SYNTHESIS AND CHARACTERIZATION OF A NOVEL FLUORINE-CONTAINING HYDROPHOBICALLY ASSOCIATING POLYMER

In this article, the synthesis and characterization of a novel fluoromonomer and its copolymer with acrylamide is reported. 2-perfluoroamyl-4-hydroxylquinoline 2 was synthesized from ethyl 2, 2-dihydroperfluoroheptanoate in high yields. The monomer 4 was then synthesized from 2 in two steps readily in high yields. Synthesis and characterization of copolymers of acrylamide (AM) and the fluoromonomer were investigated. The composition and intrinsic viscosity of these copolymers were studied. It was found that the rheological properties of aqueous solutions of polyacrylamide were modified significantly when a small proportion of the fluoromonomer 4 was incorporated on investigating the viscosity-concentration profiles, pseudoplasticity of these solutions and the effect of the presence of surfactant. These results could be explained by the hydrophobic association of the fluorocarbon segments in the aqueous solutions of these copolymers.

Synthesis and Solution Properties of Hydrophobic Associating Polymers

Acrylamide/2-acrylamido alkane sulfonic acid hydrophobic associating copolymers were synthesized by micellar copolymerization. Effects of hydrophobe content, polymer concentration, salinity and surfactant on rheological behavior of copolymers were investigated and the conformation of polymers in solution was studied by means of environmental scanning electronic microscopy and dynamic light scattering. The experimental results showed that in the dilute regime the hydrophobic parts could interact intramolecularly, while in the regime where the polymer concentration was higher than the critical association concentration, intermolecular hydrophobic association became predominant. Within the limit of the solubility, the critical association concentration of the polymer decreased with the increase of the salinity. The experimental results of the solution conformation indicated the presence of the three-dimensional network structure in deionized water and the size of the mesh in the network varied with the polymer concentration. In NaCl solution, above the critical association concentration, an increase in polymer concentration enhanced the intermolecular association and also enlarged the hydrodynamic radius. It would result in the improvement of the thickening power of polymers.

The effect of betaine surfactants on the association behavior of associating polymer

The interfacial properties and rheological behavior of surfactant/polymer complex systems were measured to investigate the association behavior of the associating polymer.Compared with the pure surfactant solution,there are two inflection points in the surface tension curve for the surfactant/polymer complex systems.The two inflection points are dependent on the surfactant type and polymer concentration.The effect of surfactant on the rheological behavior of polymer can be divided into two aspects.First,the addition of short-chain betaine surfactant is detrimental to the viscosity of polymer solution due to the electrostatic shielding effect.Second,long-chain betaine surfactant also reduces the viscosity of polymer solutions at low concentrations.However,when the concentration of the long-chain betaine surfactant is relatively high,the long-chain betaine surfactant could form worm-like micelles that promote the intermolecular association and thus increase the number of associating junctions,thereby resulting in the augmentation of viscosity.So it is necessary to apply the long-chain betaine surfactant to build the polymer/surfactant flooding system.The interaction model between surfactant and polymer is proposed,which is different from the traditional‘Three-Region Model’.

Template Effect of Hydrophobically Associating Polymers on the Construction of Cuprous Oxide Micro Structure

To determine the template effect of hydrophobically associating copolymers（HACPs） on the morphology of nano/micro structures, six HACPs were synthesized and used as templates to biomimetically synthesize cuprous oxide（Cu2O）, an important semiconductor. This experiment showed a clear relationship between the associating state of the HACP molecules and the morphology of the Cu2O particles. Cu2O hollow spheres were preferentially prepared when the HACP molecules were in an intramolecular associating state. Furthermore, a Cu2O hexapod was easily obtained when the HACP molecules were in an intermolecular associating state. The morphologies of the Cu2O crystals prepared in the presence of the HACPs also confirmed this result.

Stress-Structure Relationship of the Reversible Associating Polymer Network under Start-up Shear Flow

We adopt Langevin dynamics to explore the stress-structure relationship of telechelic reversible associating polymer gel during startup shear flow, with shear strengths varying from Wi=12.6 to Wi=12640. At weak shear flow Wi=12.6, the shear stress proportionally increases with shear strain at short times, followed by a strain hardening behavior and then passes through a maximum(σmax, γmax) and finally decreases until it reaches the steady state. During the evolution of stress, the gel network is only slightly broken and essentially maintains its framework, and the strain hardening behavior originates from the excessive stretching of chains. On the other hand, the stress-strain curve at intermediate shear flow Wi=505.6 shows two differences from that at Wi=12.6, namely, the absence of strain hardening and a dramatic increase of stress at large strains,which is caused by the rupture of gel network at small strains and the network recovery at large strains, respectively. Finally, at very strong shear flow Wi=6319.7, the gel network is immediately broken by shear flow and the stress-strain curve exhibits similar behaviors to those of classical polymeric liquids.

A study of the properties of hydrophobically associating water-soluble polymers used in drilling fluids

Hydrophobically associating water-soluble polymers (HPAP) have been synthesized from acrylamide(AM), acrylate (AA), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and hydrophobic monomer (AP) in aqueous solution by radical polymerization. New polymer drilling fluids are made up of HPAP, which is used as viscosifiers and encapsulation agents. Properties of this system are reported in this paper. Results indicate that this system has a high value of yield point to plastic viscosity (YP/PV≥0.7), high viscosity at a low-shear rate (LSRV≥30000mPa·s), excellent shear thinning behavior, good solid-carrying behavior, resistance to shear, good thermal stability (as high as 140℃) and salt resistance. The system has excellent behavior in high-density solution of NaCl and in calcium and magnesium rich saline solutions. Hence, HPAP also can be used in saltwater polymer drilling fluids.

Study and Application of a New Association Polymer System for Profile Control

A new polymer system, referred to simply as the AP-P4 polymer system, aims at solving the problems of high temperature, high salinity and the poor shearing resistance, all of which are encountered by conventional polymers (such as polyacrylamide) used in profile control, profile performance improvement and EOR operations in the Zhongyuan Oilfield, Sinopec. This system has been developed on the basis of the specific molecular structure and the better properties of high temperature resistance, high salinity resistance and strong shearing resistance of the new type of AP-P4 association polymer. Acidity modifying agents and cross-linking agents (MZ-YL, MZ-BE, MZ-XS), compatible with the new polymer system, are selected. Results of performance tests have shown that the new polymer system has excellent thickening, high temperature, high salinity and shearing resistance and anti-dehydrating properties. In 2003, it underwent its first pilot test in 26 wells in China, with remarkable effects in increasing oil production and decreasing water production. The newly developed polymer system and its application technology described in this paper may play a guiding role in polymer profile control operations in the oil reservoirs of high temperature and high salinity.

Rheological Properties of Hydrophobically Associating Polyacrylamide Solution

A temperature-resistant, salt-tolerant polyacrylamide, hydrophobically associating polymer （HAP）, was synthesized in the State Key Laboratory of Heavy Oil Processing. The rheological behavior of HAP solution was investigated by means of flow experiments in porous media and by using a HAAKE RS600 rheometer. The results of Nuclepore membrane filtration showed that filtration time increased sharply when the critical association concentration was reached. Shear rate had a greater impact on viscosity and shear stress with increasing HAP concentration. The HAP solution with a concentration of 100 mg/L （salinity 32,868 mg/L） exhibited negative thixotropy. However, at the same salinity the HAP solution showed thixotropy and its viscosity became greater when the polymer concentration increased to 1,500 mg/L. The flow experiments in cemented core samples indicated that the resistance factor and residual resistance factor of the HAP solution were 31.8 and 12 when polymer concentration and salinity were 1,500 mg/L, 32,868 mg/L at 85℃ respectively, which is favorable for flooding application. Such factors of partially hydrolyzed polyaerylamide 3530S were merely 3.14 and 1.71, so it could not be applied to polymer flooding in the oilfield with high temperature and high salinity.

Fluorocarbon- containing hydrophobically modified poly(N-isopropylacrylamide)

A fluorocarbon-modified ply( N-isopropylacrylamide) has been synthesized by copolymerization of N-isopropyl acrylamide with a small amount of acrylate or methacrylate containing a perfluoroalkyl group. It was found that the hydrophilicity of macromolecular backbone is an important factor to the solution properties of the copolymers and that hydrophobic association between fluorocarbon group is stronger than that between the corresponding hydrocarbon analogies. The viscosity of some of the copolymer solutions was very sensitive to temperature. It was dilatant at higher fluorocarbon comonomer content ( 0. 20–1.0 mol%) and was Newtonian at very low fluorocarbon comonomer content (0.03–0.2 mol%). Evidence for hydrophobic association of the fluorocarbon groups was obtained from the effects of adding NaCl and surfactants on the solution viscosity. The LC-ST properties of these copolymers were studied by DSC method and this was also found to be consistent with hydrophobic association between the fluorocarbons.