Thermal Degradation Mechanism of a Thermostable Polyester Stabilized with an Open-Cage Oligomeric Silsesquioxane

Bautista, Y.; Gozalbo, A.; Mestre, S.; Sanz, V.

doi:10.3390/ma11010022

Cited by 29 publications

(16 citation statements)

References 33 publications

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“…The HO-POSS, oppositely to amine-POSS and Gly-POSS, is an open-cage polyhedral oligomeric silsesquioxane. Bautista Y. et al [ 59 ] showed the slight positive impact of open-cage oligomeric silsesquioxanes on the thermal stability of polyester due to the shift of the temperature at 50% weight loss. Here, also, a slight shift of T 50% for all PCL POSS compositions from 421 to 424 °C was observed.…”

Section: Resultsmentioning

confidence: 99%

The Effect of Various Polyhedral Oligomeric Silsesquioxanes on Viscoelastic, Thermal Properties and Crystallization of Poly(ε-caprolactone) Nanocomposites

Lipińska

2022

Polymers

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Polyhedral oligomeric silsesquioxane POSS nanoparticles can be applied as reinforcing additives modifying various properties of biodegradable polymers. The effects of aminopropylisobutyl POSS (amine-POSS), trisilanolisooctyl-POSS (HO-POSS) and glycidyl-POSS (Gly-POSS) on the viscoelastic, thermal properties and crystallization of biodegradable poly(ε-caprolactone) PCL were studied. The analysis of the viscoelastic properties at ambient temperature indicated that aminopropylisobutyl POSS (amine-POSS) and glycidyl-POSS (Gly-POSS) enhanced the dynamic mechanical properties of PCL. The increase in the storage shear modulus G′ and loss modulus G″ was observed. The plasticizing effect of trisilanolisooctyl POSS (HO-POSS) due to the presence of long isoctyl groups was confirmed. As a result, the crystallization of PCL was facilitated and the degree of crystallinity of χc increased up to 50.9%. The damping properties and the values of tan δ for PCL/HO-POSS composition increased from 0.052 to 0.069. The TGA results point out the worsening of the PCL thermal stability, with lower values of T0.5%, T1% and T3%. Both HO-POSS and Gly-POSS facilitated the relaxation of molten PCL. The presence of Gly-POSS influenced the changes that occurred in the viscoelastic properties of the molten PCL due to the thermo-mechanical degradation of the material; a positive impact was observed.

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Section: Resultsmentioning

confidence: 99%

The Effect of Various Polyhedral Oligomeric Silsesquioxanes on Viscoelastic, Thermal Properties and Crystallization of Poly(ε-caprolactone) Nanocomposites

Lipińska

2022

Polymers

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“…Badia et al developed waterborne PSA formulations with 72% of biocontent through emulsion polymerization of commercial biobased monomers octyl acrylate and isosorbide methacrylate and achieved much higher peel strength (8.9 N/25 mm) and tackiness of 8.3 N . Our group has also previously developed UV curable PSAs derived from cardanol-based PU acrylates and lignin acrylates with acrylated linseed oil as a tackifier with ∼50% biomass content, and the peel strength was comparable to commercial tapes and plant-oil-based adhesives. ,− However, higher biomass content based PSA formulations usually involved petro-sourced monomers during polymerization to enhance the adhesion and peel for real time applications. − …”

Section: Introductionmentioning

confidence: 84%

Bio-based Pressure Sensitive Adhesives Derived from Cardanol, Vanillin, and Sebacic Acid for Removable Nonstructural Applications

Paul

Singh

Vidhya

et al. 2022

Ind. Eng. Chem. Res.

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Green and sustainable pressure sensitive adhesive (PSA) with higher biomass content is an upcoming area in the adhesive industries, owing to its potential to replace crude-oil-based nonrenewable PSAs. Herein, we report a novel bio-based PSA with 89–92% biomass content, majorly derived from cardanol, a component derived from cashew nut shell liquid (CNSL) and from vanillin, a lignin derivative. The control PSA copolyesters were synthesized by the copolymerization of epoxidized cardanol with sebacic acid. Vanillin epoxide (VE) was incorporated into the prepolymer in different proportions (10–30 wt %) to tune its functional behavior through ring opening esterification and etherification. A single glass transition temperature (T g) of all the samples revealed good miscibility of the system with desired transition temperature range (−16 to −21 °C) as applicable for PSAs. The 90° peel strength of the formulations gradually improved upon an increase in VE loading with an optimum value of 4.82 ± 0.38 N/25 mm, revealing their suitability for nonstructural and semistructural applications. A similar trend is noticed for the lap shear analysis of metal joints, wherein the PSA with 30% VE loading showcased excellent shear resistance of 2.61 ± 0.08 MPa. The PSA showed reasonable shear adhesive performance for plastics joints and also good adhesion even after exposure to water and liquid nitrogen. The viscoelastic properties of uncured PSA formulations were found to satisfy the criteria for removable PSAs. The samples are found to be thermally stable up to 180 °C without any sort of degradation, indicating potential for high temperature PSA applications. Thus, vanillin and cardanol incorporated PSAs with ∼90% biomass content pave the way for substituting the petro-based PSAs for nonstructural and semistructural applications being renewable and eco-friendly.

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“…For example, with BTSA and BTSEE, though pore size distribution patterns are similar to reactions with BTSE, they show 10% and 7% drops in this "post-curing" region of the TGA, which result in a loss of~0.2 cm 3 /g of cumulative pore volume, equivalent to half the BTSE SSA. In addition, materials with BTSEE in both solvents show oxidation peaks at around 375 • C, this indicates that the ethylene π-bonds remain chemically active for further functionalization [54,55].…”

Section: Cross-linkersmentioning

confidence: 98%

R-Silsesquioxane-Based Network Polymers by Fluoride Catalyzed Synthesis: An Investigation of Cross-Linker Structure and Its Influence on Porosity

Furgal

2020

Materials

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Silsesquioxane-based networks are an important class of materials that have many applications where high thermal/oxidative stability and porosity are needed simultaneously. However, there is a great desire to be able to design these materials for specialized applications in environmental remediation and medicine. To do so requires a simple synthesis method to make materials with expanded functionalities. In this article, we explore the synthesis of R-silsesquioxane-based porous networks by fluoride catalysis containing methyl, phenyl and vinyl corners (R-Si(OEt) 3 ) combined with four different bis-triethoxysilyl cross-linkers (ethyl, ethylene, acetylene and hexyl). Synthesized materials were then analyzed for their porosity, surface area, thermal stability and general structure. We found that when a specified cage corner (i.e., methyl) is compared across all cross-linkers in two different solvent systems (dichloromethane and acetonitrile), pore size distributions are consistent with cross-linker length, pore sizes tended to be larger and π-bond-containing cross-linkers reduced overall microporosity. Changing to larger cage corners for each of the cross-linkers tended to show decreases in overall surface area, except when both corners and cross-linkers contained π-bonds. These studies will enable further understanding of post-synthesis modifiable silsesquioxane networks.Materials 2020, 13, 1849 2 of 13 of reaction solvent and water content in modifying the overall pore size distributions of a single cross-linker system [29]. Though many reports speculate that the pore sizes obtained in sol-gel reactions are directly related to the bridging groups used, especially for rigid spacers [2,26,[30][31][32], we found that multiple pore size distributions (0.5 to 100 nm) could be obtained by simply changing the reaction solvent for the same bridge. For example, dichloromethane (DCM) favored micropores on the order of 1.2 nm and gel particles, while changing the reaction solvent to acetonitrile (ACN) gave pores centered around 3 nm and favored global gelation of the entire system. All the synthesized materials favored non-polar solvents as expected for organogels based on networked silsesquioxanes.Though high porosity materials with static or non-functionalizable pores are useful in many applications [33][34][35][36], it is often desirable to impart additional functionality to these materials for many specialized uses. such as in biology or environmental remediation. as capture and release agents [2,17,[37][38][39]. These functionalities may include hydrophilic groups, amino-acids and reversible chemistries such as "click" or complexation ligands [40][41][42][43][44]. Many researchers have been working on methods to synthesize active silsesquioxane-based networks, albeit primarily through preformed cage methods. In terms of preformed cage systems, Ervithayasuporn et al. have developed a recyclable methacrylate-POSS (polyhedral oligomeric silsesquioxanes) porous network which can efficiently bind Pd and acts as a catalyst f...

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Thermal Degradation Mechanism of a Thermostable Polyester Stabilized with an Open-Cage Oligomeric Silsesquioxane

Cited by 29 publications

References 33 publications

The Effect of Various Polyhedral Oligomeric Silsesquioxanes on Viscoelastic, Thermal Properties and Crystallization of Poly(ε-caprolactone) Nanocomposites

The Effect of Various Polyhedral Oligomeric Silsesquioxanes on Viscoelastic, Thermal Properties and Crystallization of Poly(ε-caprolactone) Nanocomposites

Bio-based Pressure Sensitive Adhesives Derived from Cardanol, Vanillin, and Sebacic Acid for Removable Nonstructural Applications

R-Silsesquioxane-Based Network Polymers by Fluoride Catalyzed Synthesis: An Investigation of Cross-Linker Structure and Its Influence on Porosity

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