Liehui Zhang

Synthesis of Star Hydrophobically Modified Acrylamide Copolymer and its Dilute Solution Behavior in Water

The primary objective of this work was to prepare star copolymers of acrylamide and N,N-dimethyl-N-vinylnonadecan-1-aminium chloride(C18DMAAC) and to investigate the dilute solution behavior of these star hydrophobically modified acrylamide (SHMPAM) copolymers with different C18DMAAC content. The SHMPAMs were prepared using photopolymerization. For the different polymer solutions, the relationship between specific viscosity and polymer concentration obeyed the Rabins relation well, which means that the conformations of these polymer chains were nearly spherical in dilute solution. The data of these dilute solutions were fitted by four different equations. The results showed that Schulz–Blaschke(S–B) and Fedors equations more accuratly described the dilute solution properties of these kinds of copolymers. The intrinsic viscosities calculated by different equations were different from each other, which is different from the results found for linear HMPAM. The equivalent hydrodynamic volume (voluminosity VE ) of these star copolymer solutions can not calculated by the regular method because the relationship between Y (Y = (ηr 0.5−1)/C (1.35ηr 0.5−0.1), ηr is relative viscosity and C is polymer concentration) and polymer concentration was abnormal.

Synthesis and Characterization of Star Polyacrylamides Using Poly(ethylene imine) as a Core via Photopolymerization in Water

Water-soluble thioxanthone-terminated poly(ethylene imine) (PEI 600, PEI 1800, PEI 3000 and PEI 10000; 600, 1800, 3000 and 10000 are the weight-average molecular weights of the above PEIs, respectively). Macrophotoinitiators were synthesized by introducing a certain amount of thioxanthone (TX) moieties into the periphery of PEI, and the products were confirmed by 1H-NMR, FT-IR, and elemental analysis. Star polyacrylamides (PAMs) were prepared using the obtained macrophotoinitiator as a core via photopolymerization. The effect of the molecular weight of the macrophotoinitiator on photoinitiation efficiency of the resulting polymers was investigated. The result shows that the choice of the macrophotoimitator has no influence on the rate of polymerization. In addition, three plots of characteristic properties with the star polymer were studied to confirm the existence of arms in the resulting star PAM.

Synthesis of Copolymer of Acrylamide and a Cationic-Nonionic Bifunctional Polymerizable Surfactant and Its Micellar Behavior in Water

A novel cationic-nonionic bifunctional polymerizable surfactant (PEP) was prepared by the quaternarization of poly (ethylene oxide-propylene oxide) block polymers (PEO-PPO) having terminal tertiary amine group with chloropropene. Polymeric surfactant (PAM-g-PEP) was prepared by the copolymerization of acrylamide and PEP in water and the product was confirmed by FTIR. PAM-g-PEP has exhibit excellent surface and interfacial activity and its surface tension and interfacial tension at cmc are 40.13 mN/m and 11.69 mN/m, respectively. The influence of temperature on the micellar behavior of the PAM-g-PEP in water was studied by the dynamic laser scatting (DLS) and ultraviolet spectroscope. The results showed that PAM-g-PEP in water is thermo-associative. In diluted PAM-g-PEP solution, the Rh of the polymeric surfactant increases with the temperature due to the interpolymeric aggregations are formed. In the case of concentrated PAM-g-PEP solution, the light transmittance of PAM-g-PEP aqueous solution decreases with the increasing temperature, which is may be caused by the increase of the number of the interpolymeric PEP chain aggregates.

Shear degradation resistance of star poly(ethyleneimine) - polyacrylamides during elongational flow

Abstract An experimental study of the flow-induced scission behaviour of four star hydrolyzed polyacrylamides (HPMA) with different arms during planar elongational flow in a cross-slot flow cell is described. The results showed that the shear stability of linear HPAM in distilled water was not essentially different from star HPAM. Polymer scission was not observed in either system in a shear rate range from 20,000 to 100,000s-1, which can be attributed to the strong polyelectrolyte behaviour of HPAM in distilled water. However, at the same shear rate, the star HPAMs exhibited superior shear stability in comparison to the linear HPAMs in aqueous solutions containing NaCl (CNaCl=0.2-1.0%wt) and, in particular, the initial reduction rate of relative viscosity (R) decreased with the degree of branching of the HPAMs. In addition, it was found that the R of five HPAMs in NaCl aqueous solutions exhibited an exponential dependence on shear rate, in which the coefficient C1 can be used to quantitatively evaluate shear stability. In star HPAM NaCl aqueous solutions, the increase of R with shear rate is very likely due to the decrease of the hydrodynamic radius (Rh) of these HPAMs, while the increase of R with NaCl concentrations can be attributed to the relatively low viscosity of these polymers at high NaCl concentrations.

Viscometric Studies of Interactions between Hydrophobically Modified Acrylamide Copolymer and Poly(N-isopropylacrylamide) in Dilute Solutions

The viscosity behavior of the dilute aqueous solutions of hydrophobically modified acrylamide copolymer (HMPAM) and poly(N-isopropylacrylamide) (PNIPAM) was investigated. A negative deviation of reduced viscosity of HMPAM + PNIPAM from the theoretical values was observed. Both a conventional viscometry method and a method using an aqueous solution of one polymer as the solvent for the other polymer were used to clarify the mechanism behind the observed viscosity behavior. With the conventional method, the theoretical predictions obtained by the Δb (or α) criterion are contradictory to the experimental results and cannot be applied to describe the interaction between HMPAM and PNIPAM, where Δb is the difference of experimental interspecific interaction coefficient bm and theoretical bm,i and α is the difference of experimental Huggins coefficient km and theoretical km,i. The change of Δ[η]/[η]i suggests that there is only an attractive interaction between HMPAM and PNIPAM, where Δ[η] is the difference of experimental intrinsic viscosity [η]m and theoretical [η]i. Results from the method using an aqueous solution of one polymer as the solvent for the other polymer confirmed the attractive interaction between HMPAM and PNIPAM and indicated that the attachment of the PNIPAM molecules to the hydrophobic groups in HMPAM can disrupt both the initial intra- and intermolecular associations between HMPAM chains simultaneously. The disruption of the original intramolecular association of HMPAM leads to an increase in the intrinsic viscosity [η], while the disruption of the original intermolecular association of HMPAM yields a negative deviation of the reduced viscosity.

Thermo-Associative and Salt-Associative Graft Copolymers of Surfactant Macromonomers and Acrylamide: Synthesis and Solution Properties in Dilute Aqueous Solutions

Three new surfactant macromonomers (SMM) with different ethylene oxide (EO)/propylene oxide (PO) ratios (for SMM1, SMM2, and SMM3, the EO/PO ratios were 1:0.5, 1:0.9, and 1:1.25, respectively) were synthesized by the reaction between PEO-PPO di-block polymers having terminal tertiary amine groups and chloropropene. Graft copolymers of acrylamide and SMM (PAM-g-SMM) were prepared with different SMMs and grafting densities in water, and the products were confirmed by FTIR and elemental analysis. Owing to the strong hydrophobicity of the graft, the PAM-g-SMM3 was not water soluble. However, PAM-g-SMM1 and PAM-g-SMM2 aqueous solutions had good surface activity and their surface tensions were 44.26 and 37.63 mN/m at a concentration of 1000 mg/L, respectively. In general, in diluted graft PAM solutions, the copolymer predominantly formed intrapolymeric associates. The PAM-g-SMM2 was both thermo-associative and salt-associative in dilute solution. For PAM-g-SMM2, when the temperature and salt concentration increased, interpolymeric aggregations were formed.

Preparation of hydrophobically-modified acrylamide copolymers using poly(ethylene imine) as a photoinitiator and its performance evaluation in Bohai oilfield

This paper presents copolymers of acrylamide, N,N-dimethyl-N-vinylnonadecan-1-ammonium chloride and N-(2,4-dimethylpentan-2-yl) acrylamide synthesized by photopolymerization using modified poly(ethylene imine) as initiator in water. These hydrophobically modified acrylamide copolymers were dissolved in the brine that was used in enhanced oil recovery in Bohai oilfield. It was found that when the content of N-(2,4-dimethylpentan-2-yl) acrylamide and N,N-dimethyl-N-vinylnonadecan-1-ammonium chloride were 0.1 mol % and 0.3 mol %, respectively, the resulting polymer could meet the demand of solution time and the polymer mechanical shear stability required in Bohai oilfield. The solution properties of synthesized copolymers were compared with the hydrophobically modified polymer currently used in enhanced oil recovery in Bohai oilfield.

Synthesis of star hydrophobically-modified acrylamide copolymers and its some properties in brine

Abstract Star copolymers of acrylamide (AM) and N,N-dimethyl-Nvinylnonadecan- 1- aminium chloride (C18DMAAC) were synthesized by photopolymerization in water. Some properties of these star hydrophobically modified acrylamide copolymers (SHMPAM) with different C18DMAAC contents and the linear hydrophobically modified acrylamide copolymers (LHMPAM) in brine were characterized. The increase in C18DMAAC content resulted in decreased intrinsic viscosity and increased Huggins constant for SHMPAM. Similar results were observed for LHMPAM. With similar intrinsic viscosity and C18DMAAC content, the Huggins constant of SHMPAM was much higher than that of LHMPAM, which might be due to the fact that SHMPAM had much stronger intramolecular interaction in dilute polymer solutions. In semi-dilute solutions, the apparent viscosity of SHMPAM was increased with increasing C18DMAAC content, which was similar to that of LHMPAM. However SHMPAM exhibited higher apparent viscosity than LHMPAM because it had more arms and thus had more chances to form three-dimensional networks in semi-dilute solutions. In the flowinduced scission experiment, SHMPAM exhibited superior shear stability in comparison with LHMPAM. When the extensional shear rate was ≈ 40000 s-1, the reduction ratios of the apparent viscosities of the four SHMPAMs after the scission were about 80%. In contrast, when the extensional shear rate was ≈20000 s-1, the reduction ratio of the apparent viscosity of LHMPAM-0.40 had already reached around 80%.

Synthesis and solution behaviors of star hydrophobically modified acrylamide copolymers

Abstract Star copolymers of acrylamide and N,N-dimethyl-N-vinylnonadecan-1-aminium chloride (C18DMAAC) were synthesized by photopolymerization in water. Solution behaviors of these star hydrophobically modified acrylamide copolymers (SHMPAMs) with different C18DMAAC contents and the linear hydrophobically modified acrylamide copolymers (LHMPAMs) were characterized. The increase in C18DMAAC content resulted in decreased intrinsic viscosity and increased the Huggins constant for SHMPAMs. Similar results were observed for LHMPAMs. With similar intrinsic viscosity and C18DMAAC content, the Huggins constant of SHMPAMs was much higher than that of LHMPAMs, which could be due to the fact that SHMPAMs had much stronger intramolecular interaction in dilute polymer solutions. In semi-dilute solutions, the apparent viscosity of SHMPAMs was increased with increasing C18DMAAC content, which was similar to that of LHMPAMs. However, SHMPAMs exhibited higher apparent viscosity than LHMPAMs because it had more arms and thus had more chances to form three-dimensional networks in semi-dilute solutions. In the flow-induced scission experiment, SHMPAMs exhibited superior shear stability in comparison with LHMPAMs. When the strain rate was ≈40,000 s-1, the reduction ratios of the apparent viscosities of the four SHMPAMs after the scission were approximately 80%. By contrast, when the strain rate was ≈20,000 s-1, the reduction ratio of the apparent viscosity of LHMPAM-0.40 had already reached around 80%.

A Novel Thermothickening Aqueous System Prepared from Hydrophobically-Modified Acrylamide Copolymer, Poly(N-isopropylacryl-amide) and Sodium Dodecyl Benzene Sulfonate and Its Mechanism Studies

A new thermothickening aqueous system was presented based on mixtures of hydrophobically-modified acrylamide copolymer (HMPAM), poly(N-isopropylacryl-amide) (PNIPAM) and sodium dodecyl benzene sulfonate (SDBS). Unique in the thermothickening system, a maximum viscosity and the temperature (T max) when reaching such viscocity change independently, reflects the presence of intermolecular interactions. The T max of the new system suggests that its thermothickening behavior is correlated to the cloud point temperature (T c) of PNIPAM, which can be easily adjusted to desired values by the addition of SDBS. The experimental data also indicate that the temperature between the rheological transition temperature (T t) and T max in HMPAM+PNIPAM+SDBS is within the range of 35–65°C, and the thermothickening behavior originates from the reinforcement of the association network between HMPAM, PNIPAM and SDBS. Consequently, the viscosity over the corresponding thermosensitive range upon cooling is higher than that upon heating.