙二醇接枝聚醋酸乙烯酯的聚合动力学研究

以过氧-2-乙基己酸叔丁酯为引发剂,进行了聚乙二醇(PEG)存在下的醋酸乙烯酯(VAc)本体接枝聚合,考察了各VAc:PEG配比下聚合速率、PEG上PVAc的接枝率、PVAc的接枝效率、PEG的被接枝效率以及接枝共聚物的分子量随聚合时间的变化规律.结果发现,随配方中VAc配比的增加,聚合速率与极限转化率明显增加,聚合反应出现明显的自动加速现象;当VAc:PEG配比较大时,综合速率参数K随聚合时间不断上升,当VAc:PEG配比较低时,K随聚合时间呈下降趋势.各VAc:PEG配比下PVAc的接枝率几乎都随转化率的增大而线性地增加,接枝效率则几乎不随聚合时间而变;接枝率的大小正比于VAc:PEG配比,接枝效率则普遍较高,低VAc:PEG配比时,接枝效率可达95%以上;PEG的被接枝效率虽随转化率和VAc:PEG配比的增加而明显增加,但总体仍较低,表明聚合体系中有相当多一部分PEG未被接枝.高的VAc接枝效率和低的PEG被接枝效率表明,该Graft From接枝聚合体系中,可能存在着Graft Onto的接枝聚合机理.根据定义用来计算PEG-g-PVAc的数均分子量,发现随聚合转化率的增大而减小,并逐渐趋于常数,配方中VAc浓度越大越大;由GPC测试、PVAc普适校正计算发现,接枝聚合产物的分子量分布指数在1.5～2.5 之间,且随单体浓度和转化率的增加而增大.这些均与聚合体系的凝胶效应有关.     

Synthesis and characterization of alginate‐g‐vinyl sulfonic acid with a potassium peroxydiphosphate/thiourea system

Alginate‐g‐vinyl sulfonic acid graft copolymer was synthesized through the graft copolymerization of vinyl sulfonic acid (VSA) onto alginate with an efficient system, i.e., potassium peroxydiphosphate (PDP)/thiourea in an aqueous medium. The effects of the concentration of thiourea, PDP, hydrogen ion, alginate, and VSA along with the time and temperature on the graft copolymerization were studied by the determination of the grafting parameters (grafting ratio, add‐on, conversion, grafting efficiency, and homopolymer). The synthesized graft copolymer was characterized by FTIR analysis. Thermogravimetric analysis showed that the alginate‐g‐vinyl sulfonic acid is thermally more stable than alginate. Water swelling capacity, metal ion sorption, flocculation, and resistance to biodegradability studies of synthesized graft copolymer have been performed with respect to the parent polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanism of enhanced impact strength of poly(vinyl chloride) modified by acrylic graft copolymer

The mechanism of enhanced PVC impact strength of poly(vinyl chloride) modified by an acrylic graft copolymer was studied by the three-point bending test on a U-notched bar. In the mechanism, the void formation from the modifier released the constrained strain. The release suppresses the stress below the fibril strength in the material; consequently, stable deformation can develop over a large area and, thus, the impact strength of PVC modified by the acrylic graft copolymer is improved. © 1996 John Wiley & Sons, Inc.     

Dehydrochlorinated poly(vinyl chloride)-g-polystyrene. II. Characterization and physical properties

Dehydrochlorinated poly(vinyl chloride)-g-polystyrene (DHPVC-g-PSt) prepared by free radical grafting was characterized, and some of its physical properties were evaluated. The presence of graft was established by the appearance of new absorption peaks in the IR spectra of the graft copolymer. GPC analysis showed increase in the average molecular weights of the graft copolymer upon increase in the PSt content. Besides, GPC revealed the uniform PSt distribution of DHPVC-g-PSt. A marked improvement in the thermal stability of DHPVC-g-PSt over that of DHPVC and DHPVC/PSt blends was observed. Graft copolymers with high percent grafting were thermally more stable than even the original PVC. Stress–strain data indicated decrease in yield stress, breaking stress and elongation, along with an increase in the initial modulus, upon increase in PSt content of the graft copolymer.