Dissertations / Theses on the topic 'Polyvinyls – chemistry'

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-23T11:17:22Z No. of bitstreams: 0
Made available in DSpace on 2017-11-23T11:17:22Z (GMT). No. of bitstreams: 0
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
A papaína é uma enzima proteolítica empregada no debridamento e cicatrização de feridas. Contudo, problemas de estabilidade na forma farmacêutica, bem como reações alérgicas reportadas por pacientes submetidos à tratamentos com a enzima, culminaram na restrição aos produtos contendo papaína para uso tópico por órgãos regulatórios internacionais. Este trabalho objetivou desenvolver hidrogel nanoestruturado contendo complexo de papaína e ciclodextrina visando obter forma farmacêutica estável e eficaz como curativo dérmico, com redução da resposta imunológica. A síntese do hidrogel foi realizada combinando fenômenos de cristalização e/ou reticulação e esterilização simultânea induzida por radiação gama, de modo a promover nanoestruturação adequada da membrana para veiculação da papaína nativa e do complexo. O complexo e o produto final tiveram suas propriedades biológicas e físico-químicas avaliadas. O hidrogel a base de PVA contendo complexo de papaína-ciclodextrina apresentou características adequadas para aplicação como curativo, além de apresentar indícios de redução na resposta imunológica e melhora na citocompatibilidade quando comparado à papaína nativa, isso devido ao encapsulamento molecular com a ciclodextrina e à alta retenção do complexo por parte da matriz. Por outro lado, a irradiação, não alterou o perfil citotóxico da enzima, mas acarretou leve diminuição em seu potencial imunogênico. O hidrogel se mostrou promissor para uso como curativo e demonstrou potencial redução nas reações adversas desencadeadas pelo uso da papaína.
Tese (Doutorado em Tecnologia Nuclear)
IPEN/T
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP
FAPESP:10/10935-9

Nano-cellulose fibers/suspension has very high viscosity, its viscosity has to be lower before it can be applied in the paper coating recipe. For this purpose the adsorption behaviour of polyvinyl alcohol on nano-cellulose fibers were investigated using method developed by Zwick in 1960, based on the formation of PVA-iodide blue complex in the presence of boric acid. The experiments showed that the maximum adsorbed amount i.e. 0.13 g PVA/g NFC was obtained in a dispersion with 0.2 % PVA concentration. It should be possible to further increase the PVA adsorption as the adsorbed amount didn’t reach a saturation point where the PVA adsorption attained a constant value. It was also found that adsorption of PVA on NFC is time dependent. The absorbance measurement after four days of mixing PVA/NFC suspension showed only partially adsorption of PVA on nano-cellulose surface.  An equilibrium time of 10-13 days was needed for PVA to fully adsorb on nano-cellulose fibers surface. Another important observation was that PVA adsorption also depends on the concentration of nano-cellulose fibers. A lower concentration of NFC easily allows PVA to adsorb on its surface, as compared to higher NFC concentration. An important finding during the methodology development was the method to get rid of formation of flocs in the blue iodide complex solution; by slowly addition of reactants, especially the KI/I2 solution under continuous stirring around 60oC the tendency to flocs formation was suppressed.

Thesis (MSc)--Stellenbosch University, 2011.
ENGLISH ABSTRACT: Needle-electrospinning is an uncomplicated and highly versatile nanofiber (fiber diameter of 50 to 500 nm) production technique. Nevertheless the process can only produce 0.01 to 1.0 g/h/m2 of nanofibers, unpractical for large-scale productions. Bubble-electrospinning, in the presence of surfactants, is a novel nanofiber mass-production technique developed at Stellenbosch University.[1] The technique is similar to needle-electrospinning only that the surface area of a bubble surpasses that of a solution droplet, making it possible for multiple jets to form on the bubble surface at high field strengths. Thus far little research has been done on the influence of solution properties on the bubble-electrospinning technique. During electrospinning the solution experiences three competing forces, namely, surface tension (contracting force), charge repulsion (expanding force), and viscosity (resistance to flow). The first aim of this study was to obtain better understanding on the influence of three significant solution properties (viscosity, conductivity and surface tension) on bubble-electrospinning in terms of bubble lifetime, bubble size, average number of jets and the resultant fibers. The solution properties were varied using a range of polymer and surfactant concentrations. A second aim was to obtain better understanding on the comparison of the bubble-electrospinning process between two polymer solutions, namely Polyvinyl alcohol (PVOH) solutions containing sodium lauryl ether sulphate (SLES) surfactant, and Polyacrylonitrile (PAN) solutions containing silicone surfactant. Results indicated that the solution viscosity and conductivity increased with increasing polymer concentrations for both polymer solutions. In addition, both the solution surface tensions were not influenced by polymer concentration. With regards to bubble-electrospinning of PVOH solutions, results indicated that the average number of jets per bubble was influenced by the polymer concentration. Regarding PAN solutions, bubble lifetime and the average number of jets was influenced by polymer concentration. Results indicated that the solution viscosity increased and surface tension decreased with increasing surfactant concentration for both polymer solutions. PVOH solution conductivity increased whilst PAN solution conductivity decreased with increasing surfactant concentrations. With regards to bubble-electrospinning of PVOH solutions, the bubble lifetime and bubble size was significantly influenced by the SLES concentration. Regarding PAN solutions, the silicone surfactant concentration had no significant effect on the bubble-electrospinning process. Overall, PVOH fiber diameters decreased with increasing surfactant concentration. There was no common trend between the bubble-electrospinning of PVOH and PAN solutions in relation to their solution properties. It was concluded that solution viscosity, conductivity and surface tension are not the only significant contributing parameters to the bubble-electrospinning process.
AFRIKAANSE OPSOMMING: Die naald-elektrospinproses is 'n eenvoudige, hoogsaanpasbare tegniek wat gebruik word vir die maak van nanovesels. Nanovesels het tipies 'n deursnee van 50nm tot 500nm. Ongelukkig is dit onprakties vir grootskaalse produksie omdat die uitset daarvan beperk is tot 0.01 tot 1.0 g/h/m2. Die borrel-elektrospinproses, waar elektrospinstrale gespin word vanaf die oppervlak van borrels op die oppervlak van die spinoplossing en waar die borrels gestabiliseer is m.b.v. sepe, is 'n nuwe tegniek wat ontwikkel is by die Universiteit van Stellenbosch. [1]. Die tegniek is soortgelyk aan die naald-elektrospinproses in dié sin dat die elektrospinstraal vorm vanaf 'n gelaaide halfsfeervormige oppervlak in die spinoplossing, maar die aansienlik groter oppervlakarea van die borrel in die borrel-elektrospinproses maak dit moontlik om verskeie elektrospinstrale gelyktydig op die oppervlak van die borrel te onderhou. Dit lei tot baie hoër doeltreffendheid in die saamgroeppering van die strale en gevolglik tot hoër nanoveseluitsette. Tot dusver is daar weinig navorsing aangaande die invloed van oplossingseienskappe op die borrel- elektrospintegniek gedoen. Tydens die elektrospinproses ervaar die oplossing drie kompeterende kragte, naamlik: oppervlakspanning (sametrekkende krag), elektrostatiese afstoting (afstotende krag) en viskositeit (vertragende effek op vloei van die oplossing). Die hoofdoelwit van hierdie navorsing was om 'n beter begrip te kry van die invloed van drie gemete oplossingswaardes, d.w.s. viskositeit, elektriese geleidingsvermoë en oppervlakspanning op die borrel-elektrospinproses. Die impak van hierde waardes is spesifiek geëvalueer in terme van borrellewensduur, borrelgrootte, gemiddelde hoeveelheid elektrospinstrale per borrel en die morfologie van die vesels wat in die proses gevorm is. Die tweede doelwit van die studie was om 'n vergelyking te tref tussen die mees optimale oplossingswaardes in die borrel-elektrospinproses van twee baie uiteenlopende polimeerspinoplossings, naamlik polivinielalkohol (PVOH), met natrium dodesieletersulfaat (SLES) as die borrelstabiliserende seep en poliakrilonitriel (PAN) oplossing, met 'n silikoonseep as die borrelstabiliserende seep. Resultate het getoon dat die viskositeit en elektriese geleidingsvermoë toeneem met toename in polimeerkonsentrasie vir beide PVOH- en PAN-oplossings. Verder is oppervlakspanning in beide gevalle nie beduidend beïnvloed deur die polimeerkonsentrasie nie. In die geval van die borrel-elektrospin van die PVOH-oplossings het resultate daarop gedui dat die gemiddelde aantal elektrospinstrale per borrel moontlik beïnvloed kon word deur die polimeerkonsentrasie. In die geval van borrel-elektrospin van PAN-oplossing is bevind dat polimeerkonsentrasie die borrelleeftyd en die gemiddelde aantal elektrospinstrale per borrel beïnvloed. Resultate het ook getoon dat die viskositeit vermeerder en die oppervlakspanning afneem met toename in die konsentrasie van die sepe in beide die polimeeroplossings. Die PVOH-oplossing se elektriese geleidingsvermoë het vermeerder terwyl dit verminder in die geval van die PAN-oplossings met 'n toename in die seepkonsentrasie. Tydens borrel-elektrospin van die PVOH-oplossings is beide borrelleeftyd en borrelgrootte beduidend beïnvloed deur die SLES konsentrasie. By die borrel-elektrospin van PAN-oplossings het die silikoonseepkonsentrasie nie 'n beduidende invloed gehad op die borrelleeftyd en borrelgrootte nie. Oor die algemeen het die gemiddelde PVOH veseldeursnee afgeneem met toename in seepkonsentrasie. Geen algemene tendens kon waargeneem word tussen die optimale oplossingswaardes vir borrel-elektrospin van die PVOH- en die PAN-oplossings onderskeidelik nie. Die gevolgtrekking is dat die viskositeit, elektriese geleidingsvermoë en oppervlakspanning nie die enigste beduidende waardes is wat bepaal of die borrel-elektrospinproses sal werk vir 'n spesifieke polimeeroplossing nie.

We report on a new framework for preparing high-refractive index polymeric materials which combines the selective thiol radical mono-addition to phenyl-acetylene derivatives with hyperbranched architectures. Using this strategy we have synthesized a series of linear and hyperbranched polyvinyl sulfide (PVS) materials, employing different dithiol (A₂ and A'₂) and di- and trialkyne (B and B₃) monomers. The process requires only a simple radical initiator, such as AIBN, in lieu of expensive or toxic catalysts and this chemistry produces polymers in high yield (up to 96%) and high molecular weight (up to 123 000 g mol⁻¹). The polymers are optically transparent, thermally stable (up to 420 °C) and readily form highquality films. The end group composition of the hyperbranched materials can be easily adjusted by changing the A₂/B₃ feed ratio. The sulfur incorporation and conjugation resulting from thiol–yne coupling with selective mono-addition results in materials with high refractive indices in the visible and IR region (nD = 1.68–1.75) and optical dispersions as low as 0.004. Moreover, we demonstrate that the hyperbranched architecture produces materials with better performance in terms of light reflection and chromatic dispersion compared to linear structures.

Green chemistry principles served as a guide for three industrially-relevant projects. In the first project, silylamines were applied as reversible ionic liquids for carbon dioxide capture from post-combustion flue gas streams. The effect of silylamine structure was thoroughly researched to develop a comprehensive library of silylamines and an accompanying set of structure-property relationships. The proposed solvent systems have the potential to present significant energy savings, as design has focused on their use in a non-aqueous, solvent-free environment. The second project also dealt extensively with carbon dioxide capture, as a reversible, in-situ protecting group for amines. Three strategies for the reversible protection of amines using carbon dioxide were developed and evaluated. Further, a chemoselective reaction was performed using carbon dioxide to protect a reactive amine and consequentially direct reactivity elsewhere within the same molecule. The carbon dioxide-protection technology developed has significant impact in multi-step industrial syntheses, as reversible, in-situ protection with carbon dioxide could eliminate the need for separate protection and deprotection unit operations. Lastly, a study was performed on the thermal degradation and stabilization of PVC in the presence of both plasticizers and thermal stabilizers. The study combined both model compound experiments as well as work with bulk PVC blends to gain a holistic understanding of the processes that take place during the degradation and stabilization of PVC. A bio-based plasticizer was investigated as a replacement for petroleum-based phthalate plasticizers. Additionally, two novel thermal stabilizers for PVC were presented and evaluated.

Pharmaceutical Sciences
Ph.D.
The purpose of this study was to improve the melt extrusion processability of polyvinyl acetate phthalate (PVAP) and investigate its use as a stabilizing polymer for supersaturated solutions of itraconazole (ITZ) in neutral pH aqueous media and in the solid-state during storage over time. Polyvinyl pyrrolidone vinyl acetate (PVPVA) was incorporated into PVAP as a carrier matrix with the aim of lowering the melt viscosity and increasing the plasticity of PVAP while maintaining its high glass transition temperature (Tg). Amorphous solid dispersions of ITZ (40% w/w) in a 30:70% w/w PVAP:PVPVA mixture were produced by melt extrusion. Solid-state analyses of the composition were performed using differential scanning calorimetry and X-ray diffraction. Dissolution analysis was conducted using a pH-change method. Solid-state analyses demonstrated that the extruded composition was entirely amorphous and ITZ was largely distributed in PVAP- and PVPVA-rich portions of the ternary dispersion. Dissolution analysis revealed that PVAP functioned to prolong the release of supersaturated levels of ITZ from the dispersion following an acidic-to-neutral pH transition. In the solid state, ITZ remained in its amorphous form throughout 6 months of storage. The results of this study suggest that substantial improvements in melt extrusion with PVAP can be achieved by incorporating PVPVA and that the PVAP-PVPVA polymer combination can stabilize amorphous ITZ.
Temple University--Theses

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009.
In papermaking, the addition of filler can be detrimental to the properties of the resulting paper hence the use of additives that enhance paper properties are of paramount importance. Syndiotacticity rich poly(vinyl alcohol) (PVA) microfibrils were prepared for use as filler retention aids. They were prepared via in situ fibrillation during the saponification of high molecular weight poly(vinyl pivalate). The resulting fibers had high thermal stability and crystalline melting temperature. They were not fully soluble in water even at 100 oC. In order to make them less water resistant the syndiotacticity of the PVA microfibrils was varied by copolymerizing vinyl pivalate with vinyl acetate and saponifying the resultant copolymer. It was observed that changes in syndiotacticity had a significant effect on the crystallinity, morphology and thermal properties of the resultant PVA. The surfaces of the fibers were modified by first crosslinking using glyoxal (a dialdehyde), and then attaching cationic and anionic groups by grafting and by carboxymethylation. Crosslinking prior to modification was beneficial in minimizing the solubility of the fibers in the aqueous media in which they were modified. Heterogeneous modification techniques were employed so that fiber properties could be preserved. Carboxymethylation was carried out using the two step Williamson’s ether synthesis. The first step involves the formation of a highly reactive alkoxide by the reaction of PVA with a strong base and the second its etherification using a functional alkyl halide. Poly(methacryloyloxy ethyl trimethyl ammonium chloride) and poly(acrylic acid) were grafted from the PVA microfibrils using the KPS/Na2S2O3 redox initiation system. Grafting was confirmed by FTIR and NMR spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were carried out on both modified and unmodified PVA microfibrils. The results showed that crosslinking resulted in an enhancement of the thermal properties of the microfibrils. A decline in the onset temperature for thermal degradation and crystalline melting temperature were observed, and were attributed to the modification of the PVA microfibrils.

Indiana University-Purdue University Indianapolis (IUPUI)
Fabrications of desirable fixed or removable dental prostheses depend upon accurate casts or dies. Recently, the most frequently used impression materials have been polyether (PE) and polyvinyl siloxane (PVS). However, both have their limitations: PVS is inherently hydrophobic, and PE is rigid. In order to take advantage of the desirable qualities of both PVS and PE impression materials, a new generation of impression material is being developed called vinyl polyether silicone (VPES, GC). The purpose of the present study was to compare the properties of hydrophilic PVS, PE, and VPES in regard to surface detail reproduction, contact angle, and tear strength. The hypotheses to be tested were: 1) VPES will show a significant superiority insurface detail reproduction compared with PVS and PE impression materials; 2) VPES will show a significant superiority in wettability compared with PVS and PE impression materials; 3) VPES will show a significant superiority in tear strength compared with PVS and PE impression materials. In order to test the surface detail reproduction, impressions were made of stainless steel dies with a parallel series of 15 different width lines on the surface and tested under dry and moist conditions. The wettability was assessed by contact angles of saturated CaSO4 aqueous solution drops on flat impression surfaces. A trouser tear test was employed to test the tear strength. The trouser-shaped specimens were prepared and tested in the Instron Universal Testing Machine. The data were analyzed by one-way ANOVA and Pearson‘s Chi square, (p < 0.05). All the materials showed better detail reproduction under the dry conditions than the moist conditions. There were no differences between the three materials in detail reproduction when impressing under either moist conditions or dry conditions. All the materials showed good wettability in the contact angle test. PVS rendered a contact angle as low as 34.19º. The contact angle of VPES was 44.84º, which was lower than 54.76º for PE. In the tear strength test, PE showed nearly two time higher tear strength than the other two impression materials. VPES showed slightly lower tear strength than PVS. The tear strength of the three materials tested in increasing order was VPES, PVS, PE. VPES showed comparable detail reproduction to PVS and PE and better wettability than PE, but showed the lowest tear strength compared with PE and PVS.

A new approach to surface modification of materials has been formulated and explored in great detail. It was shown that polyvinyl alcohol (PVOH) quickly and irreversibly adsorbs to hydrophobic surfaces producing smooth, continuous, hydrophilic, robust films in the thickness range of tens of angstroms. Surfaces of all hydrophobic materials studied could be successfully turned hydrophilic by this adsorption, which is performed from dilute aqueous solutions of PVOH. The ultra-thin films of adsorbed PVOH were studied by means of contact angle, ellipsometry, XPS, AFM, FT-IR, and DSC. Adsorption conditions, such as time, polymer concentration and molecular weight, temperature, salt type and concentration, and polymer composition all have an effect on the properties of the adsorbed film. The unique character of PVOH irreversible adsorption among other water-soluble polymers is explained by polymer crystallization that occurs concurrently with adsorption. Crystallinity within adsorbed films is demonstrated by the means of FT-IR and DSC. Chemical properties of adsorbed PVOH were studied, and a number of synthetic procedures were developed for further modification of PVOH ultra-thin films. Cross-linking of adsorbed PVOH imparted great stability in hot water. PVOH in the ultra-thin films was successfully converted into a variety of polyvinyl esters and urethanes; polyethylene glycol was grafted “to” and “from” these films. Prospective applications of PVOH adsorption and its ultra-thin films were studied. Improved adhesion in glued joints of polyethylene was demonstrated when PVOH was pre-adsorbed on PE before applying adhesive. PVOH adsorption and subsequent PEG grafting significantly reduced protein adsorption on a hydrophobic surface. A possibility to create defined features on PVOH surface by chemical patterning was demonstrated. A novel design of vapor sensing devices based on the adsorbed and modified PVOH was proposed and studied in detail. It was shown that remarkable reproducibility in PVOH adsorption on surface acoustic wave devices can be achieved and that further chemistry of the adsorbed films permits the preparation of sensitive and selective vapor sensors.

M.Sc. (Chemistry)
The fabrication of multiwalled carbon nanotube/polyvinyl chloride (PVC) composites and a study of their thermal, fire retardancy and mechanical properties are reported. Triphenylphosphine linked - multiwalled carbon nanotube (TPP-MWCNT) and pristine MWCNT were used. The MWCNT were embedded in the polymer matrix through melt blending and solvent casting. The phosphorylation of the MWCNT and their dispersion in the PVC matrix was characterized by scanning electron microscopy and Raman spectroscopy. Thermal analysis of the nanocomposites by thermal gravimetric analysis (TGA) in both solvent casting and melt bending processes, showed different results when compared with the neat PVC. The modulus of the MWCNTs / PVC nanocomposites synthesized via melt blending increased, whilst there was a reduction in their tensile strength, indicating a decrease in polymer toughness. The tensile modulus and strength of MWCNTs / PVC nanocomposite synthesized via Solvent casting decreased whilst there was an increase in Tpp-MWCNT/PVC nanocomposite when compared with its counterpart MWCNTs / PVC nanocomposite, indicating an increase in stiffness and strength. The limited oxygen index (LOI) fire retardant tests of all the neat PVC and its nanocomposites showed no value difference.