High-molar mass acrylamide-co-diacetoneacrylamide graft copolymers as viscosity enhancer for polymer flooding oil recovery

One of the most widely applied enhanced oil recovery processes is the polymer flooding, in which aqueous solution of polymer viscosifier is introduced in oil reservoirs to increase the recuperation of the remaining oil. From the current challenges of this process, it can be referred to a high cost of materials regarding their substantially required amount and the low impact on the mobility ratio during the process due to the reduction of solution viscosity at high temperatures and high salinity environments. The purpose of this study is to investigate the concept of acrylamide-based thermosassociating copolymer (TAP), with a specific morphology and chemistry (hydrophilic main backbone made of polyacrylamide with grafted amide functionalized pending chains) as viscosity enhancer at harsh conditions of high temperature and salinity. For that aim, a specific TAP microstructure was targeted (very high molar mass linear polymer chains with improved copolymer homogeneity). It is achieved in this study throughout applying the reaction engineering approach, such as synthesis in semi-batch mode or/and in heterogeneous dispersed media. As a result, the synthesized TAP presented excellent behavior as viscosity enhancer especially under high temperature and salinity conditions with improved performance in comparison to TAP synthesized by a conventional solution polymerization approach and to actual commercial high molar mass acrylamide-based polymer.     

Synthesis of graft copolymers based on 1-hexene oligomers and their trials as viscosity additives

Copolymers of decyl methacrylate with 1-hexene were prepared and tested as viscosity additives to petroleum oils. The influence of the concentration of the synthesized copolymers on the viscosity-temperature characteristics of petroleum oils was examined, and the thermal and mechanical stability of the copolymers in oils was evaluated.     

Polystyrene-nylon 6 graft copolymers

The synthesis of well-defined polystyrene-g-Nylon 6 copolymers is described. The materials were prepared for study of their rheological behaviour and to compare it with the recent findings for 2-phase block copolymer systems.The anionic polymerization of ?-caprolactam in the presence of polystyrene-ethyl acrylate copolymer was chosen as the preparative route. The reasons for the choice were (1) the fact that ester groups are known to be good initiators for the lactam polymerization and (2) that it has been previously established that uniform copolymers can be obtained from styrene and acrylate esters. The present paper describes initial results on preparation and characterization of graft copolymers.It was found that cross-linked materials resulted when the polystyrene copolymer contained more than 1 per cent by weight of ethyl acrylate. At lower ester concentrations, soluble and thermoplastic materials were obtained. The cross-linking reaction was tentatively identified as arising from the presence of the tertiary hydrogen alpha to the ester group. In agreement with this postulate, methacrylate copolymers produced soluble, thermoplastic grafts at concentrations as high as 5 weight per cent.The mechanical properties and the modulus-temperature behaviour of the 2-phase graft copolymer systems are also presented.     

Chromatography of amphiphilic graft copolymers

Amphiphilic comb polymers were prepared through grafting poly(ethylene glycol) methyl ether (MPEG 2000) onto acrylic and methacrylic copolymers. The graft copolymers were purified from unreacted MPEG by partition chromatography on methanol pretreated fibrous cellulose using ethyl acetate and methanol as eluents. The separation was found to depend on the water contents of the cellulose and the eluents. It is proposed that one parameter of importance for the chromatographic separation is the formation of hydrated inverted micelles. The amphiphilic comb polymers were shown by gel chromatography on Sepharose to form high molecular weight aggregates in water. On addition of sodium lauryl sulphate or inorganic salts to the eluent at low ionic strengths these aggregates dissociated and were fractionated by the gel. It was also shown that on GPC in THF solution on Styragel columns the polymers exhibited apparent molecular weights equal or smaller than those of the corresponding backbones. This effect may be a consequence of the graft copolymers having relatively small hydrodynamic volumes, and this idea is supported by the fact that their intrinsic viscosities generally were lower than those of the backbones. However, adsorption on the Styragel columns also may be of importance.     

In-situ preparation of graft copolymers

Graft copolymers are closer to supermolecular structures than any other class of polymers. Most grafting reactions proceed in demixed blends or lead in situ to such blends The competition of chemical chain coupling and physical phase separation generates complex phase morphologies that cannot (or not so directly) be produced otherwise. To demonstrate potential and problems of graft copolymer systems, high-impact thermoplastics, block-graft copolymers and reactive blending are discussed.     

Synthesis of well-defined all-acrylic graft copolymers

Well defined all-acrylic graft copolymers have been synthesized using the macromonomer technique. Poly(methyl methacrylate) (PMMA) macromonomers of controlled molecular weight and narrow molecular weight distribution have been synthesized by group transfer polymerization (GTP) using a protected hydroxyl functional initiator. These macromonomers were quantitatively functionalized with a polymerizable acrylic and group and copolymerized under free radical conditions with 2-ethylhexyl acrylate (2EHA) to form the desired well defined graft copolymers in high yields. The macromonomers and the copolymers have been characterized by a variety of spectroscopic, chromatographic and thermal analysis methods. Transparent, multiphase materials with glass transition temperature (Tg) values of approximately -65 °C and 115 °C were obtained. The reaction conditions necessary to generate these materials most effectively have also been investigated and are described herein.     

Dynamic viscosity of polymer solutions

The dynamic viscosity of different long chain polymers in Aroclor permits an easy extrapolation to zero concentration only in the limiting cases of Newtonian, i. e., constant viscosity at low and high frequency, respectively. The first intrinsic viscosity []₀ is independent of any concept of the internal viscosity. In the case of polystyrene it is proportional toM ^0,65 which shows that Aroclor is a good solvent for this polymer. The second intrinsic viscosity [] turns out to be independent ofM. It is best reproduced by the model where the internal viscosity resists only the deformation rate of the single link. The displacement rate of more distant beads is affected by the internal viscosity only in the case that it involves the deformation rate of the links. The angles between successive links may be changed at any rate.In the intermediate range of frequencies the extrapolation of the observed dynamic viscosity to the intrinsic value was never made. The experimental data are so much affected by the concentration, i. e., by the interaction of adjacent molecules, that no conclusion may be derived from them about the properties of the isolated macromolecule. A master curve independent ofM andc is obtained by plotting of (G- )K/c over ₁. This means that the deformation mode in the whole molecular weight and concentration range investigated is the same. But this mode is different from that of the independent macromolecule in infinite dilution. The master curve may be described by the excess intrinsic viscosity of the Rouse model with the internal viscosity acting either between the beads on the same link only or between any distinct beads. As a consequence of the concentration effects, however, no conclusions about the properties of the single molecule can be derived from such an agreement.Dedicated to Prof. Dr. F. H. Müller.     

Water-soluble graft copolymers from macromonomer method

Water-soluble graft copolymers of well-defined structure having hydrophobic polymethacrylate branches with different ester groups were prepared by the macromonomer method. Methacrylate macromonomers of controlled molecular weights having a methacryloyloxyl end group were synthesized by radical polymerization of the corresponding monomer in the presence of thioglycolic acid followed by the reaction of glycidyl methacrylate with the terminal carboxyl group. These macromonomers were copolymerized with methacrylic acid and methyl methacrylate to prepare tailor-made graft copolymers composed of a hydrophlic backbone and different kinds of hydrophobic branches, which were characterized by elemental analysis, NMR, and GPC. The viscosities of the aqueous solutions of the sodium salts of these graft copolymers were measured. It was found that the viscosity of the dilute solution of the graft copolymer was remarkably high compared with the corresponding random copolymer irrespective of the ester group in branch segments. Solubilizing behavior of Orange-OT in aqueous solutions of the graft copolymers and the random copolymer were also investigated to study the nature of the hydrophobic domain of the graft copolymers.     

Effect of supersaturation on the viscosity of solutions

Ohne Zusammenfassung     

Influencing the morphology of polymer blends through graft copolymers

Graft copolymers have a potential as compatibilizers in two-component thermoplastic polymer blends, and also as impact-modifiers in one-component thermoplastics. The compatibility of the blocks of the copolymer (i.e. the grafts and the main chain) with the chains of the matrix polymers must be adjusted carefully. Blends of various polymers, especially of polystyrene (PS) and poly(vinyl chloride) (PVC), with graft copolymers on the basis of polybutadiene are discussed. An excellent compatibilizer, for blends PS/PVC, is a block-graft copolymer, derived from a diblock copolymer of Styrene and butadiene, with grafts of cyclohexyl methacrylate monomelic units.     

Morphologies and bridging properties of graft copolymers

Morphologies and bridging properties of graft copolymers in the bulk state were studied by using a real-space algorithm of self-consistent field theory in two dimensions. The phase transition from cylindrical to lamellar phase can be triggered by changing the position of graft points and the number of branches. The fraction of bridged conformation, f(bridge), shows a tendency to decrease with increasing the length of free end blocks, tau1, and the number of branches, m. The value of f(bridge) has a discontinuous drop when the transition from cylindrical to lamellar phase takes place. The relationship between m and the number of bridged chains per unit area, nb, which is associated with the mechanical properties of copolymers, was also examined. It was found that nb increases with increasing m in the cylindrical phase. However, in the lamellar phase, nb decreases when m increases. It is proposed that the position of graft points and the number of branches are two important parameters for material design.     

Molecular weights of backbones in graft copolymers

Copolymerization of a monomer X with an existing polymer yields a copolymer contaminated by poly-X homopolymer and ungrafted polymer. Measurements on the pure copolymer can yield only the molecular weights of the cumulative backbone portion and of the cumulative graft portion. However, if the grafts can be isolated, then the molecular weights of their individual chains may be determined also. Since it is not isolatable, the backbone is not amenable to similar treatment. Equations are derived for the molecular weights (of any average) of individual backbone chains; they are expressed in terms of the following experimentally accessible quantities: (i) molecular weight of original polymer; (ii) molecular weight of ungrafted portion: and (iii) fraction by weight of the original polymer which remains ungrafted. The procedure is thus the analogue, applied to the backbone, of chemical isolation applied to the grafts. The treatment has been examined for copolymers prepared by grafting acrylic acid to nylon-6 by mutual irradiation.     

Block and graft copolymers of 2-oxazolines

The cationic ring-opening polymerization of 2-oxazolines is known to be initiated by alkyl halides, Lewis acids and esters of strong acids. The polymerization proceeds by a living mechanism. Numerous block and graft copolymers have already been described. Recently it was found that chloroformates (R-O-CO-CI) are also useful initiators. The mechanism of the initiation and propagation is discussed. This type of initiators allows the synthesis of different novel two-block and three-block copolymers, star-shape polymers, and a graft copolymer with a polyvinylacetate backbone.     

Synthesis of graft copolymers of xyloglucan and acrylonitrile

Xyloglucan (XG), a water‐soluble food grade polysaccharide is reported as a substrate for the graft copolymerization of acrylonitrile (AN). XG was extracted from tamarind seed mucilage. Polymerization was initiated both by ceric ion in aqueous medium under N₂ atmosphere and with microwave (MW) irradiation. The progress of the reaction was monitored gravimetrically. The effect of different reaction parameters such as monomer concentration, level of ceric ammonium nitrate/HNO₃ (CAN) initiator, reaction time and temperature, and MW power on the percent grafting (PG) was studied. Grafting of polyacrylonitrile (PAN) onto XG was confirmed by Fourier‐transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscope (SEM) techniques have been used to study the thermal and morphological changes in the materials. Copyright © 2007 John Wiley & Sons, Ltd.