Effect of comonomer sorption on radiation-induced copolymer grafting onto polyethylene and EVA films in the vapor phase

Radiation-induced copolymer grafting of acenaphthylene and maleic anhydride onto polyethylene or EVA film in the vapor phase was carried out and the effect of comonomer sorption on the grafting was studied. When polyethylene film was used as a backbone polymer, the sorption of the binary monomers during the grafting increased linearly as the grafting reaction proceeded. The marked increase was probably caused by the formation of a grafted layer. Particularly, the sorption of maleic anhydride was brought about by the existence of a grafted layer. In grafting onto EVA film, the content of maleic anhddride in the grafted copolymer increased with the increasing content of vinyl acetate in EVA. Continuous measurements of sorption of the comonomers onto EVA and grafted EVA films were carried out by use of an electrobalance. The distinctive feature of the sorption was that the equilibrium sorption of acenaphthylene or maleic anhydride onto the grafted EVA film increased and the diffusion constants for both comonomers decreased markedly with increasing percentage of graft. The copolymer grafting was explained from these results by assuming that the monomer molecules are supplied to the propagating chain ends mostly through a sorbed state on the polymer film.     

Synthesis of maleic anhydride grafted polyethylene and polypropylene,with controlled molecular structures

This article discusses a new chemical route to prepare maleic anhydride (MA) grafted polyethylene and polypropylene polymers with controlled molecular structure, that is, MA grafted content and polymer molecular weight and composition distributions. The chemistry involves a free radical graft reaction of maleic anhydride with poly(ethylene‐co‐p‐methylstyrene) and poly(propylene‐co‐p‐methylstyrene) copolymers. Under a suspension reaction condition, the grafting reaction takes place selectively on the p‐methylstyrene units in the copolymer, due to high reactivity of p‐methyl group and favorable mixing between p‐methylstyrene units and chemical reagents in the swollen amorphous phases. The resulting polymer shows no detectable molecular weight change during the reaction, and the MA grafted content increases with the increase of initiator and p‐methylstyrene concentrations. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1337–1343, 2000     

Effect of the initial maleic anhydride content on the grafting of maleic anhydride onto isotactic polypropylene

A series of ¹³C‐enriched maleic anhydride grafted isotactic polypropylene samples were prepared in solution at 170 °C by changes in the initial maleic anhydride content. The NMR spectra of the samples showed that the signals of the maleic anhydride attached to the tertiary carbons of the isotactic polypropylene chains increased considerably with increasing maleic anhydride content, whereas the signals of the maleic anhydride on the radical chain ends (with a single bond) arising from β scission did not. On the other hand, the signals of the maleic anhydride on the radical chain ends with double bonds increased markedly with increasing maleic anhydride content, and this suggested that β scission could occur extensively after maleic anhydride was attached to the tertiary carbons. As a result, the molecular weight of the grafted polypropylene decreased significantly with increasing maleic anhydride content in this study. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5529–5534, 2005     

Vapor-phase graft copolymerization of binary solid monomers onto poly(ethylene-co-vinyl acetate) film by ultraviolet irradiation

Vapor-phase graft copolymerizations of acenaphthylene–maleimide or acenaphthylene–maleic anhydride binary solid monomers onto poly(ethylene-co-vinyl acetate) films were carried out under ultraviolet irradiation. The extent of sorption of single or binary monomers increased with the increasing vinyl acetate content in the backbone polymers. The sorbed binary monomers were mainly composed of acenaphthylene, but the maleimide or maleic anhydride fraction increased with the increasing vinyl acetate content of the films and the composition was little affected by surface hydrolysis. In all series of graft polymerization of single or binary monomers the overall extent of grafting increased with the vinyl acetate content and was suppressed by the surface hydrolysis of the backbone film. The composition of the grafted copolymer, however, differed markedly, depending on the combination of binary monomers. The grafted copolymer in the acenaphthylene–maleimide system was composed mainly of acenaphthylene units, whereas that in the acenaphthylene–maleic anhydride system was composed mainly of maleic anhydride units. The results were compared with those of γ-ray grafting, and it was suggested that the contribution of a direct supply of monomers from vapor phase and the existence of an acetoxy group on the surface of the film should play an important role in the grafting reaction.     

Radical cyclocopolymerization of divinyl ether and maleic anhydride. A 13C-NMR study of the polymer structure

The structure of the 1:2 copolymer of divinyl ether and maleic anhydride was investigated by ¹³C-NMR spectroscopy. The polymer contains the bicyclic unit composed of one molecule of each monomer and the maleic anhydride unit. The carbon chemical shift for these units was calculated on the basis of the chemical shift of many model compounds. The major peaks of the cyclopolymer prepared in chloroform were consistent with the presence of the symmetrical bicyclic unit with cis junction and the trans monocyclic anhydride unit. The carbonyl carbon spectrum for the copolymer obtained in a mixed solvent of acetone and CS₂ suggested the predominant formation of the unsymmetrical bicyclic unit. The polymerization process was discussed on the basis of these results.     

Polymerization initiated by the charge-transfer complex of styrene and maleic anhydride in the presence of cumene and of cumene and liquid sulfur dioxide

A polymerization was induced with a charge-transfer type of complex consisting of styrene and maleic anhydride in the presence a solvent such as ethyl benzene, cumene, or p-cymene. No polymer was obtained either when the solvent was missing from the polymerization system or when benzene, toluene, or xylene, which are relatively stable to hydrogen abstraction, was added to the polymerization system. An effective initiation, however, took place when cumene or p-cymene, each of which has a labile hydrogen on an α carbon, was added. On the basis of elementary analysis and infrared spectroscopy the formation of copolymer containing substantially equimolar amounts of styrene and maleic anhydride was ascertained. This polymerization was inhibited by the addition of DPPH, suggesting that the system styrene–maleic anhydride–cumene functions much as a conventional free-radical initiator. On the other hand, when a solution of cumene and liquid sulfur dioxide was added to the polymerization system, polystyrene was obtained. This polymerization was inhibited by the addition of a base such as dimethyl-formamide or dimethyl sulfoxide, indicating that the polymerization proceeds through carbonium ion intermediates. The addition of ethyl benzene or of p-cymene brought about the same result as cumene. It is conceivable that the polymerization is induced by the abstraction of hydrogen attached at the α position of cumene by means of the charge-transfer complex of styrene and maleic anhydride.     

Reactive compatibilization of SAN/EPR blends: effect of the kinetics of the compatibilization reaction on the interfacial adhesion

The very poor adhesion between films of styrene and acrylonitrile random copolymer (SAN) and maleic anhydride grafted polypropylene (PP‐g‐MA) can be dramatically improved by an intermediate thin layer of SAN bearing groups reactive toward maleic anhydride. The rate of the interfacial reaction, which is controlled by the reactive groups attached to SAN (amine vs. carbamate) and by the method used to build up the sandwich assembly, has a decisive effect on the capability of the SAN‐g‐PP graft copolymer formed at the interface to improve the fracture toughness in direct dependence on its molecular architecture.     

Interfacial deposition of functionalized copolymers onto nanoemulsions produced by the solvent displacement method

Cationic nanoemulsions containing an oily core as potential carriers of nucleic acids were prepared by a solvent displacement method in the presence of a nonionic surfactant (Pluronic F68). With a view to functionalize such nanoemulsions for further incorporation of a fusogenic peptide, a poly(maleic anhydride-alt-methyl vinyl ether) (M _n=67,000) grafted with variable amount of acetylspermine (or acetylspermidine) and decylamine was nanodeposited during the nanoemulsion formation step. Functionalized nanoemulsions were characterized in terms of particle size (by quasi-elastic light scattering and electron microscopy), electrophoretic mobility and long-term stability as a function of the amount of polymer used in the formulation. It was found that increases in the level of the copolymer led to a reduction in the particle size and a decrease in colloidal stability. In addition, the incorporation of the grafted copolymers at the interface of the nanoemulsions was clearly evidenced, a shift towards low pH at the point of zero charge being attributed to the formation of carboxylic groups induced by hydrolysis of the residual maleic anhydride groups of the copolymer. Received: 1 September 2000 / in revised form: 29 November 2000 Accepted: 12 December 2000     

Glass bead grafting with poly(carboxylic acid) polymers and maleic anhydride copolymers

Glass beads were etched with acids and bases to increase the surface porosity and the number of silanol groups that could be used for grafting materials to the surfaces. The pretreated glass beads were functionalized using 3‐aminopropyltriethoxysilane (APS) coupling agent and then further chemically modified by reacting the carboxyl groups of carboxylic acid polymers with the amino groups of the pregrafted APS. Several carboxylic acid polymers and poly(maleic anhydride) copolymers, such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), poly(styrene‐alt‐maleic anhydride) (PSMA), and poly(ethylene‐alt‐maleic anhydride) (PEMA) were grafted onto the bead surface. The chemical modifications were investigated and characterized by FT‐IR spectroscopy, particle size analysis, and tensiometry for contact angle and porosity changes. The amount of APS and the different polymer grafted on the surface was determined from thermal gravimetric analysis and elemental analysis data. Spectroscopic studies and elemental analysis data showed that carboxylic acid polymers and maleic anhydride copolymers were chemically attached to the glass bead surface. The improved surface properties of surface modified glass beads were determined by measuring water and hexane penetration rates and contact angle. Contact angles increased and porosity decreased as the molecular weights of the polymer increased. The contact angles increased with the hydrophobicity of the attached polymer. The surface morphology was examined by scanning electron microscopy (SEM) and showed an increase in roughness for etched glass beads. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and characterization of anhydride-functional polycaprolactone

Polycaprolactone-graft-maleic anhydride (PCL-g-MA) copolymer was prepared by grafting maleic anhydride onto PCL in a batch mixer and in an extruder using dicumyl peroxide as the initiator. The graft content was determined with the volumetric method by converting the anhydride functions to acid groups and then titrating with ethanolic potassium hydroxide. The grafted polymer was extracted with xylene to remove any unreacted monomer before the estimation step. The effect of temperature and the various concentrations of the initiator and monomer used for the grafting reaction were investigated. The presence of residual initiator in the reaction product was checked using thin-layer chromatography. Molecular weight determination was carried out for the pure and grafted polymer using gel permeation chromatography to determine if chain scission was present. Results indicate that maleic anhydride is grafted onto PCL using free radical initiators. The grafting reaction was confirmed by FTIR and NMR techniques. FTIR spectra showed absorption bands around 1785 and 1858 cm⁻¹. NMR spectra gave signals for methine proton at 3.47 ppm. For a given peroxide level, a higher temperature or residence (reaction) time gave higher percentage of grafted MA. There was an optimum temperature and initiator concentration after which the percentage of MA grafted on PCL decreased. The number-average molecular weight, tensile strength, and the percent elongation of PCL-g-MA were comparable to those of PCL before grafting. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1139–1148, 1997     

Graft formation and chain scission in blends of polyamide-6 and -6.6 with maleic anhydride containing polymers

The in situ formation of a compatibilizer, consisting of a copolymer of PA grafted onto a maleic anhydride (MA) containing polymer, is essential for the morphology and properties of the corresponding PA blends. In this study four blends, containing PA-6 or PA-6.6 and EPDM-g-MA or poly(styrene-co-maleic anhydride) (SMA; 28 wt % MA), were prepared and characterized. Chemical analyses showed that the amount of PA graft is independent of the blend composition. Going from EPDM-g-MA to SMA the MA content of the original MA-containing polymer increases, which in the corresponding blends results in an increase in the number of PA grafts and a decrease in the length of the PA grafts. In the SMA blends the number averaged molecular weight of the grafted PA is only about 200 g/mol. It is postulated that the water molecule, released upon imide formation at the PA/(MA-containing polymer) interface, hydrolyses a PA amide group, resulting in a new amine end group, which in its turn reacts with the MA-containing polymer, etc. Differential scanning calorimetry shows that the degree of crystallinity of the PA phase is decreased only when the size of the PA phase between the MA-containing polymer domains approaches the PA crystalline lamellar thickness. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 179–188, 1998     

Reactive blending of polypropylene and butadiene-acrylonitrile elastomer

Graft copolymer of polypropylene and butadiene-acrylonitrile random copolymer was prepared by reactive polymer blending in a melt without solvents. The process was performed by preliminary grafting of maleic anhydride groups to polypropylene and of isocyanate groups to butadiene-acrylonitrile copolymer, followed by blending of the modified polymers. The chemical reactions occurring in the process and the fraction composition of the copolymer were studied.     

4-PEG接枝苯乙烯-马来酸酐交替共聚物的合成及功能化

采用普通自由基聚合和可逆加成一断裂链转移（RAFT）自由基聚合方法合成了对位PEG取代苯乙烯（PEG-g-St）和马来酸酐的交替共聚物（P（（PEG—g—St）-alt-MA））,”CNMR分析表明PEG-g-St和马来酸酐单元采取交替的序列结构．利用反应性基团-马来酸酐单元的水解以及胺解可以制备功能性的PEG聚合物．以月桂胺为模型小分子研究了该聚合物的胺解,得到4-PEG-苯乙烯与羧酸基团以及疏水烷烃的交替序列聚合物,该双亲聚合物在水溶液中形成组装体．     

Kinetic studies of grafting of maleic anhydride to hydrocarbon substrates

The kinetics of grafting of maleic anhydride to various hydrocarbon substrates has been investigated. Grafting to eicosane and squalane was effected in the pure hydrocarbons and in 1,2-dichlorobenzene solution, while polyethylene was grafted only in solution. The initiator was 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne which has a half life of about 1 h at a typical reaction temperature of 150°C. At high concentrations of initiator (Ca. 0.02M), the rate of disappearance of maleic anhydride is linear with time. In the pure hydrocarbons the order with respect to initiator is close to 0.5. In squalane, the overall activation energy is 112 kJ mol^?1; the average number of maleic anhydride molecules grafted per molecule of peroxide decomposed varies from 8 at high rates of initiation to 57 at low rates of initiation. The results are interpreted in terms of a chain mechanism, including a slow propagation step in which a succinic anhydride radical abstracts hydrogen from the same or a different chain. The same general mechanism is proposed for grafting of maleic anhydride to polyethylene and the hydrocarbons in 1,2-dichlorobenzene solution.     

Polymer-Modified Silica Adsorbent with Reversed-Phase and Weak Cation-Exchange Groups

Micro-spherical silica gel has been modified with a polymer containing two different functional groups (C₁₈ and COOH) by use of a copolymer of octadecyl methacrylate and butyl acrylate and introduction of maleic anhydride. The chromatographic properties of these stationary phases in reversed-phase high-performance liquid chromatography (HPLC) have been studied over a broad pH range. Introduction of maleic anhydride as the third component of the polymer layer on the surface of micro-spherical silica leads to repartitioning of C₁₈ groups, which affects the hydrophobicity of the materials obtained. The presence of maleic anhydride secures the availability of carboxyl groups on the surface, and thus the acidic properties of the material.     

Alternating copolymerization of ethylene with maleic anhydride

The copolymerization of ethylene with maleic anhydride was carried out with γ-radiation and a radical initiator, i.e., 2,2′-azobisisobutyronitrile and diisopropyl peroxydicarbonate under pressure at various reaction conditions. The homopolymerization of neither monomer was observed in this system. In the γ-ray-initiated copolymerization the G value (polymerized monomer molecules per 100 e.v.) was shown to be between 10³ and 10⁴. It was found that the dose rate exponent of the rate is approximately unity, and the rate is proportional to the amount of ethylene monomer. Apparent activation energies of 1.8 and 27.5 kcal./mole were obtained for γ-ray-initiated and AIBN-initiated copolymerization, respectively. Since the composition of copolymer is independent of monomer molar ratio and the molar ratio of ethylene to maleic anhydride in the polymer is approximately unity, the monomer reactivity ratios were obtained as r_E ? 0 and r_M ? 0 for γ-ray-initiated polymerization at 40°C. Alternating copolymerization was, therefore, concluded to occur. Infrared analysis of the copolymer is almost consistent with this. The copolymer in the solid state is amorphous. It is soluble in water, cyclohexane, and dimethylformamide and insoluble in lower alcohols, ether, and aromatic hydrocarbons. The aqueous solution of polymer gave a strong acid.     

Effect of maleic anhydride‐grafted polytetrafluoroethylene on the tensile and tribological properties of blending polytetrafluoroethylene with polyamide‐6

Blending polytetrafluoroethylene (PTFE) to polyamide‐6 (PA6) with and without maleic anhydride‐grafted polytetrafluoroethylene (PTFE‐g‐MA) was produced in a corotating twin screw extruder, where PTFE acts as the polymer matrix and PA6 as the dispersed phase. The effect of PTFE‐g‐MA on the tensile properties and tribological propertiesof PTFE/PA6 polymer blends is studied. Results show that the structural stability and morphology of the blends were greatly improved by PTFE‐g‐PA6 grafted copolymers, which were formed by the in situ reaction of anhydride groups with the amino end groups of PA6 during reactive extrusion forming an imidic linkage. The presence of PTFE‐g‐PA6 in the PTFE continuous phase improves the interfacial adhesion, as a result of the creation of an interphase that was formed by the interaction between the formed PTFE‐g‐PA6 copolymer in situ and both phases. Compared with thePTFE/PA6 without PTFE‐g‐MA, the PTFE/PA6 with PTFE‐g‐MAhad the lowest friction coefficient and wear under given applied load and reciprocating sliding frequency. The interfacial compatibility of the composite prevented the rubbing‐off of PA6, accordingly improved the friction and wear properties of the composite. Copyright © 2009 John Wiley & Sons, Ltd.     

Morphology of Nylon-6 blends with styrenic polymers

The morphology of blends of styrenic polymers in a matrix of 75% Nylon-6 prepared in a Brabender Plasti-Corder was examined by scanning electron microscopy. Styrene/acrylonitrile copolymers (SAN) form smaller particles as the AN level increases owing to the corresponding decrease in the SAN–polyamide interfacial tension. Various styrenic polymers containing functional groups, maleic anhydride or oxazoline type, that can react with Nylon-6 during melt processing were added to the SAN phase which also led to a decrease in the particle size owing to the graft copolymer formed in situ. The effects of functional group type, amount of functional groups per chain, amount of functional polymer added, and the miscibility of the styrene/maleic anhydride (SMA) and SAN copolymers on the morphology of the styrenic phase in the Nylon-6 matrix are described. © 1992 John Wiley & Sons, Inc.     

SYNTHESIS AND CHARACTERIZATION OF POLYMER DERIVATIVES OF cis-PLATINUM COMPLEXES

Cis-platinum complexes used as antitumor drugs were attached onto preformed polymers toreduce the toxicity. Either alternating copolymer of styrene and maleic anhydride (CPSMA) orpolyacrylic acid (PAA) is readily dissolved in alkaline solution. The cis-platinum complexes areeasily converted into water soluble species when treated by silver nitrate in water. The expectedproducts could be obtained when the two aqueous solutions were brought together. The productswere characterized by elementary analysis, IR and XPS. The polymer derivatives could exchangeligands with nucleophilic groups in biological environment and also exhibit antineoplastic activity.     

Grafting of maleic anhydride to n-eicosane

Maleic anhydride was grafted to the linear hydrocarbon, n-eicosane, at 165°C in the presence of the free radical initiator, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. The anhydride has a low solubility in eicosane and a multiple addition procedure was adopted. Grafted product which separated from the reaction mixture was fractionated and analyzed. The fractions contained on average 2–5.5 anhydride units/eicosane residue. ¹H- and ¹³C-NMR studies show that the grafts consist of single succinic anhydride rings. At the concentrations of maleic anhydride chosen for homogeneous reaction ( < 0.02 M) and at 165°C, poly(maleic anhydride) is above its ceiling temperature, so that succinic anhydride radicals cannot add maleic anhydride to form polymer side chains. Instead, these radicals abstract hydrogen atoms to yield grafts consisting of single anhydride units.