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.

Hydrophobic Small-Molecule Polymers as High-Temperature-Resistant Inhibitors in Water-Based Drilling Fluids

Water-based drilling fluids can cause hydration of the wellbore rocks,thereby leading to instability.This study aimed to synthesize a hydrophobic small-molecule polymer(HLMP)as an inhibitor to suppress mud shale hydration.An infrared spectral method and a thermogravimetric technique were used to characterize the chemical composition of the HLMP and evaluate its heat stability.Experiments were conducted to measure the linear swelling,rolling recovery rate,and bentonite inhibition rate and evaluate accordingly the inhibition performance of the HLMP.Moreover,the HLMP was characterized through measurements of the zeta potential,particle size distribution,contact angles,and interlayer space testing.As confirmed by the results,the HLMP could successfully be synthesized with a favorable heat stability.Furthermore,favorable results were found for the inhibitory processes of the HLMP on swelling and dispersed hydration during mud shale hydration.The positively charged HLMP could be electrically neutralized with clay particles,thereby inhibiting diffusion in the double electron clay layers.The hydrophobic group in the HLMP molecular structure resulted in the formation of a hydrophobic membrane on the rock surface,enhancing the hydrophobicity of the rock.In addition,the small molecules of the HLMP could plug the spaces between the layers of bentonite crystals,thereby reducing the entry of water molecules and inhibiting shale hydration.

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.

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.

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 Characterization of a HydrophilicHydrophobic IPN Composed of Poly(vinyl alcohol)and Polystyrene

A hydrophilic/hydrophobic interpenetrating polymer network （IPN） of poly （vinyl alcohol） / polystyrene was prepared by conversion of the IPN of poly （vinyl acetate）/polystyrene. The hydrophilic/hydrophobic IPN was characterized by FT-IR and DSC, and the swelling ratios of the IPN in different solvents were measured.

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.

Novel nanofiltration membranes with tunable permselectivity by polymer mediated phase separation in polyamide selective layer

Microstructure in selective layer has played a decisive role in permselectivity of nanofiltration(NF) membranes,and nanomaterials were well-known additives that had been applied to mediate the microstructure and permeability of polyamide NF membranes. However, nanoadditives generally displayed a poor dispersion in membranes or in fabrication process. To solve this problem, we showed an interesting concept that novel NF membranes with hybrid selective layer consisting of flexible polyisobutylene(PIB) and rigid polyamide could be fabricated from well-defined interfacial polymerization. The hydrophobic polymer mediated phase separation and microdomains formation in polyamide layer were found. The immiscibility between the rigid polyamide and flexible PIB as well as the resultant interface effect was interpreted as the reason for the polymer enhanced permselectivity, which was similar with the well-known thin film nanocomposite(TFN) membranes that nanoparticles incorporated contributed significantly to membrane permeability and rejection performance.Our results have demonstrated that novel NF membranes with enhanced performance can be prepared from immiscible polymers, which is a new area that has not been extensively studied before.

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.