Kinetic, Thermodynamic and Process Modeling of Synthesis of UV Curable Glyceryl and Neopentyl Glycol Acrylates

Curing of paints by exposure to UV radiations is emerging as one of the best film forming technique as an alternative to traditional solvent borne oxidative and thermal curing coatings. The composition and chemistry of UV curable coatings and role of multifunctional and monofunctional monomers, oligomers, and photoinitiators have been discussed. The limitations imposed by thermodynamic equilibrium and tendency for acrylic double bond polymerizations during synthesis of multifunctional acrylates have been presented. Aim of present investigation was thus to explore the reaction variables associated with synthesis of multifunctional acrylates. Zirconium oxychloride was evaluated as catalyst against regular acid functional catalyst. The catalyzed synthesis of glyceryl acrylate and neopentyl glycol acrylate was conducted by variation of following reaction parameters: two different reactant molar ratios- 1:4 and 1:6; catalyst usage in % by moles on polyol- 2.5, 5.0 and 7.5 and two different reaction temperatures- 45 and 75 0C. The reaction was monitored by determination of acid value and hydroxy value at regular intervals, besides TLC, HPLC, and FTIR analysis of intermediates and products. On the basis of determination of reaction progress over 1-60 hrs, the esterification reaction was observed to follow 2nd order kinetics with rate constant varying from 1*10-4 to 7*10-4. The thermal and catalytic components of second order rate constant and energy of activation were also determined. Uses of these kinetic and thermodynamic parameters in design of reactor for manufacture of multifunctional acrylate ester have been presented. The synthesized multifunctional acrylates were used to formulate and apply UV curable clear coat followed by determination of curing characteristics and mechanical properties of cured film. The overall curing rates less than 05 min. were easily attained indicating economical viability of radiation curable system due to faster production schedules

Generalized Predictive Control of Batch Polymerization Reactor

This paper describes the application of a model predictive controller to the problem of batch reactor temperature control. Although a great deal of work has been done to improve reactor throughput using batch sequence control, the control of the actual reactor temperature remains a difficult problem for many operators of these processes. Temperature control is important as many chemical reactions are sensitive to temperature for formation of desired products. This controller consist of two part (1) a nonlinear control method GLC (Global Linearizing Control) to create a linear model of system and (2) a Model predictive controller used to obtain optimal input control sequence. The temperature of reactor is tuned to track a predetermined temperature trajectory that applied to the batch reactor. To do so two input signals, electrical powers and the flow of coolant in the coil are used. Simulation results show that the proposed controller has a remarkable performance for tracking reference trajectory while at the same time it is robust against noise imposed to system output.

Thermo-Sensitive Hydrogel: Control of Hydrophilic-Hydrophobic Transition

The study investigated the hydrophilic to hydrophobic transition of modified polyacrylamide hydrogel with the inclusion of N-isopropylacrylamide (NIAM). The modification was done by mimicking micellar polymerization, which resulted in better arrangement of NIAM chains in the polyacrylamide network. The degree of NIAM arrangement is described by NH number. The hydrophilic to hydrophobic transition was measured through the partition coefficient, K, of Orange II and Methylene Blue in hydrogel and in water. These dyes were chosen as a model for solutes with different degree of hydrophobicity. The study showed that the hydrogel with higher NH values resulted in better solubility of both dyes. Moreover, in temperature above the lower critical solution temperature (LCST) of Poly(N-isopropylacrylamide) (PNIAM)also caused the collapse of NIPAM chains which results in a more hydrophobic environment that increases the solubility of Methylene Blue and decreases the solubility of Orange II in the hydrogels with NIPAM present.

Modification and Characterization of Bacterial Cellulose Biopolymer as Proton Conducting Membrane

This study describes the preparation of a novel proton conducting membranes based on bacterial cellulose (BC) modified by grafting of 2-acrylamido-2-methyl-1 -propanesulfonic acid (AMPS) through UV-induced graft polymerization. These AMPS-g-BC membranes have been characterized by various techniques including FTIR, SEM and TGA, to find their successful grafting of AMPS on BC, surface morphology and thermal stability, respectively. Physical properties of AMPS-g-BC membranes have been assessed in terms of Lamda value( λ ), ion exchange capacity(IEC) and proton conductivity. The relationship between degree of grafting and AMPS concentration used for grafting has been determined by weight gain method. An optimum proton conductivity equal to 2.89x10-2 S cm-1 and IEC value equal to 1.79 mmol g-1 have been obtained when 20 wt% AMPS concentration is used for grafting (i.e. the corresponding membrane is notated as AMPS20-g-BC).

Spectroscopic and SEM Investigation of TCPP in Titanium Matrix

Titanium gels doped with water-soluble cationic porphyrin were synthesized by the sol–gel polymerization of Ti (OC4H9)4. In this work we investigate the spectroscopic properties along with SEM images of tetra carboxyl phenyl porphyrin when incorporated into porous matrix produced by the sol–gel technique.

Development and Characterization of Normoxic Polyhydroxyethylacrylate (PHEA) Gel Dosimeter using Raman Spectroscopy

Raman spectroscopy are used to characterize the chemical changes in normoxic polyhydroxyethylacrylate gel dosimeter (PHEA) induced by radiation. Irradiations in the low dose region are performed and the polymerizations of PHEA gels are monitored by the observing the changes of Raman shift intensity of the carbon covalent bond of PHEA originated from both monomer and the cross-linker. The variation in peak intensities with absorbed dose was observed. As the dose increase, the peak intensities of covalent bond of carbon in the polymer gels decrease. This point out that the amount of absorbed dose affect the polymerization of polymer gels. As the absorbed dose increase, the polymerizations also increase. Results verify that PHEA gel dosimeters are sensitive even in lower dose region.

A Review on Application of Chitosan as a Natural Antimicrobial

In recent years application of natural antimicrobials instead of conventional ones, due to their hazardous effects on health, has got serious attentions. On the basis of the results of different studies, chitosan, a natural bio-degradable and non-toxic biopolysaccharide derived from chitin, has potential to be used as a natural antimicrobial. Chitosan has exhibited high antimicrobial activity against a wide variety of pathogenic and spoilage microorganisms, including fungi, and Gram-positive and Gramnegative bacteria. The antimicrobial action is influenced by intrinsic factors such as the type of chitosan, the degree of chitosan polymerization and extrinsic factors such as the microbial organism, the environmental conditions and presence of the other components. The use of chitosan in food systems should be based on sufficient knowledge of the complex mechanisms of its antimicrobial mode of action. In this article we review a number of studies on the investigation of chitosan antimicrobial properties and application of them in culture and food mediums.

Universal Kinetic Modeling of RAFT Polymerization using Moment Equations

In the following text, we show that by introducing universal kinetic scheme, the origin of rate retardation and inhibition period which observed in dithiobenzoate-mediated RAFT polymerization can be described properly. We develop our model by utilizing the method of moments, then we apply our model to different monomer/RAFT agent systems, both homo- and copolymerization. The modeling results are in an excellent agreement with experiments and imply the validity of universal kinetic scheme, not only for dithiobenzoate-mediated systems, but also for different types of monomer/RAFT agent ones.

Effect of Substituent on Titanocene/MMAO Catalyst for Ethylene/1-Hexene Copolymerization

Copolymerization of ethylene with 1-hexene was carried out using two ansa-fluorenyl titanium derivative complexes. The substituent effect on the catalytic activity, monomer reactivity ratio and polymer property was investigated. It was found that the presence of t-Bu groups on fluorenyl ring exhibited remarkable catalytic activity and produced polymer with high molecular weight. However, these catalysts produce polymer with narrow molecular weight distribution, indicating the characteristic of single-site metallocene catalyst. Based on 13C NMR, we can observe that monomer reactivity ratio was affected by catalyst structure. The rH values of complex 2 were lower than that of complex 1 which might be result from the higher steric hindrance leading to a reduction of 1- hexene insertion step.

Preparation of Polylactic Acid Graft Polyvinyl Acetate Compatibilizers for 50/50 Starch/PLLA Blending

Polylactic acid-g-polyvinyl acetate (PLLA-g-PVAc) was used as a compatibilizer for 50/50 starch/PLLA blend. PLLA-g- PVAc with different mol% of PVAc contents were prepared by grafting PVAc onto PLLA backbone via free radical polymerization in solution process. Various conditions such as type and the amount of initiator, monomer concentration, polymerization time and temperature were studied. Results showed that the highest mol% of PVAc grafting (16 mol%) was achieved by conducting graft copolymerization in toluene at 110°C for 10 h using DCP as an initiator. Chemical structure of the PVAc grafted PLLA was confirmed by 1H NMR. Blending of modified starch and PLLA in the presence compatibilizer with different amounts and mol% PVAc was acquired using internal mixer at 160°C for 15 min. Effects of PVAc content and the amount of compatibilizer on mechanical properties of polymer blend were studied. Results revealed that tensile strength and tensile modulus of polymer blend with higher PVAc grafting content compatibilizer showed better properties than that of lower PVAc grafting content compatibilizer. The amount of compatibilizer was found optimized in the range of 0.5-1.0 Wt% depending on the mol% PVAc.

Properties of MWCNTs/PAN Nanofiber Sheet Prepared from Chemically Modified MWCNTs

The nanofiber sheet of Multiwall Cabon Nanotube (MWCNTs)/Polyacylonitile (PAN) composites was fabricated from electrospun nanofiber. Firstly the surface of MWCNTs was chemically modified, comparing two different techniques consisting of admicellar polymerization and functionalization to improve the dispersion and prevent the aggregation in the PAN matrix. The modified MWCNTs were characterized by the dispersion in dimethylformamide (DMF) solvent, Laser particle size, and FTRaman. Lastly, DSC, SEM and mechanical properties of the nanofiber sheet were examined. The results show that the mechanical properties of the nanofiber sheet prepared from admicellar polymerization-modified MWCNTs were higher than those of the others.

Kinetics of Polyethylene Terephthalate (PET)and Polystyrene (PS) Dynamic Pyrolysis

Thermo-chemical treatment (TCT) such as pyrolysis is getting recognized as a valid route for (i) materials and valuable products and petrochemicals recovery; (ii) waste recycling; and (iii) elemental characterization. Pyrolysis is also receiving renewed attention for its operational, economical and environmental advantages. In this study, samples of polyethylene terephthalate (PET) and polystyrene (PS) were pyrolysed in a microthermobalance reactor (using a thermogravimetric-TGA setup). Both polymers were prepared and conditioned prior to experimentation. The main objective was to determine the kinetic parameters of the depolymerization reactions that occur within the thermal degradation process. Overall kinetic rate constants (ko) and activation energies (Eo) were determined using the general kinetics theory (GKT) method previously used by a number of authors. Fitted correlations were found and validated using the GKT, errors were within ± 5%. This study represents a fundamental step to pave the way towards the development of scaling relationship for the investigation of larger scale reactors relevant to industry.

Novel Glycopolymers Containing Carbohydrate Moiety: Copolymerization and Thermal Properties

Polymers are one of the most widely used materials in our every day life. The subject of renewable resources has attracted great attention in the last period of time. New polymeric materials derived from renewable resources, like carbohydrates draw attention to public eye especially because of their biocompatibility and biodegradability. The aim of our paper was to obtain environmentally compatible polymers from monosaccharides. Novel glycopolymers based on D-glucose have been obtained from copolymerization of a new monomer carrying carbohydrate moiety with methyl methacrylate (MMA) via free radical bulk polymerization. Differential scanning calorimetry (DSC) was performed in order to study the copolymerization process of the monomer into the chosen co-monomer; the activation energy of this process was evaluated using Ozawa method. The copolymers obtained were characterized using ATR-FTIR spectroscopy. The thermal stability of the obtained products was studied by thermogravimetry (TG).

Realignment of f-actin Cytoskeleton in Osteocytes after Mechanical Loading

F-actin fibrils are the cytoskeleton of osteocytes. They react in a dynamic manner to mechanical loading, and strength and reposition their efforts to reinforce the cells structure. We hypothesize that f-actin is temporarly disrupted after loading and repolymerizes in a new orientation to oppose the applied load. In vitro studies are conducted to determine f-actin disruption after varying mechanical stimulus parameters that are known to affect bone formation. Results indicate that the f-actin cytoskeleton is disrupted in vitro as a function of applied mechanical stimulus parameters and that the f-actin bundles reassemble after loading induced disruption within 3 minutes after cessation of loading. The disruption of the factin cytoskeleton depends on the magnitude of stretch, the numbers of loading cycles, frequency, the insertion of rest between loading cycles and extracellular calcium. In vivo studies also demonstrate disruption of the f-actin cytoskeleton in cells embedded in the bone matrix immediately after mechanical loading. These studies suggest that adaptation of the f-actin fiber bundles of the cytoskeleton in response to applied loads occurs by disruption and subsequent repolymerization.