Study on the Effect of Carboxyl Terminated Butadiene Acrylonitrile (CTBN) Copolymer Concentration on the Decomposition Kinetics Parameters of Blends of Glycidyl Epoxy and Non-Glycidyl Epoxy Resin

The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo gravimetric analysis (TGA) technique under a nitrogen atmosphere. The blends were prepared by physical mixing and were cured with diamine. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. From this value of reaction order, activation energy (E), and pre-exponential factor (Z) were calculated. It was found that the activation energy increased with the addition of liquid elastomer.

Surface Photografting of Novel Sulfobetaine Copolymers on Silica

A couple of novel sulfobetaine copolymer is developed via Michael-type addition reaction. The comonomers, diamines and maleimide react via Michael reaction through UV irradiation using AIBN as photoinitiator producing polyamine chain. Further, sulfobetaine copolymers were obtained on treatment of the polyamine with sulfopropylating agent, 1,3-propane sultone. These novel sulfobetaine polymers were grafted on silica surface to produce responsive biocompatible surface. This easy straightforward, catalyst free facile protocol for synthesis of polymer grafted surface is useful for developing biomedical devices. Additionally, both the copolymers show fluorescence characteristics.

Development and characterization of nifedipine-amino methacrylate copolymer solid dispersion powders with various adsorbents

Solid dispersions of nifedipine(NDP), a poorly water-soluble drug, and amino methacrylate copolymer(AMCP) with aid of adsorbent, that is, fumed silica, talcum, calcium carbonate,titanium dioxide, and mesoporous silica from rice husks(SRH), were prepared by solvent method. The physicochemical properties of solid dispersions, compared to their physical mixtures, were determined using powder X-ray diffractometry(PXRD) and differential scanning calorimetry(DSC). The surface morphology of the prepared solid dispersions was examined by scanning electron microscopy(SEM). The dissolution of NDP from solid dispersions was compared to NDP powders. The effect of adsorbent type on NDP dissolution was also examined. The dissolution of NDP increased with the ratio of NDP:AMCP:adsorbent of 1:4:1 when compared to the other formulations. As indicated from PXRD patterns, DSC thermograms and SEM images, NDP was molecularly dispersed within polymer carrier or in an amorphous form, which confirmed the better dissolution of solid dispersions. Solid dispersions containing SRH provided the highest NDP dissolution, due to a porous nature of SRH, allowing dissolved drug to fill in the pores and consequently dissolve in the medium.The results suggested that solid dispersions containing adsorbents(SRH in particular) demonstrated improved dissolution of poorly water-soluble drug when compared to NDP powder.

Comparison of selective flocculation of low grade goethitic iron ore fines using natural and synthetic polymers and a graft copolymer

This study aims to beneficiate low grade goethitic iron ore fines using a selective flocculation process. Selective flocculation studies were conducted using different polymers such as starch amylopectin(AP), poly acrylic acid(PAA), and a graft copolymer(AP-g-PAA). The obtained results were analyzed; they indicate the enhancement of the iron ore grade from 58.49% to 67.52% using AP-g-PAA with a recovery of 95.08%. In addition, 64.45% Fe with a recovery of 88.79% was obtained using AP. Similarly, using PAA, the grade increased to 63.46% Fe with a recovery of 82.10%. The findings are also supported by characterizing concentrates using X-ray diffraction(XRD) and electron probe microanalysis(EPMA) techniques.

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.

Control of Microdomain Orientation in Block Copolymer Thin Films by Electric Field for Proton Exchange Membrane

Owing to the recent push toward efficient energy storage/conversion devices, fuel cells have become a strong candidate for energy conversion equipments. On the other hand, block copolymer polyelectrolytes are interesting materials for proton exchange membranes in fuel cells. Thus a considerable attention has been paid to the development of block copolymer polyelectrolyte membranes. In this study, the microdomains in block copolymer polyelectrolytes were controlled by external electric fields to develop high performance membranes with improved proton conductivity. The microdomain alignments in sulfonated polystyrene-b-hydrogenated poly butadiene-b-polystyrene block copolymer electrolyte were monitored by cross-sectional transmission electron microscopy analysis. The proton conductivities of the block copolymer electrolyte membranes were measured before and after exposure to electric field. In addition, the morphological features of the block copolymer electrolyte were observed with small angle x-ray scattering and atomic force microscopy.

Non-Isothermal Degradation Kinetics of Hybrid Copolymers Containing Thermosensitive and Polypeptide Blocks

Novel, self-associating hybrid copolymers were synthesized via controlled ring-opening polymerization of N-carboxyanhydride of Z-L-lysine (Z-L-Lys-NCA), initiated by amino-functional macroinitiators. A poly(N-isopropylacry-lamide) (PNIPAm)-based macroinitiator containing 10 mol% of polyoxyethylene grafts and a terminal primary amine group in the form of ammonium hydrochloride (PNIPAm-g-PEО) was synthesized and used to initiate the ammonium- mediated ring-opening polymerization of NCA described by Dimitrov and Schlaad [1]. Thus, hybrid copolymers ((PNIPAm-g-PEO)-b-PLys) with controlled molar-mass characteristics and functionality were obtained. The potential applications of PNIPAm-based copolymers in the systems for controlled drug release, immobilization of enzymes and protein purification have aroused great interest in the studies of their properties and behaviour. The thermal stability and thermodynamic properties of the copolymers obtained were studied. The differential thermal analysis of polyfunctional hybrid copolymers (PNIPAm-g-PEO)-b-PLys) showed that thermooxidative destruction occurs in two stages: primary, of the unstable fragments (grafted chains of PEO);and secondary, of the main polymer chains of poly(N-isopropylacry-lamide) and poly(L-lysine). The kinetics of thermal degradation was evaluated and the values of the activation energy of the degradation process, changes of Gibbs free energy, enthalpy and entropy for the formation of the activated complex were also calculated.

An Overview of the Synthesis and Gene Transfer Properties of Triblock Copolymers Poly(2-Methyl-2-Oxazoline-b-Tetrahydrofurane-b-2-Methyl-2-Oxazoline)

The synthesis of poly(2-methyl-2-oxazoline-b-tetrahydrofurane-b-2-methyl-2-oxazoline) triblock copolymer of low molar mass has been carried out. Characterization of the purified polymer by 1H and 13C NMR spectroscopies is described. These block copolymers did not give DNA containing polyplexes. The in vivo transfection properties were investigated by injection of tibialis muscles and intratracheal administration of female Swiss mice. These triblock copolymers with a molar ratio [2-methyl-2-oxazoline units]/[tetrahydrofurane units] in the 3 - 5 range gave a higher transfection efficiency than that of Lutrol or of PE6400 which are the gold standards of this transfection technique. Hydrolysis increased the performances of muscle transfection, showing the beneficial effect of the presence of positive charges, but was clearly detrimental to the transfection efficiency of pulmonary epithelium.

Mechanism for the Self-Assembly of Hollow Micelles from Rod-Coil Block Copolymers

The mechanism for the self-assembly of hollow micelles from rod-coil diblock copolymers is proposed. In a coilselective solvent, the diblock copolymers self-assemble into a layered structure. It is assumed that the rigid rods form an elastic shell whose properties are dictated by a bending energy. For a hollow micelle, the coils outside the micelle form a brush, while the coils inside the micelle can be in two different states, a brush or an adsorption layer, corresponding to symmetric or asymmetric configurations, respectively. The total energy density of a hollow micelle is calculated by combining the interfacial energy, elastic bending energy and the stretching energy of the brushes. For the asymmetric configuration with a polymer brush on one side, the competition between the elastic bending energy and the brush stretching energy leads to a finite spontaneous curvature, stabilizing hollow spherical micelles. Comparison of the free energy density for different geometries demonstrates that transitions for the different geometry micelles are controlled by the degree of polymerization of the coils and the length of the rods. These results are in agreement with the experimental results.

Blood Compatibility of Amphiphilic Poly(N-α-acrylamide-L-lysine-<i>b</i>-dimethylsiloxane) Block Copolymers

Amphiphilic block copolymers poly(LysAA-b-DMS) consisting of a hydrophilic poly(N-α-acrylamide-L-lysine) [poly(LysAA)] segment with different molecular weights and a hydrophobic polydimethylsiloxane (PDMS) segment were prepared as follows. The precursor copolymer poly(Boc-LysAA-OtBu-b-PDMS) was obtained from radical polymerization of N-α-acrylamide-N-ε-tert-butoxycarbonyl-L-lysine-tert-butylester (Boc-LysAA-OtBu) initiated with 4,4’-azobis(polydimethylsiloxane 4-cyanopentanoate) (azo-PDMS) with the molecular weight of PDMS Mw = 4.3 × 103 in the presence of 2-mercaptoethanol (2-ME) as a chain-transfer agent. Removal of the protecting groups of the precursor copolymer was carried out in 80% trifluoroacetic acid aqueous solution to give poly(LysAA-b-DMS)-1-3. The weight average molecular weight of poly(LysAA-b-DMS)-1-3 was Mw = 1.02 × 104 – 2.52 × 104. From the 1H-NMR and fluorescence spectra measurements, poly(LysAA-b-DMS)-1-3 was determined to self-organize and form core-shell micelles in water. The critical micelle concentration (CMC) increased to 1000 - 4000 mg·L–1 with increasing molar ratio of the poly(LysAA) segment from 0.42 to 0.65. From morphological analysis with a scanning probe microscope (SPM), poly(LysAA-b-DMS) has microphase-separated structures made up of hydrophilic and hydrophobic regions with the domain size ranging from several tens to several hundreds of nanometers. Inhibition of thrombin activity of poly(LysAA-b-DMS) was evaluated from the Michaelis constant (KM) and catalytic activity (kcat) for the enzymatic reaction of thrombin and synthetic substrate S-2238 in the presence of poly(LysAA-b-DMS). The KM and kcat were 0.10 - 0.11 mM and 4.04 × 105 – 4.26 × 105 min–1, respectively. Fibrinolytic activity was also verified from the transformation of plasminogen to plasmin by tissue plasminogen activator (t-PA) using synthetic substrate S-2251 in the presence of poly(LysAA-b-DMS). The KM and kcat were 0.07 mM and 5.73 × 106 –5.95 × 106 min–1, respectively.

Mechanical, Thermal and Morphology Properties of Thermoplastic Polyurethane Copolymers Incorporating α,ω-Dihydroxy-[poly(propyleneoxide)-poly (dimethylsiloxane)-poly(propyleneoxide)] of Varying Poly(propyleneoxide) Molecular Weight

Novel segmented thermoplastic polyurethane (TPU) copolymers were synthesized using two-step solventless bulk polymerization. 4,4’-methylenediphenyl diisocyanate (MDI) and 1,4-Butanediol (BDO) were used to form hard segment of TPU and α,ω-dihydroxy-[poly(propyleneoxide)-poly (dimethylsiloxane)-poly(propyleneoxide)] (α,ω-dihydroxy-(PPO-PDMS-PPO)) was used to form soft segment of TPU, where the molar ratio of the –N=C=O/OH was 1.02 and the hard segment weight percentage was 30%. A series of TPUs were characterized by fourier transform infrared spectroscopy (FT-IR). The investigation of triblock oligomer’s PPO molecular weight impact on the derived TPU’s mechanical properties, thermal performance, surface water repellency and morphology performance was carried by Instron material tester, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), water contact angles (WCA), scanning electron microscope and energy dispersive X-ray spectroscopy (SEM-EDX) and wide angle X-ray diffraction (WAXD), respectively. FT-IR confirmed α,ω-dihydroxy-(PPO-PDMS-PPO) well cooperating into urethane structure and analyzed hydrogen bonding between N-H group with hard segment C=O group and N-H group with soft segment C-O-C group. DSC and WAXD results showed α,ω-dihydroxy-(PPO-PDMS-PPO) segments crystallization. SEM-EDX results showed that the presence of a spherulitic morphology, which arose from the crystallization of the PPO segments. The thermal properties measured by TGA and DSC were slightly affected by molecular weight of PPO and microphase separation. The weight loss of TPUs started between 294°C and 300°C, and Tg was in the range of -70°C to -107°C. TPU copolymers’ surface hydrophobicity property was excellent with WCA range of 95°?to 112°. TPU-3 with 1000 molecular weight PPO has the optimized mechanical properties with tensile strength 16.4 MPa and the modulus at 100% elongation 6.2 MPa and elongation 398%.

Comparative Toxicity of “Tin Free” Self-Polishing Copolymer Antifouling Paints and Their Inhibitory Effects on Larval Development of a Non-Target Organism

Toxic substances released as a result of leaching from painted surfaces to the aquatic environment affect both fouling organisms and “non-target” biota. Artemia fransiscana nauplii have been considered a useful test system for the examination of toxicity for antifouling paints. In this study, we examined the effect of four “tin free” self-polishing copolymer (SPC) antifouling paints on the larval development of Artemia nauplii. Based on the L(S/V)50 values the order of toxicity of the antifouling paints was: ANTI F > SHARKSKIN > OCEAN T/F > MICRON. Furthermore, the body size of Artemia nauplii was significantly affected at lethal and above lethal L(S/V)5024h values. The body size of 48 h-aged nauplii exposed for the last 24 hours to each of the four SPC antifouling paints was significantly lower than that of the 48 h-aged controls (0.88 ± 0.030 mm). In addition, the body size of 72 h-aged nauplii maintained for the last 24 hours to pure synthetic seawater after exposure for 24 hours to each of the four SPC antifouling paints was significantly lower than that of the 72 h-aged controls (0.96 ±0.027 mm). Overall, the SPCs examined here were substantially toxic to Artemia nauplii, but with different toxicities and modes of action, as a result of the synergistic action of distinct components of the antifouling paints.

Crystallization Behavior of Poly(Tetramethylene Oxide) Influenced by the Crystallization Condition of Poly(Butylene Succinate) in Their Copolymers

The effect of crystallization conditions of poly(butylene succinate)(PBS) component on the crystallization of poly(tetramethylene oxide)(PTMO) component in their segment block copolymer, with a higher PTMO content(PTMO mass fraction is 67%), was investigated by DSC and temperature-dependent FTIR. It is found that the isothermal crystallization time(tIC) of PBS has an effect on the crystallization behavior of PTMO component. Perturbation correlation move-window two-dimensional(PCMW2 D) correlation analysis and generalized 2 D correlation analysis(2 DIR) were performed to explore the origin of this phenomenon. The PCMW2 D and 2 DIR results show that the correlation intensity peak observed at around 20 ℃ for PTMO is due to the PTMO chains movements forced by the PBS chains folded movements. If tIC of PBS at temperature of 20 ℃ is prolonged, more PTMO components are incorporated in the region between PBS lamellae and the peak at-7.6 ℃(belonging to less-constricted PTMO chains) changes smaller and even disappears, while the peak at-16.3 ℃ belonging to more-constricted PTMO chains gets bigger. A crystallization model was also established in this study. The results of tensile testing showed that tensile strength slightly increased and elongation at break decreased with increasing heat treatment time at 40 ℃.

HOMOPOLYMERS AND COPOLYMERS OF GLYCOLIDE AND LACTIDE

The homopolymerization and copolymerization of glycolide (GA) and lactide (LA) are des-cribed. The resulting polymers are characterized by differential scanning calorimetry (DSC),thermogravimetric analysis (TGA), 300 MHz proton nuclear magnetic resonance spectroscopy(NMR), infrared spectroscopy, and X-ray diffraction. The rheological properties of PGA andPGLA 910 are evaluated by shear experiments. The biodegradation has been studied in vivo. Theresults show that the polyesters can be absorbed by the muscles of rabbits after 60 days.

Synthesis of new EVA graft copolymer and its pour point depressant performance evaluation for Daqing crude oil

EVA was widely used as the pour point depressant for waxy oil.In order to improve its effect,some graft copolymerization methods should be used to modify EVA's property.EVA has long side chains and nitrogen polar groups to enforce its adaptability and effect of waxy oil.The pure amine,maleicanhydride and their reaction product were tested using infrared spectra and the NMR spectral.The results show that when the modified EVA is added into oil,the wax deposits not only on the main chain but also on the side chains.And the polar groups have the function to avoid and resist the wax crystals connection each other to form the net.Using the reaction product of maleicanhydride and high carbonic amine(C12,C16,C18 amine) as the graft component,the toluene as the solvent and BPO as the initiator,the series of new EVA graft copolymer with special side chains are prepared under controlled condition.A series of cylmaleimide exist indeed in modified EVA and the highest grafted percentage is 18.8%.EVA-16,the new graft copolymer,is better than EVA about 3 ℃ more in depressant the pour-point of Daqing waxy crude oil.

Selective swelling of polysulfone/poly(ethylene glycol) block copolymer towards fouling-resistant ultrafiltration membranes

Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.

Exploring the effect of cooling rate on non-isothermal crystallization of copolymer polypropylene by fast scanning calorimetry

Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.

Synthesis of Cobalt Containing Block Copolymers Via Ring Opening Metathesis Polymerizastion (ROMP)

In order to realize a metal containing nano-structure, a block-copolymer containing alkynyl groups in one block was designed and synthesized by living ring opening metathesis polymerization (ROMP) technique. The newly developed bis-3-bromopyridine complex of Grubbs catalyst was employed in the series of polymerization and it yielded the desired polymers with great molecular weight control and narrow polydispersities. The characteristics of the block copolymers were investigated by gel permeation chromatography, H- and 13H- NMR spectroscopy. Complexation of the alkynyl group containing block copolymers by treatment with dicobalt octacarbonyl occurred smoothly in 5 min at room temperature. GPC analysis before and after cobalt complexation indicated a significant increase of the hydrodynamic volume. AFM images of the films before and after the complexation also showed a noticeable change in its morphology where grain sizes become smaller and more regular upon complexation.

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.