“Living” free radical graft copolymers I: Preparation and properties

Polymers substituted with thio groups are useful for the photochemical synthesis of graft copolymers. Such copolymers have been prepared by the initial conversion of backbone polymers containing chlorinated substituents into polymers containing diethyldithiocarbamate (TC), isopropyl xanthate (IX) or mercaptobenzothiazole (BT) functionality. The photochemical reaction of monomers with these products produced graft copolymers. A variety of halogenated polymers were investigated as starting materials for these syntheses, including poly(vinyl chloride), chlorinated polyvinyl chloride), chlorinated polyethylene, chlorobutyl rubber and neoprene. Characteristics of the grafting reactions, including “pseudo-living” behavior and tandem grafting aspects, were investigated. Glass transitions of the grafted polymers were found to vary uniformly with composition for most of the grafted products.     

Grafting of Polymers Having Pendant Peroxycarbonate Groups Onto Carbon Black and Postpolymerization of Vinyl Monomers

Abstract

Postpolymerization of vinyl monomers initiated by pendant peroxycarbonate groups of grafted polymer chains on carbon black (CB) was investigated. The grafting of polymers having pendant peroxycarbonate groups onto CB was achieved by the trapping of polymer radicals formed by the thermal decomposition of copolymers of t-butylperoxy-2-methacryloyloxyethyl-carbonate (HEPO) with vinyl monomers such as vinyl acetate (VAc), styrene (St) and methyl methacrylate (MMA). The copolymers having pendant peroxycarbonate groups were prepared by copolym-erization of HEPO with vinyl monomers using azo initiator under irradiation of UV light at room temperature. The amount of remaining pendant peroxycarbonate groups of the poly(VAc-co-HEPO)-grafted CB obtained from the reaction at 90°C was maximum and decreased above the temperature. Furthermore, the postpolymerization of vinyl monomers, such as St, MMA, and VAc was initiated in the presence of poly(VAc-co-HEPO)-grafted and poly(St-co-HEPO)-grafted CB and the corresponding polymers were postgrafted onto CB to give branched polymer-grafted CB. The percentage of poly(St)-postgrafting (proportion of post-grafted poly(St) to poly(MMA-co-HEPO)-grafted CB used) increased with increasing polymerization time, but became constant at 20% after 4 hours.     

Photografting of polymers onto nanosized silica surface initiated by eosin moieties immobilized onto the surface

The photograft polymerization of various vinyl monomers onto nanosized silica surfaces was investigated. It was initiated by eosin moieties introduced onto the silica surface. The preparation of the silica with eosin moieties was achieved by the reaction of eosin with benzyl chloride groups on the silica surface.These were introduced by the reaction of surface silanol groups with 4‐(chloromethyl)phenyltrimethoxysilane in the presence of t‐butyl ammonium bromide as a phase‐transfer catalyst. The photopolymerization of various vinyl monomers, such as styrene, acrylamide, acrylic acid, and acrylonitrile was successfully initiated by eosin moieties on the silica surface in the presence of ascorbic acid as a reducing agent and by oxygen. The corresponding polymers were grafted from the silica surface. The grafting efficiency (percentage of grafted polymer to total polymer formed) in the photoinitiation system was much larger than that in the radical polymerization initiated by surface radicals; these radicals were formed by the thermal decomposition of azo groups introduced onto the silica surface. It was found that the polymer‐grafted silica gave stable dispersions in good solvents of grafted polymer and the wettability of the surfaces can be easily controlled by grafting of polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 600–606, 2005     

Cationic Grafting of Vinyl Polymers onto a Carbon Whisker,Initiated by Acylium Perchlorate Groups Introduced onto the Surface

Abstract

The cationic graft polymerization of vinyl monomers onto a carbon whisker, vapor-grown carbon fiber, initiated by acylium perchlorate groups introduced onto the surface, was investigated. The introduction of acylium perchlorate groups onto a carbon whisker was achieved by the treatment of a carbon whisker having acyl chloride groups, which were introduced by the reaction of surface carboxyl groups with thionyl chloride, with silver perchlorate in nitrobenzene. It was found that the cationic polymerization of vinyl monomers, such as styrene, indene, N-vinyl-2-pyrrolidone, and n-butyl vinyl ether, is initiated by acylium perchlorate groups on a carbon whisker. In the polymerization, the corresponding vinyl polymers were grafted onto a carbon-whisker surface based on the propagation of polymer from the surface: the percentage of grafting of polystyrene and polyindene reached 42.5 and 100.3%, respectively. The percentage of polystyrene grafting decreased with increasing polymerization temperature because of preferential chain transfer reactions at higher temperatures. Polymer-grafted carbon whisker gave a stable colloidal dispersion in a good solvent for grafted polymer.     

Effective grafting of polymers onto ultrafine silica surface: Photopolymerization of vinyl monomers initiated by the system consisting of trichloroacetyl groups on the surface and Mn2(CO)10

The effective grafting of vinyl polymers onto an ultrafine silica surface was successfully achieved by the photopolymerization of vinyl monomers initiated by the system consisting of trichloroacetyl groups on the surface with Mn₂(CO)₁₀ under UV irradiation at 25 °C. The introduction of trichloroacetyl groups onto the surface of silica was achieved by the reaction of trichloroacetyl isocyanate with surface amino groups, which were introduced by the treatment of silica with 3‐aminopropyltriethoxysilane. During the polymerization, the corresponding polymers were effectively grafted onto the surface, based on the propagation of polymer from surface radicals formed by the interaction of trichloroacetyl groups and Mn₂(CO)₁₀. The percentage of poly(methyl methacrylate) grafting onto the silica reached 714.6% after 90 min. The grafting efficiency (proportion of grafted polymer to total polymer formed) in the polymerization of methyl methacrylate was very high, about 80%, indicating the depression of formation of ungrafted polymer. Polymer‐grafted silica gave a stable colloidal dispersion in good solvents for grafted polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2157–2163, 2001     

二元单体在棉纤维上的γ辐射接枝

在氮气气氛下用γ射线辐照的方法在棉纤维上接枝苯乙烯/马来酸酐、苯乙烯/甲基丙烯酸二甲胺乙酯、苯乙烯/醋酸乙烯酯二元单体. 研究了溶液中单体的浓度和二元单体的摩尔比等条件对接枝率的影响, 并探讨了两种单体的竞聚率对接枝率、接枝膜的组成及性能的影响. 结果表明决定二元接枝生成物结构比例的是二元单体的比例及其竞聚率. 接枝产物的红外、热重分析进一步佐证了竞聚率对不同二元单体体系接枝生成物结构的影响. X射线衍射结果表明棉纤维素上接枝不同的二元单体后均引起结晶度的下降, 而且结晶度随接枝率的增加而降低, 证明二元接枝反应是从纤维素无定型区通过第三相向结晶区逐步扩展的.     

Polymerization of vinyl monomers in the presence of silica having surface functional groups

The surface of silica was modified by mercaptopropyl, chloropropyl, aminopropyl, and methacryloxypropyl groups by the treatment of silica with the corresponding silane coupling agents, and the effects of functional groups on the surface on the polymerization of vinyl monomers initiated by benzoyl peroxide or 2,2-azobisisobutyronitrile were investigated. Although the rate of the polymerization of vinyl monomers in the presence of silica was almost equal to that in the absence of silica, a part of polymer formed was grafted onto silica surface. The polymerization was considerably retarded in the presence of these functionalized silicas and the corresponding polymers were effectively grafted onto the surface. The molecular weight of ungrafted polymer formed in the presence of the functionalized silica was lower than that formed in the presence of unmodified silica. This indicates that the chain transfer reaction of growing polymer radical to functionalized silica surface forms radicals on the surface, which then couples with growing polymer radical and/or reinitiates the polymerization to give rise to the grafting of polymers onto the surface. In the case of silica having methacryloxypropyl groups, the grafting based on the copolymerization of vinyl monomer with the surface methacryloxypropyl groups was considered to successfully proceed.     

Reactive processing and blending of polymers making use of mechanoradicals

The grafting of various vinyl monomers on polyethylene and on ethylene-propylene copolymers has been initiated by mechanoradicals in an internal mixer. This is possible if the polymer has been slightly cross-linked by γ-radiation before processing or is dynamically cross-linked by peroxides during processing. Some properties such as adhesion to metals or impact resistance of blends containing the modified polymers are improved.     

Monomer reactivity ratios in graft copolymerization

This paper discusses monomer reactivity ratios in various radiation- and redox-initiated graft copolymerizations. The polymers studied were polyethylene, cellulose acetate, poly(vinyl chloride), polytetrafluoroethylene, poly(vinyl alcohol), and poly(methyl methacrylate); the comonomer mixtures were styrene–acrylonitrile, methyl acrylate–styrene, acrylonitrile–methyl acrylate, and vinyl acetate–acrylonitrile. The polymer–comonomer mixture systems were so chosen as to permit study of both homogeneous and heterogeneous systems. The homogeneous systems included systems of low and high viscosity. The heterogeneous systems included both polymers swollen by the comonomer mixture and polymers not swollen by the comonomer mixture. None of the homogeneous grafting systems studied showed deviations from the normal copolymerization behavior under a variety of experimental conditions. Monomer reactivity ratios in graft copolymerization were the same as the values in nongraft copolymerization. The heterogeneous systems in which the polymer was swollen by the comonomer mixture yielded grafted copolymer compositions which were the same as those in nongraft copolymerization. The heterogeneous grafting system polytetrafluoroethylene/styrene–acrylonitrile showed deviations from normal copolymerization behavior at low degrees of grafting when the reaction was only on the polymer surface. The behavior became normal at higher degrees of grafting when the system approaches that in which the polymer is swollen by the comonomers. In all reaction systems, it was found that the use of radiation to initiate the reaction does not in any way affect the copolymerization behavior of the two monomers in a comonomer pair.     

Grafting of polymers onto and/or from silica surface during the polymerization of vinyl monomers in the presence of γ‐ray‐irradiated silica

The effects of radicals on silica surface, which were formed by γ‐ray irradiation, on the polymerization of vinyl monomers were investigated. It was found that the polymerization of styrene was remarkably retarded in the presence of γ‐ray‐irradiated silica above 60 °C, at which thermal polymerization of styrene is readily initiated. During the polymerization, a part of polystyrene formed was grafted onto the silica surface but percentage of grafting was very small. On the other hand, no retardation of the polymerization of styrene was observed in the presence of γ‐ray‐irradiated silica below 50 °C; the polymerization tends to accelerate and polystyrene was grafted onto the silica surface. Poly(vinyl acetate) and poly(methyl methacrylate) (MMA) were also grafted onto the surface during the polymerization in the presence of γ‐ray‐irradiated silica. The grafting of polymers onto the silica surface was confirmed by thermal decomposition GC‐MS. It was considered that at lower temperature, the grafting based on the propagation of polystyrene from surface radical (“grafting from” mechanism) preferentially proceeded. On the contrary, at higher temperature, the coupling reaction of propagating polymer radicals with surface radicals (“grafting onto” mechanism) proceeded to give relatively higher molecular weight polymer‐grafted silica. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2972–2979, 2006     

Characterization of the collagen–vinyl graft copolymers prepared by the ceric ion method. I. Solution properties

Graft copolymerization of vinyl monomers on to collagen was carried out by the ceric ion method. The grafted vinyl polymer chains were isolated by both acid and enzymatic hydrolysis of the collagen backbone in order to characterize the graft copolymers. Proof of grafting was obtained through the detection of amino acid endgroups in the grafts isolated by both the methods. The grafts isolated gave the characteristic blue color normally associated with the presence of amino acids. The presence of amino acid endgroups was further confirmed by dinitrophenylation of the isolated grafts. The absorption spectra of the dinitrophenylated(DNP) grafts showed absorption maximum in the ultraviolet region of 340–360 mμ, characteristic of DNP-amino acids. Soluble collagen grafted with polyacrylamide(PAA) formed fibrils on heating to 37°C at neutral pH but, unlike the native collagen, these fibrils did not redissolve on cooling at 2°C. These results show that the redispersion property of soluble collagen was impaired, probably by attachment of the PAA side chains to the collagen molecule. The turbidimetric titration behavior of the grafts, their general behavior of swelling in different solvents, and the intrinsic viscosity of the copolymers in mixed solvents also provided additional proof of grafting.     

Physical properties of some low polymer content radiation-grafted wool copolymers

Wool copolymers with low polymer content (6–18%) have been prepared by radiation grafting techniques. Supercontraction, density, and formic acid vapor sorption measurements have been used to assess changes in the keratin structure produced by the grafting processes. Kinetic studies of the contractile forces developed in the first (reversible) stage of the supercontraction of wool in lithium bromide showed that grafting with poly(N-methylol acrylamide) or polyacrylonitrile has a “repairing” action which offsets changes in the wool structure produced by the small radiation dose (2 Mrad) used for the grafting process. By contrast, grafting with poly(vinyl acetate) had no repairing effect. The bonds formed by grafting of poly(N-methylol acrylamide) or polyacrylonitrile to keratin do not reduce swelling of the wool by formic acid, which is a measure of effective crosslink density. Grafting with poly(vinyl acetate) led to increased swelling by formic acid, indicating some disruption of the keratin structure during polymerization. It is suggested that the role of the grafted polymer is mainly to stabilize the hydrogen-bonded secondary network by interaction between the polypeptide and polymer chains.     

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.     

Surface grafting of cobalt complexes on polymeric supports: Evidence for site isolation and applications to reversible dioxygen binding

Imprinted polymers were synthesized using the surface‐grafting technique with [Co(III) 1 (vpy)(dmap)]PF₆ { 1 , bis[2‐hydroxy‐4‐(4‐vinylbenzyloxy)benzaldehyde]ethylene‐diimine; vpy: 4‐vinylpyridine; dmap: N,N′‐dimethyl‐4‐aminopyridine} as the template. The metallated sites were probed using spectroscopic techniques including UV–vis, Fourier transform infrared, and electron paramagnetic resonance (EPR) spectroscopies to investigate the site architecture and isolation of the immobilized sites in the surface‐grafted polymers. EPR studies showed a distribution of four and five coordinated sites similar to the bulk copolymers, and the surface‐grafted polymer showed reversible binding to dioxygen in multiple cycles. Both results indicated site isolation in the surface‐grafted polymers analogous to the bulk polymers. Although the dioxygen binding in surface‐grafted polymers is reversible, the spin density decreases to 50% in the third cycle as opposed to bulk copolymers. This indicates that the sites are more heterogeneous and more exposed to the environment than the analogous sites in bulk copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 888–897, 2001     

Peroxide-Initiated crosslinking of styrene-grafted polymers and copolymers of butadiene

Low molecular weight polymers and copolymers of butadiene were grafted with styrene. The graft products were then crosslinked by using dicumyl peroxide as initiator. The optimum peroxide concentration was established (5 phr). Infrared analysis showed that the reactivity of 1,2-vinyl and that of 1,4-trans double bonds in styrene-grafted polybutadiene is similar. Crosslinking of the graft product seems to involve a radical-chain polymerization of double bonds in the polymer. The reaction rate is proportional to the square root of peroxide concentration and to the concentration of polymer double bonds. Activation energy, reaction heat, reaction order, and crosslinking efficiency were also determined from DSC measurements. No relation was found between the activation energy of crosslinking and the molecular weight of backbone polymer or density of grafting. Crosslinking efficiency was to 25–50 crosslinks per molecule of decomposed peroxide. The crosslinking efficiency for grafted butadiene–styrene copolymers is somewhat lower than that for grafted polybutadienes. From thermogravimetric measurements it was found that the crosslinked grafted polymers show lower resistance to thermal degradation than ungrafted polymers.     

Polymerization of water soluble cationic vinyl monomers

This paper summarizes investigations on the radical polymerization of cationic vinyl monomers with respect to the peculiarities of the reaction in aqueous solution, the synthesis of model polymers and polyelectrolytes with regular structure as well as to a new process of stabilized precipitation polymerization. The rate of polymerization depends on the ionic strength of the solution. Random copolymers of diallyldimethylammonium chloride and acrylamide with variable charge density but equal molecular weight were synthesized by a feeding technique. Block copolymers consisting of charged and uncharged monomelic units with different hydrophilicity are available using macroazoinitiators. The novel polymers are powerful stabilizers in the precipitation polymerization of water soluble cationic vinyl monomers in aqueous salt solution leading to a dispersion of fine polymer particles. Polyampholytes with alternating positively and negatively charged monomelic units in the backbone were obtained by cyclocopolymerization of diallylanmine compounds and derivatives of maleic acid.     

Radiation-induced grafting of perfluorinated vinyl ether into fluorinated polymer films

We report herein the first successful grafting of perfluorinated vinyl ether monomer into base polymer films by simultaneous radiation method. 2-Bromotetrafluoroethyl trifluorovinyl ether (BrTFF) could be grafted into poly(ethylene-co-tetrafluoroethylene) (ETFE) films by γ-rays irradiation at room temperature. The grafting yield increased linearly with an increase in the dose up to 1400 kGy. The required dose for a satisfactory grafting yield, such as 20%, was as high as ca. 400 kGy probably due to low polymerization reactivity of fluorinated monomers. However, the solvent and catalyst had no positive influence for improving the grafting yield. FTIR spectra and SEM-EDS testified that BrTFF was successfully grafted into ETFE films homogeneously in the perpendicular direction. The thermal analysis of the grafted films further indicated no phase separation between poly(BrTFF) grafts and ETFE films, probably owing to high compatibility of the fluorinated grafts and base polymers.     

Influence of the molecular architecture on the adsorption onto solid surfaces: comb-like polymers

The processes of adsorption of grafted copolymers onto negatively charged surfaces were studied using a dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The control parameters in the study of the adsorption are the existence or absence on the molecular architecture of grafted polyethyleneglycol (PEG) chains with different lengths and the chemical nature of the main chain, poly(allylamine) (PAH) or poly(L-lysine) (PLL). It was found out that the adsorption kinetics of the polymers showed a complex behavior. The total adsorbed amount depends on the architecture of the polymer chains (length of the PEG chains), on the polymer concentration and on the chemical nature of the main chain. The comparison of the thicknesses of the adsorbed layers obtained from D-QCM and from ellipsometry allowed calculation of the water content of the layers that is intimately related to the grafting length. The analysis of D-QCM results also provides information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. It is shown that the adsorption of polymers with a charged backbone is not driven exclusively by the electrostatic interactions, but the entropic contributions as a result of the trapping of water in the layer structure are of fundamental importance.     

Graft polymerization of vinyl monomers onto nanosized alumina particles

To enhance the interfacial interaction in alumina nanoparticles filled polymer composites, an effective surface modification method was developed by grafting polystyrene and polyacrylamide onto the particles. That is, the alumina surface was firstly treated with silane, followed by radical grafting polymerization in aqueous or non-aqueous systems. Results of infrared spectroscopy and dispersiveness in solvents demonstrated that the desired polymer chains have been covalently bonded to the surface of the alumina particles. They also greatly changed their surface characteristics. In addition, effects of polymerization conditions, including ways of monomer feeding, concentrations of monomer and initiator, and reaction time, on the grafting reaction were presented. It was found that the growing polymer radicals and/or the grafted polymer chains had a blocking effect on the diffusion of radicals or monomers towards the surface of nanoalumina. This was due to the fact that the interaction between the solvent and the grafted polymers was weaker than that between the grafted polymers and the nanoparticles.     

Chemical modification of butyl rubber. I. Synthesis and properties of poly(ethylene oxide)-grafted butyl rubber

A new amphiphilic polymer, i.e., poly(ethylene oxide) (PEO)-grafted butyl rubber (IIR-g-PEO), was synthesized by chemical modification of chlorinated butyl rubber (CIIR). This synthesis was based on the reaction between chlorine in CIIR and potassium salt of polyethylene glycol monomethyl ether (PEGM). PEGM's with molecular weights of 750 and 2000 were used. The maximum grafting percent of the resulted copolymers after the purification was ca. 45%, regardless of the molecular weight of PEGM. The microphase separated structure was observed in the films of IIR-g-PEOs. IIR-g-PEO, whose PEO molecular weight was 2000 and whose PEO content was 23.8 wt %, swelled 3.1% in water, and it was six times larger than the swelling of CIIR. The hydrophilicity of grafted polymers depended on the molecular weight of PEO side chains and PEO content. Even when the PEO contents were same in the polymers which were grafted PEGM-750 and PEGM-2000, their swellings in organic solvents were not equal. It was due to the difference of the microphase-separated structures of the grafted polymers. IIR-g-PEO, whose PEO molecular weight was 750 and whose PEO content was 10.3 wt %, swelled 1.5% in water, but showed an excellent emulsifying ability, where an oil-in-water-type emulsion was formed. © 1993 John Wiley & Sons, Inc.