On Single Compartment Pharmacokinetic Model Systems that Obey Free Radical Copolymerization Kinetics and Multiplicity

This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comonomers for well mixed case was derived. For some cases, such as DEF-AN, diethyl fumarate and acrylonitrile system multiplicity in composition were found. The analysis is extended to n monomers. State space model expressions are used and the QSSA assumption is stated in state space equation form. Conditions when damped oscillations can be expected are noted. In addition to multiplicity in product composition, an account of reactivity ratios and other instances of multi- plicity were found during the pharmacodynamics of the free radical polymerization reactions. A careful study of initiated case, thermal case, 1 CSTR and 2 CSTRS was undertaken and results were presented. Numerical integration techniques were employed on the desktop computer. Steady state and transient state conversion for initiated case and thermal case for 1 CSTR and 2 CSTRs were calculated and plotted in Figures 7-9 and 12. No multiplicity was found in the thermal case for 1 CSTR in the dynamics of transient monomer conversion. Multiplicity was found in the initiated case for 1 CSTR in the dynamics of transient conversion of monomer. The multiplicity was found in the second CSTR for the case of 2 CSTRs in series. No multiplicity was found in the case of initiator decay.

Graft Copolymerization of N,N-Dimethylacrylamide to Cellulose in Homogeneous Media Using Atom Transfer Radical Polymerization for Hemocompatibility

In homogeneous media, N,N-Dimethylacrylamide (DMA) was grafted copolymerization to cellulose by a metal-catalyzed atom transfer radical polymerization (ATRP) process. First, cellulose was dissolved in DMAc/LiCl system, and it reacted with 2-bromoisobutyloyl bromide (BiBBr) to produce macroinitiator (cell-BiB). Then DMA was polymerized to the cellulose backbone in a homogeneous DMSO solution in presence of the cell-BiB. Characterization with FT-IR, NMR, and GPC measurements showed that there obtained a graft copolymer with cellulose backbone and PDMA side chains (cell-PDMA) in well-defined structure. The proteins adsorption studies showed that the cellulose membranes modified by the as-prepared cell-PDMA copolymer owns good protein adsorption resistancet.

Development of Hydrogel Polyelectrolyte Membranes with Fixed Sulpho-Groups via Radical Copolymerization of Acrylic Monomers

Electrolyte hydrogels are perspective materials for applications in electrochemical devices, which work at ambient temperatures. In this work, hydrogel sulpho-modified membranes were formed by radical co-polymerization of sodium styrensulphonate and potassium sulphopropyl acrylate with acrylamide and acrylonitrile. The hydrogel membranes were obtained in the form of thin films. Properties of the membranes were studied by thermogravimetry, mass-spectrometry and IR-spectrometry. The prepared membranes were thermally stable up to 70°C - 90°C, and showed ion exchange capacity and swelling coefficients sufficient for use as ion-exchange or proton-conducting membranes.

Research on the Graft Copolymerization of EH-lignin with acrylamide

Lignin isolated from enzymatic hydrolyzed corn-stalks (EH-lignin) is a renewable natural polymer noted for its versatility and applicability in a vari-ety of uses. Graft copolymerization of EH-lignin with acrylamide (AM) and the application of this copolymer as a flocculant in dye wastewater treatment were studied in this article. The influ-ences of some factors on yield of copolymer and the grafting ratio were investigated and the structure of EH-lignin/AM graft copolymer was characterized by FT-IR. According to the yield and the grafting ratio, the optimum conditions for graft copolymerization were as follows: initiator K2S2O8-Na2S2O3 with a quantity 3 wt% of EH-lignin, mass ratio of AM to EH-lignin was 2~3, reaction time 4h and temperature at 50℃. It was found that the absorption capacity of graft copolymer to two azo-dyes was enhanced with the increase of grafting ratio. Furthermore, the residue concen-tration of EH-lignin/AM graft copolymer remained in the supernatant after flocculation was much lower than that of pure EH-lignin.

Copolymerization of Acrylonitrile/1-Vinyl-3-Ethylimidazolium Bromide and Rheological, Thermal Properties of the Copolymer

Acrylonitrile(AN)/1-vinyl-3-ethylimidazolium bromide(VIMB) copolymer was prepared via solution polymerization using dimethyl sulfoxide(DMSO) as a solvent and azodiisobutyronitrile as an initiator. The effects of comonomer VIMB on the polymerization, rheological properties of the polymer solution and thermal properties of the copolymer were investigated. The ionic liquid VIMB resulted in higher polymerization conversion ratio and higher average molecular weight when copolymerized with AN than itaconic acid(ITA). Rheological measurements indicated that the transition shear rate increased linearly with increasing temperature for P(AN/ITA)/DMSO solution, while an exponential growth with temperature was observed for P(AN/VIMB)/DMSO solution. The exothermic peaks of DSC curves in N_2 appeared at 276.67 and 257.34 °C for P(AN/VIMB) and P(AN/ITA), respectively. As a potential comonomer of AN for PAN carbon fibers, the VIMB resulted in about 7% higher char yield in N_2, and 23.7% less weight loss at 600 °C in air than ITA copolymer.

Effects of Polymerization Conditions on Copolymerization of Acrylonitrile with Maleic Anhydride in Water

A acrylonitrile-maleic anhydride copolymer was pre-pared by precipitation polymerization with（NH4）2S2O8-NaHSO3 as oxidation-reduction initiator in water.The effects of polymerization conditions（such as contentof adjustment reagent of molecular weight,concentrationof monomers,reaction time and temperature,ratio ofinitiator to monomer and ratio of reductant to oxidizer inmole）on composition,molecular weight and conversionof the copolymer were investigated.The copolymer wascharacterized with IR and Elementary Analysis.Its ther-mal property and crystallinity were determined with DTAand WAXD,respectively.

<i>In Situ</i>UV–Vis Spectroelectrochemical Studies on the Copolymerization of Diphenylamine and <i>o</i>-Phenylenediamine

The in situ ultraviolet-visible (UV-Vis) spectroelectrochemical study on the copolymerization of diphenylamine (DPA) and o-phenylenediamine (OPD) has been performed at a constant potential of 0.8 V using indium tin oxide (ITO)-coated glass electrodes as working electrode. And also, as a comparison, the electrochemical homopolymerizations of DPA and OPD have been investigated by using the in situ spectroelectrochemical technique. The intermediate species generated during the electrochemical homopoly-merization of DPA and OPD, and the copolymerization of DPA with OPD have been identified by using the in situ spectroelectrochemical procedure. The results reveal the formation of an intermediate in the initial stage of copolymerization through the cross-reaction of the cation radicals of DPA and OPD, and the absorption peak located at 538 nm in the UV–Vis spectra is assigned to this intermediate. To further investigate the copolymerization of DPA with OPD, cyclic voltammetry (CV) has been used to study the electrochemical homopolymerization of DPA and OPD and also the copolymerization of DPA and OPD with different concentration ratios in solution. The different voltammetric characteristics between the homopolymerization and copolymerization processes exhibit the occurrence of the copolymerization, and the difference between the copolymerization of DPA and OPD with different concentration ratios shows the dependence of the copoly-merization on the concentrations of DPA and OPD. The copolymer has also been characterized by Fourier transform infrared spectroscopy (FT-IR).

Research on poly(styrene-acrylic acid)-supported neodymium complex in catalytic copolymerization of styrene and 4-vinylpyridine

The catalytic activity of poly（styrene-acrylic acid） （PSAA） supported neodymium chloride （NdCl3） complex for the copolymerization of styrene and 4-Vinylpyridine was studied. The influence of various factors, such as Al/Nd molar ratio, reaction time, macromolecular carder （PSAA）, and ratio of styrene to 4-vinypyridine （g/g）, on the copolymerization yield of styrene and 4-Vinylpyridine was investigated. The results showed that the copolymerization of polar monomers with olefins occurred efficiently and the catalytic activity of polymer-supported catalyst was higher than that of the similar small molecular catalysts. The activity of PSAA.Nd complex increased with in- creasing Al/Nd molar ratios and decreased with increasing polymerization time. The highest activity of PSAA＇Nd was observed at 120 min, and the highest yield was found at the ratio of styrene to 4-vinylpyridine of 4：2. DSC analysis presented that the resulted polymer had only one glass transition temperature, and showed very good thermal stability.

Study on Copolymerization of Rare Earth-Carboxylic Acid Complex

Complex of rare earth with carboxylic acid was prepared by precipitation and direct method. It was copolymerized with such monomers as acrylic acid and other ones to synthesize ionomer of rare earth and organic polymer with different rare earth contents. Its glass-transition temperature and heat stability were analyzed by TG and DTA. Infra-red detector was used to show its structure. The effect of rare earth complex prepared by different methods on copolymerization and properties of copolymers was also discussed.

Photo-Grafting Copolymerization of PP Nonwoven Fabric and Its Application for Acidic Dye Adsorption and Filtration

The monomer methacrylamido propyl trimethy ammonium chloride( MAPTAC) was copolymerized onto the fiber surface of polypropylene( PP) nonwoven fabric under ultroviole radiation. The weak acid red GN dye adsorption and adsorptive filtration performance of the resulted PP fabrics were investigated.The results showed that the grafting copolymerization preferred to happen in the inner layer of the fabrics. The water flux of the grafted fabrics decreases with the increase of grafting yield. The collapse of the grafted polymer chains causes the flux increase in acidic condition,or vice versa at alkaline version. The coiling of the polyelectrolyte chains upon the dye adsorption seems to violate the routine assumption of the rigid substrate, and this gets the adsorption energy constant negative. The static adsorption process follows the Lagergren's pseudo-second order kinetic equation. The removals of circa( ca.) 100% of the total permeation volume3 500 mL simulated dye wastewater was reached during permeation.The dye adsorbed fabrics were regenerated by the mixed media of the cationic surfactant / ethanol /water. The grafted fabric assumes stable fabric integrity and stability during permeation,and presents excellent dye adsorption capacity,easy desorption, and repeatable utilization.

单茂钛/甲基铝氧烷催化剂乙烯/丙烯共聚合研究

改性甲基铝氧烷(mMAO)激活五甲基茂基三氯化钛(Cp TiCl3)催化乙烯 丙烯共聚合,控制两种单体的进料配比,得到单元序列分布不同的共聚物.混合单体中含有少量丙烯,共聚合活性高于相同聚合条件下乙烯均聚合的活性.用1 3C -NMR测定共聚物分子链的微观结构和单元序列分布,计算出单体的竞聚率;结果表明共聚物分子链中两种单体的序列分布均匀.混合单体中丙烯含量较大时,共聚物为完全无规共聚物;而当丙烯含量少时,丙烯链节或短的聚丙烯链段均匀分布于聚乙烯链段之间.共聚物经DSC分析,也证明不存在长序列的聚乙烯链段;因此,即便在进料气体中丙烯含量很少的情况下,共聚物仍然没有明显的熔融温度和结晶性.

Research on Poly(Styrene-Crylicacid)-Suported Neodymium Complex Catalytic Copolymerization of Styrene and 4-Vinylpyridine

The catalytic activity of poly（styrene-cryli- caeid） （PSAA） supported neodymium chloride （NdCl3） complex for the copolymerization of styrene and 4-vinylpyridine was studied. The influence of various factors, such as Al/Nd molar ratio, reaction time, and ratio of styrene to 4-vinypyridine （g· g^-1 ）, on copolymerization of styrene and 4-Vinylpridine was investigated. The results show that the copolymerization of polar monomers with olefins occurs efficiently. The catalytic activity of polymer-supported catalyst is higher than that of the similar small molecule catalysts. The activity of PSAA· Nd complex increases with increasing Al/Nd ratios and decreases with increasing polymerization time, the highest activity of PSAA· Nd is observed at 120 min. High yield is found at the ratio of styrene to 4-vinylpyridine is 4：2. The resulted polymer shows very good thermal stability.

THE EFFECTS OF MAGNETIC FIELD ON GRAFT COPOLYMERIZATION OF METHYL METHACRYLATE ONTO POLYVINYL ALCOHOL IN THE PRESENCE OF BENZOPHENONE DURING UV IRRADIATION

The effects of magnetic field on the graft ratio and stereoregularity of grafts of PVA-g-MMA in the presence ofbenzophenone during UV irradiation are discussed. By means of IR, it was found that the graft ratio was increased with the increment of magnetic field strength. Furthermore, application of relative weak magnetic field of 0.4 Tesla had been shown to substantially enhance the stereo-regularity of graft copolymer. The maximum stereo-regularity appeared when the graft ratio approached to 85% with the magnetic field of 1.2 Tesla (T). The resistance to moisture and heat resistance of the grafted copolymer in the presence of magnetic field were also improved.

STUDY ON IMMOBILIZED YEAST CELLS WITH HRDROPHILIC POLYMER CARRIER BY RADIATION - INDUCED COPOLYMERIZATION

In this paper, various kinds of monomers 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA) and methoxy polyethylene glycol methylacrylate (M-23G) were eopolymerized by radiation technique at low temperature (-78℃) and several kinds of copolymer carriers were obtained. Yeast cells were immobilized through adhesion and multiplication of yeast cells themselves on these carriers. The etharol productivity of immobilized yeast cells with these carriers was related to the monomer composition and water content of copolymer carriers and the optimum monomer composition was 20%:10% in poly (HEA-M23G). In this case, the ethanol productivity of immobilized yeast cells was 26 mg /( ml·h), which was 4 times as high as that of free cells. In this study, the effect of adding of crosslinking reagent (4G) in copolymer on activity of yeast cells immobilized with the carriers were also studied. It was found that the effect of adding crosslinking reagent (4G) in lower monomer composition of poly(HEA-M23G) on the ethanol productivity of immobilized cells was better than that in higher one in this work.

Study on Alternating Copolymerization of Polyester-amides

The preparing methods, choice of catalysts and reaction kinetics of one of the monomers, diesteramide(DEA), of polyester-amides were investigated in details. The chemical structure of DEA was analyzed. And the Polyester-amides (PEA) were obtained by melt copolymerization with DEA. It is shown that DEA can be synthesized by DMT and hexamethylene diamine with the catalyst EX - 1 or EX - 2. The relationship between reaction rate of synthesizing monomer and concentration of hexamethylene diamine is first order kinetic relation.

CATALYTIC COPOLYMERIZATION OF STYRENE AND ETHYLENE BY NEUTRAL NICKEL(Ⅱ) COMPLEXES IN EMULSION

Emulsion copolymerization of styrene and ethylene catalyzed by a series of neutral nickel(Ⅱ) complexes was carried out in an aqueous system to give high-molecular-weight copolymers.The copolymers and emulsions were characterized by an array of techniques including NMR,GPC,TEM,WAXD and DSC.The results indicate that the copolymers obtained are mostly block copolymers of polyethylene with random insertion of styrene units,and their M_W is in the range of 10~5-10~6.By enhancing the electron withdrawing of the s...

COPOLYMERIZATION OF PROPYLENE WITH HINDERED PIPERIDINE MONOMER OVER A HIGH ACTIVITY SUPPORTED ZIEGLER-NATTA CATALYST

Copolymerization of propylene and hindered piperidine monomers was carried out over a high activity supported Ziegler-Natta catalyst, using Al(C2H5)(3) as cocatalyst. Factors which affect the copolymerization were studied, The copolymers exhibited high light stability without adding extra light stabilizers. A self-stabilized polypropylene was prepared.

RING OPENING COPOLYMERIZATION OF SUCCINIC ANHYDRIDE-ETHYLENE OXIDE BY Al(Ⅲ) ORGANOMETALLIC CATALYSTS

Ring opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO)was successfully carried out by using a series of aluminum-based catalyst in 1,4-dioxane at62±2℃. The results showed that in-situ AlR_3-H_2O (R=ethyl, iso-butyl) catalysts gavehigher molecular weight (M_w～10~4), while Al(OR)_3 catalysts gave the higher alternatingcopolymer structure with slightly lower molecular weight. The in-situ AlR_3-H_2O systemshave been evaluated in more detail for the reaction which showed the optimum H_2O/Almolar ratio to be 0.5. The copolymers with different composition (F_(SA)/F_(EO)= 36/64to 45/55 mol/mol) were synthesized by using different monomer feed ratio. The melt-ing point (T_m), glass transition temperature (T_g) and enthalpy of fusion (ΔH_f) of thesecopolymers are depended on the copolymer composition and in the range of 87～102℃,-12～-18℃, and 37～66J/g, respectively. The second heating scan of DSC also in-dicated that the higher alternating copolymer was more easily recrystallized. The onsetdecomposition temperature was more than 300℃ under nitrogen and influenced by thecopolymer composition.

ELECTROCHEMICAL COPOLYMERIZATION OF DIBENZOFURAN AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...