An Ion-imprinted Silica Gel Polymer Prepared by Surface Imprinting Technique Combined with Aqueous Solution Polymerization for Selective Adsorption of Ni(Ⅱ) from Aqueous Solution

A novel Ni（Ⅱ） ion-imprinted silica gel polymer was prepared via the surface imprinting technique combined with aqueous solution polymerization by using 2-acrylamido-2-methyl-1-propanesulfonic acid（AMPS） as a functional monomer for the selective separation of Ni（Ⅱ） from aqueous solution. The sorbent showed good chemical and thermal stability. Kinetics studies indicated that the equilibrium adsorption was achieved within 10 min and the adsorption kinetics fitted well with the pseudo-second-order kinetic model. The maximum adsorption capacity of the ion-imprinted polymer towards Ni（Ⅱ） at the optimal p H of 7.0 was 66.22 mg·g^（-1）. The relative selectivity coefficients of the sorbent were 9.23, 15.71, 14.72 and 20.15 for Ni（Ⅱ）/Co（Ⅱ）, Ni（Ⅱ）/Cu（Ⅱ）, Ni（Ⅱ）/Zn（Ⅱ） and Ni（Ⅱ）/Pb（Ⅱ）, respectively. The adsorption isotherm fitted well with Langmuir isotherm model. The thermodynamic results indicated that the adsorption of Ni（Ⅱ） was a spontaneous and endothermic process. The sorbent showed good reusability evidenced by six cycles of adsorption/desorption experiments. The precision of this method is satisfactory. Thus, the prepared sorbent can be considered as a promising sorbent for selective separation of Ni（Ⅱ） in real water samples.

PREPARATION OF LOW MOLECULAR WEIGHT POLY(GLYCIDYL METHACRYLATE) BY PHOTOPOLYMERIZATION

Low molecular weight poly（glycidyl methacrylate）s （PGMAs） were prepared by photopolymerization in ethyl acetate, with benzophenone （BP） as photoinitiator, and triethylamine （TEA） as hydrogen donor. The existence of semipinacol dormant end groups in PGMA was confirmed by FT-IR and ^1H-NMR, and the content of the semipinacol dormant groups was determined quantitatively by ^1H-NMR measurement. The effects of various thctors, such as reaction time, BP concentration and monomer concentration on the synthesis of the polymers were investigated systematically. The molecular weights of the polymers were also investigated with GPC. It is shown that increasing BP concentration and decreasing irradiation time and monomer concentration led to a significant decrease of the molecular weights.

Study of action mechanisms and properties of Cr^(3+) cross-linked polymer solution with high salinity

Performance characteristics of partially hydrolyzed polyacrylamide （HPAM） and cross- linked polymer （CLP, Cr^3＋ as the cross linker） solutions have been investigated. A Brookfield viscometer, rheometer, dynamic light scattering system, and core flow device have been used to measure the viscosity, viscoelasticity, polymer coil dimensions, molecular configuration, flow characteristics, and profile modification. The results show that, under conditions of high salinity and low HPAM and Cr^3＋ concentrations, cross-linking mainly occurred between different chains of the same HPAM molecule in the presence of Cr^3＋, and a cross-linked polymer （CLP） system with a local network structure was formed. Compared with an HPAM solution of the same concentration, the apparent viscosity of the CLP solution increased slightly or remained almost unchanged, but its viscoelasticity （namely storage modulus, loss modulus, and first normal stress difference） increased, and the resistance coefficient and residual resistance coefficient increased significantly. This indicates that the CLP solution exhibits a strong capability to divert the sequentially injected polymer flood from high-permeability zones to low- permeability zones in a reservoir. Under the same HPAM concentration conditions, the dimensions of polymer coils in the CLP solution increased slightly compared with the dimensions of polymer coils in HPAM solution, which were smaller than the rock pores, indicating that the cross-linked polymer solution was well adapted to reservoir rocks. Core flood experiments show that at the same cost of reagent, the oil recovery by CLP injection （HPAM-1, Cr^3＋ as the cross linker） is 3.1% to 5.2% higher than that by HPAM- 2 injection.

A NOVEL INTERPRETATION OF CONCENTRATION DEPENDENCE OF VISCOSITY OF DILUTE POLYMER SOLUTION

The concentration dependence of the reduced viscosity of dilute polymer solution is interpreted in the light of a new concept of the self-association of polymer chains in dilute solution. The apparent self-association constant is defined as the molar association constant divided by the molar mass of individual polymer chain and is numerically interconvertible with the Huggins coefficient. The molar association constant is directly proportional to the effective hydrodynamic volume of the polymer chain in solution and is irrespective of the chain architecture. The effective hydrodynamic volume accounts for the non-spherical conformation of a short polymer chain in solution and is a product of a shape factor and hydrodynamic volume. The observed enhancement of Huggins coefficient for short chain and branched polymer is satisfactorily interpreted by the concept of self-association. The concept of self-association allows us to predict the existence of a boundary concentration C-s(dynamic contact concentration) which divides the dilute polymer solution into two regions.

Influence of dissolved oxygen content on oxidative stability of linked polymer solution

The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.

EFFECT OF ADSORPTION ON THE VISCOSITY OF DILUTE POLYMER SOLUTION

Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinyl alcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves at extremely dilute concentration levels similar to the phenomena observed for many polymer solutions in the early 1950's. Upon observation of the changes of the flow times of pure water in and the wall surface wettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosity abnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymer chains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isotherms was proposed and a mathematical; analysis for data treatment was performed. The theory could adequately describe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymer solutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.

Rheological Behavior for Polymer Melts and Concentrated Solutions——Part Ⅶ: A Quantitative Verification for the Molecular Theory of Non-linear Viscoelasticity with Entanglement Constraints in Polymer Melts

Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between and shear rate (), and topologically constrained dimension number and a were derived. Linear viscoelastic parameters and and topologically constrained dimension number and as a function of the primary molecular weight, molecular weight between entanglements and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters G and topologically constrained dimension number a and and molecular weight and from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.

Rheological Behaviour for Polymer Melts and Concentrated Solutions Part Ⅲ: A New Multiple Entanglement Model to Predict the Dependence of Linear Viscoelastic Function (η_0, Ψ_(10)~0,η_(ext)~0) on the Ranges of Primary Molecular Weights and th

It is shown theoretically that the viscoelasticity of polymer melts is determined by three combining factorst they are the primary molecular weight and its distribution, the number of entanglement sites on polymer chain and the sequence distribution of constituent chains in entanglement spacings. A unified quantity for the three combing factors is the average constrained dimensional number of constituent chains in the long entanglement spacings (v). A new relation of v to the primary molecular weight and the number of testing polymers were derived from the multiple entanglement and reptation model, and a new method for determining v was proposed. The dependences of linear viscoelastic functions on the primary molecular weight and its distribution were derived by the statistical method. When Mn=6Me to 18 Me, the values of (v) can range from 3.33 to 3.70. Their values are in a good agreement with the experiment data, and it can slightjy vary with the different species of polymers and the different ranges of molecular weight of polymers

Rheological Behaviour for Polymer Melts and Concentrated Solutions Part Ⅰ:A New Multiple Reptation Model to Predict the Nonlinear Visco-elasticity with Nagai Chain Constraints in Entangled Polymer Melts

An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results

ASSOCIATION OF ETHYLENE VINYL ACETATE COPOLYMER IN DILUTE SOLUTIONS IV. SOLVENT MIXTURE AND ADDITIVE EFFECT ON C_A

Critical association concentration (Ca) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent) was investigated. DCE is a good solvent for polyvinyl acetate (PVAc) and a poor solvent for paraffin, whereas CYH is a good solvent for the paraffin and a precipitant for PVAc. Viscosities of EVA in different compositions of the solvent mixture with and without additives were measured. Viscosity results were used to determine the C-A value of the systems. It is shown that C-A was markedly dependent on the composition of the solvent mixture and concentration and structure of the additive. Solvation and competition between hydrogen bonding and micellisation were suggested for qualitative description of the changing of C-A value observed.

COMPUTER SIMULATION OF POLYMER SOLUTION THERMODYNAMICS

The statistical counting method for the computer simulation of the thermodynamic quantities of polymer solution has been reviewed. The calculating results for a single athermal chain confirm the theory of the renormalization group. The results for the athermal solution are consistent with the scaling law of the osmotic pressure with the exponent 2.25. The results for a single chain with the segmental interaction are in a good agreement with the exact results obtained by the direct counting method. The results for the polymer solution show us that the Flory-Huggins parameter is strongly dependent on both the polymer concentration and the interaction energy between segments. (Author abstract) 15 Refs.

STUDY ON THE CONFORMATIONAL PROPERTIES OF RIGID POLYELECTROLYTE SPU IN SOLUTION

The conformation and dimension of SPU polyanion have been studied by viscosity and quasi-elastic light scattering methods. The rigidity of SPU is somewhat similar to CMC and its hydrodynamic radius decreases only slowly with increasing concentration of NaCl.

Theoretical analysis of microscopic oil displacement mechanism by viscoelastic polymer solution

The microscopic oil displacement mechanism in viscoelastic polymer flooding is theoretically analyzed with mechanical method.The effects of viscoelasticity of polymer solution on such three kinds of residual oil as in pore throat,in sudden expansion pore path,and in dead end are analyzed.Results show that the critical radius of mobile residual oil for viscoelastic polymer solution is larger than that for viscous polymer solution,which makes the oil that is immobile in viscous polymer flooding displaced under the condition of viscoelastic polymer solution.The viscous polymer solution hardly displaces the oil in dead ends.However,when the effect of viscoelasticity is considered,the residual oil in sudden expansion pore paths and dead ends can be partly displaced. A dimensionless parameter is suggested to denote the relative dominance of gravity and capillary pressure.The larger the dimensionless parameter,the more accurate the increment expressions.

Pressure Effects on Thermodynamics of Phase Behavior in Polystyrene/Methylcyclohexane Solutions

The calculations presented in this paper are based on the Sanchez-Lacombe（SL）lattice fluid theory.The interaction energy parameter,g12/k,required in this approach was obtained by fitting the cloud points of polystyrene（PS）/methylcyclohexane（MCH）polymer solutions under pressure.The SL lattice fluid theory was used to calculate the spinodals,the binodals,and the Flory-Huggins（FH）interaction parameter of the solutions.The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well.However,the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions.Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.

PREDICTION OF THE RHEOLOGICAL PROPERTIES OF STAR—TYPE BRANCHED POLYMER SOLUTIONS BY MEANS OF THE FIXED SPECTRUM MODEL

The Rouse-Zimm model with slippage was improved and the basic parameters of modelwere modified to explain the rheological properties of star-type branched polymersolutions. The theoretical results show good agreement with experimental data.

STUDY ON STYRENE-BUTADIENE BLOCK COPOLYMER FOR THE MODIFICATI0N OF TIRE TREAD

This paper mainly deals with the design and synthesis of a novel styrene-butadieneblock copolymer. When this copolymer is used in the tread portion of tyres, it can improvewet skid resistance and reduce rolling resistance without sacrificing its general physical-mechanical properties. The visco-elastic curve of tire tread using the novel copolymer asits rubber portion was showed. Reactivity ratios for two monomers in the polymerizingsystem were calculated. The diagrams of differelitial, integral and finite difference calculithroughout the whole molecular chain were presented. The influence of the micro- andmacro-structure of the copolymer chain on wet skid resistance and rolling resistance wasdiscussed

Influence of Solvent Conditons on Average Relative Molecular Weight of Polyoctadecyl Acrylate

Polymerization of octodecyl acrylate is studied in four solvents — carbon tetrachloride, chloroform, methylbenzene and tetrachloroethane. Experimental results indicate that the sequence of chain transfer constants in solvents is: carbon tetrachloride>chloroform>methylbenzene>tetrachloroethane in the polymerization of octadecyl acrylate. Influences of four solvents on solubility of polyoctadecyl acrylate prove not the same. In chloroform, polyoctadecyl acrylate shows the highest relative viscosity and the lowest chain termination rate constant. In higher conversion, the average relative molecular weight of polyoctadecyl acrylate depends mainly on the chain transfer constant of the solvent. Under the circumstance of monomer conversion higher than 30%, the viscosity effect induced by polymeric molecular shape in the solvents have a strong influence on the relative molecular weight of the polymer obtained.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅲ. Effect of the Polymer Solvents

The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the two parameters indicates Arrhenius behavior. The polymer solventeffects on diffusion and electron transfer dynamics of ferrocene were discussed

Synthesis and Characterization of Poly (ether imide)s Containing Phthalazinone and Isopropyl Moieties

A novel poly(ether imide)s containing phthalazinone and isopropyl moieties derived from 2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl]-phthalazin-1-one and bisphenol-A diphthalic anhydride was synthesized by one-step solution condensation polymerization in nr-cresol. The polymer was characterized by FTIR, NMR, molecular weights, glass transition temperature, thermal degradation temperature and WAXD.

STUDY ON THE CONCENTRATION EFFECTS IN GPC IV A NEW METHOD FOR DETERMINATION OF SECOND VIRIAL COEFFICIENTS FROM THE CONCENTRATION EFFECTS

In this paper a new relation between the second virial coefficients A_2, (?)_w and (dV_(es)/dC)_c→0=K_s was derived from proposed model theory of concentration effects in GPC for mono-and poly-dispersed polymers. Based on this relation a new method for determination of second vifial coefficients from the combination of (dV_(es)/dC)_c→0=K_3, (?)_w and K_H measurements was proposed.The values of A_2 for mono-and poly-dispersed polystyrenes with molecular weight range from 10~4 to 10~6 in good and theta solvents were determined by proposed method. Results show that their values of A_2 are in agreement with those obtained by light scattering.