Abstract:Epoxidized soybean oil (ESO) is the oxidation product of soybean oil with hydrogen peroxide and either acetic or formic acid obtained by converting the double bonds into epoxy groups, which is non-toxic and of higher chemical reactivity. ESO is mainly used as a green plasticizer for polyvinyl chloride, while the reactive epoxy groups imply its great potential in both the monomer synthesis and the polymer preparation fields. Functional polymers are obtained by different kinds of reactions of the ESO with co-mon… Show more
“…1 D), indicating that heating in air increases C–OH group formation 34 , 35 and hydrogen bond formation between the molecules. On the other hand, both thermal and UV treatments intensified the SF-oil degradation by chain scission at the ester position and epoxy ring opening (decrease in 874 cm −1 peak) to form –OH and C=C chemistry 31 , 36 . Figure 1 Infrared spectra of virgin (control), UV exposed (UV treatment) and heated (thermal treatment) SFSB oils.…”
Section: Resultsmentioning
confidence: 99%
“…13 describes different possible chemical effects of UV and O 2 oxidation agents on oil/PET chemical transformations and degraded oil/degraded PET surface interactions over time. Figure 13 Schematic for UV/O 2 effects on SF-oil and PET interactions: UV/O 2 , temperature, and humidity yields intermolecular crosslinking and increased hydrogen bonding between oxidized oil and PET, and oil-degraded PET fractions 1 , 22 , 23 , 26 , 27 , 31 , 36 , 40 . …”
Polyethylene terephthalate (PET) fibers and fabrics are widely used for medical device applications such as vascular and anterior cruciate ligament prostheses. Several years ago, we began functionalizing PET fabrics using anionic polymers to enhance their biocompatibility, cell adhesion, proliferation and functional performance as PET ligament prostheses. Polymer functionalization followed a grafting-from process from virgin PET surfaces subject to spin-finish oil additive removal under Soxhlet extraction to remove residual fiber manufacturing oil. Nevertheless, with increasing time from manufacture, PET fabrics stored without a spin finish removal step exhibited degradation of spin finish oil, leading to (1) incomplete surface cleaning, and (2) PET surface degradation. Moreover, oxidizing agents present in the residual degraded oil prevented reliable functionalization of the prosthesis fibers in these PET fabrics. This study compares effects of PET fabric/spin finish oil storage on PET fabric anionic polymer functionalization across two PET fabric ligament storage groups: (1) 2- and 10- year old ligaments, and (2) 26-year old ligaments. Strong interactions between degraded spin finish oil and PET fiber surfaces after long storage times were demonstrated via extraction yield; oil chemistry changed assessed by spectral analysis. Polymer grafting/functionalization efficiency on stored PET fabrics was correlated using atomic force microscopy, including fiber surface roughness and relationships between grafting degree and surface Young’s modulus. New PET fabric Young’s modulus significantly decreased by anionic polymer functionalization (to 96%, grafting degree 1.6 µmol/g) and to reduced modulus and efficiency (29%) for 10 years storage fabric (grafting degree ~ 1 µmol/g). As fiber spin finish is mandatory in biomedically applicable fiber fabrication, assessing effects of spin finish oil on commercial polymer fabrics after longer storage under various conditions (UV light, temperature) is necessary to understand possible impacts on fiber degradation and surface functionalization.
“…1 D), indicating that heating in air increases C–OH group formation 34 , 35 and hydrogen bond formation between the molecules. On the other hand, both thermal and UV treatments intensified the SF-oil degradation by chain scission at the ester position and epoxy ring opening (decrease in 874 cm −1 peak) to form –OH and C=C chemistry 31 , 36 . Figure 1 Infrared spectra of virgin (control), UV exposed (UV treatment) and heated (thermal treatment) SFSB oils.…”
Section: Resultsmentioning
confidence: 99%
“…13 describes different possible chemical effects of UV and O 2 oxidation agents on oil/PET chemical transformations and degraded oil/degraded PET surface interactions over time. Figure 13 Schematic for UV/O 2 effects on SF-oil and PET interactions: UV/O 2 , temperature, and humidity yields intermolecular crosslinking and increased hydrogen bonding between oxidized oil and PET, and oil-degraded PET fractions 1 , 22 , 23 , 26 , 27 , 31 , 36 , 40 . …”
Polyethylene terephthalate (PET) fibers and fabrics are widely used for medical device applications such as vascular and anterior cruciate ligament prostheses. Several years ago, we began functionalizing PET fabrics using anionic polymers to enhance their biocompatibility, cell adhesion, proliferation and functional performance as PET ligament prostheses. Polymer functionalization followed a grafting-from process from virgin PET surfaces subject to spin-finish oil additive removal under Soxhlet extraction to remove residual fiber manufacturing oil. Nevertheless, with increasing time from manufacture, PET fabrics stored without a spin finish removal step exhibited degradation of spin finish oil, leading to (1) incomplete surface cleaning, and (2) PET surface degradation. Moreover, oxidizing agents present in the residual degraded oil prevented reliable functionalization of the prosthesis fibers in these PET fabrics. This study compares effects of PET fabric/spin finish oil storage on PET fabric anionic polymer functionalization across two PET fabric ligament storage groups: (1) 2- and 10- year old ligaments, and (2) 26-year old ligaments. Strong interactions between degraded spin finish oil and PET fiber surfaces after long storage times were demonstrated via extraction yield; oil chemistry changed assessed by spectral analysis. Polymer grafting/functionalization efficiency on stored PET fabrics was correlated using atomic force microscopy, including fiber surface roughness and relationships between grafting degree and surface Young’s modulus. New PET fabric Young’s modulus significantly decreased by anionic polymer functionalization (to 96%, grafting degree 1.6 µmol/g) and to reduced modulus and efficiency (29%) for 10 years storage fabric (grafting degree ~ 1 µmol/g). As fiber spin finish is mandatory in biomedically applicable fiber fabrication, assessing effects of spin finish oil on commercial polymer fabrics after longer storage under various conditions (UV light, temperature) is necessary to understand possible impacts on fiber degradation and surface functionalization.
“…[28][29][30][31] Elastic moduli of the order of 10 MPa have been reported for these polymers. [28][29][30][31] Elastic moduli of the order of 10 MPa have been reported for these polymers.…”
“…21 Another study reported the synthesis of hybrid latexes from soybean oil-based waterborne polyurethane and acrylics via emulsion polymerization. [28][29][30][31] The purpose of this study was to synthesize a rigid and stable polymer using CSO. For example, styrene was copolymerized with CSO molecules.…”
Traditional plastics are usually obtained from nonrenewable petroleum feedstocks. In this study, crosslinked polymers were synthesized from cottonseed oil. Unsaturated fatty acids, the major components of cottonseed oils, were initially epoxidized. A network polymer was then formed by crosslinking the epoxidized oil with maleic anhydrate. Mechanical properties of these polymers were altered by varying the amount of maleic anhydrate. These polymers have a tensile modulus of the order 1 MPa and are stable in the acidic and alkaline environment. Our results provide a new synthetic strategy to obtain a network polymer from cottonseed oil.
“…1D), indicating that heating increases C-OH group formation [32,33] and hydrogen bond formation between the molecules. On the other hand, both thermal and UV treatments intensi ed the SFoil degradation by chain scission at the ester position and epoxy ring opening (decrease of 874 cm − 1 peak) to form -OH and C = C chemistry [29,34].…”
Spin finish oil applied to poly(ethylene terephthalate) (PET) fibers is shown to alter the surface properties of commercial PET fibers in storage over extended storage times. Oil removal by solvent extraction as required for their applications is shown to be changed; fiber surface chemistry, particularly surface functionalization with anionic polymer grafts, is altered, and surface mechanical properties are altered. Spin finish oxidation in storage is proposed to produce these fiber changes in storage important to their biomedical performance. Background: Poly(ethylene terephthalate) (PET) fabrics surface-functionalized using anionic polymer grafts to enhance their biocompatibility, cell adhesion, proliferation and functional performance as PET ligament prostheses have been developed for medical application in vascular and ligament prostheses. Here, we provide new evidence for deleterious effects of uncontrolled storage times and conditions on the final properties of PET medical fabrics and devices, specifically alteration and degradation of applied spin finish oil and fabric fiber surface properties, and limits to surface functionalization of PET fibers important to for medical uses.Results: Textile spin finish oil effects from 2- to 25-year storage times on PET fiber degradation and surface functionalization with anionic polymers were analyzed using FTIR, DSC and by quantitative AFM nano-mechanical profiling. Degradation of the spin-finish oil/fiber interface reduced oil Soxhlet extraction efficiency due to oil solubility changes in diethyl ether or n-hexane extraction solvents. However, solvent tetrahydrofuran was shown to be the most efficient extraction solvent even after long fabric storage times, facilitating further efficient surface functionalization of PET fabrics. Surface mechanical properties of PET fibers and fabrics over storage times spanning 2 to 25 years were investigated by using AFM-Peakforce QNM. Results showed significant and dramatic reduction of the surface elastic modulus of degraded PET fiber surfaces, with surface stiffness decreasing from 2.3 GPa for optimal (2-year) conditions of storage (PET 2018) to 50-85 MPa for extended storage (to 25 year) periods (PET2009 and PET1993). Conclusion: The ambient aging of textile spin finish oil with PET surfaces was shown to induce PET surface degradation, limiting oil removal, limiting further PET fiber surface graft functionalization, and compromising mechanical properties. Moreover, residual degraded finishing oils likely contained oxidation products from extended storage that alter PET fabrics.
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