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Silicones
(2014)
Silicones are found in a variety of applications with requirements that range from long life at elevated temperatures to fluidity at low temperatures. This chapter first considers silicone elastomers and their application in room temperature vulcanizing (RTV) and heat curing systems (HTV). Also, new technologies for UV curing are introduced. Coverage of RTVs includes both one-component and two-component systems and the different cure chemistries of each, and is followed by a separate discussion of silicone laminates. Due to the high importance of silicone fluids, they are also discussed. Fluids include polishes, release agents, surfactants, and dielectric fluids.
The intelligent recycling of plastics waste is a major concern. Because of the widespread use of polyethylene terephtalate, considerable amounts of PET waste are generated that are ideally re-introduced into the material cycle by generating second generation products without loss of materials performance. Chemical recycling methods are often expensive and entail environmentally hazardous by-products. Established mechanical methods generally provide materials of reduced quality, leading to products of lower quality. These drawbacks can be avoided by the development of new recycling methods that provide materials of high quality in every step of the production cycle. In the present work, oligomeric ethylene terephthalate with defined degrees of polymerization and defined molecular weight is produced by melt-mixing PET with different quantities of adipic acid as an alternative pathway of recycling PET with respect to conventional methods, offering ecofriendly and economical aspects. Additionally, block-copolyesters of defined block length are designed from the oligomeric products.
Ethylene terephthalate and ethylene naphthalate oligomers of defined degree of polymerization were synthesized via chemical recycling of the parent polymers. The oligomers were used as defined building blocks for the preparation of novel block-co-polyesters having tailored sequence compositions. The sequence lengths were systematically varied using Design of Experiments. The dispersive surface energy and the specific desorption energy of the co-polymers were determined by inverse gas chromatography. The study shows that polyethylene terephthalate-polyethylene naphthalate (PET-PEN) block-co-polyesters of defined sequence lengths can be prepared. Furthermore, the specific and dispersive surface energies of the obtained block-co-polyesters showed a linear dependence on the oligomer molecular weight and it was possible to regulate and control their interfacial properties. In contrast, with the corresponding random-block-co-polyesters no such dependence was found. The synthesized block-co-polyesters could be used as polymeric modifying agents for stabilizing PET-PEN polymer blends.
Clay minerals play an increasingly important role as functional fillers and reinforcing materials for clay polymer nanocomposites (CPN) in advanced applications. Among the prerequisites necessary for polymer improvement by clay minerals are homogeneous and stable Distribution of the clay mineral throughout the CPN, good compatibility of the reinforcement with the Matrix component and suitable processability. Typically, clay minerals are surface-modified with organic interface active compounds like detergents or silanes to obtain favorable properties as filler. They are incorporated into the polymer matrix using manufacturing Equipment like extruders, batch reactors or other mixing machines. In order for the surface modification to survive the stresses and strains during incorporation, the modified clay minerals must display sufficient thermal and mechanical stability to retain the compatibilizing effect. In the present study, thermogravimetry was used in combination with isoconversional kinetic analysis to determine the thermal stability of a silane-modified clay mineral based on bentonite. These findings were compared with the stability of the same clay mineral that was only surfactant-modified. It was found that silane modification leads to significantly improved thermal stability, which depends strongly on the type of silane employed.
Block-copolyesters of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) were synthesized via reactive extrusion. The influence of processing parameters on the material properties on a molecular scale like degree of trans-esterification, block length, and degree of randomness were investigated. The varied process factors were extrusion temperature and rotational speed. The effects of process parameter variation were investigated by 1H-NMR-spectroscopy. The experimental results show a clear dependence of the molecular properties on the processing conditions. By using statistical experimental design (DoE), it was possible to prepare defined copolyesters from PET and PEN without addition of further chemicals. With a degree of randomness between 0.05 and 0.5, the presence of an actual copolyester was confirmed when appropriate extrusion conditions were applied. The reactive extrusion process was confirmed to be suitable to produce defined block-copolyesters in a predictable and reproducible way. It was possible to produce designed sequence lengths, which could be adjusted within a range of 11–136 repeating units in the case of PET and, in the case of PEN, of 2.5–26. The produced materials can be used as barrier materials or barrier coatings to protect substrates against molecular oxygen and water vapour, e.g., in organic photovoltaic applications or food packaging. The described method is a one-pot alternative method to the previously described chemical recycling pathway.
The interfacial compatibility between polymers and nanoclay fillers as well as the thermostability of both components are important characteristics for processing them into polymer composites. While the polymer component is often grafted using common polymerization reactions, the nanoclay component is usually surface modified by surfactant treatment to improve compatibility. In the present study, the polymer ethylene vinyl alcohol and a nanoclay filler based on natural bentonite are both surface modified by different silanes, 3-glycidoxypropyltrimethoxysilane and methacryloxymethyltrimethoxysilane and their interfacial properties are investigated by inverse gas chromatography. The silane-modified samples had improved interfacial properties as reflected by a significant increase in dispersive and specific surface energies. Lewis acidities were determined using chloroform and 1,4-dioxane as polar probes and showed a good match between polymer and nanofiller interfaces. Lewis acidity was generally lower after silane-modification. Silanization yielded increased thermal stability of the treated samples. Thus, silanization led to improved compatibility and enhanced thermal stability which facilitates further processing.
Recycling of poly(ethylene terephthalate) (PET) is of crucial importance, since worldwide amounts of PETwaste increase rapidly due to its widespread applications. Hence, several methods have been developed, like energetic, material, thermo-mechanical and chemical recycling of PET. Most frequently, PET-waste is incinerated for energy recovery, used as additive in concrete composites or glycolysed to yield mixtures of monomers and undefined oligomers. While energetic and thermo-mechanical recycling entail downcycling of the material, chemical recycling requires considerable amounts of chemicals and demanding processing steps entailing toxic and ecological issues. This review provides a thorough survey of PET-recycling including energetic, material, thermo-mechanical and chemical methods. It focuses on chemical methods describing important reaction parameters and yields of obtained reaction products. While most methods yield monomers, only a few yield undefined low molecular weight oligomers for impaired applications (dispersants or plasticizers). Further, the present work presents an alternative chemical recycling method of PET in comparison to existing chemical methods.
A series of novel biomedical TPCUs with different percentages of hard segment and a silicone component in the soft segment were synthesized in a multi stage one-pot method. The kinetic profiles of the urethane formation in TPCU-based copolymer systems were monitored by rheological, in line FTIR spectroscopic (React IR) and real-time calorimetric (RC1) methods. This process-analytically monitored multi step synthesis was successfully used to optimize the production of medical-grade TPCU elastomers on preparative scale (in lots of several kg) with controlled molecular structure and mechanical properties. Various surface and bulk analytical methods as well as systematic studies of the mechanic response of the elastomer end-products towards compression and tensile loading were used to estimate the bio-stability of the prepared TPCUs in vitro after 3 months. The tests suggested that high bio-stability of all polyurethane formulations using accelerating in vitro test can be attributed to the synthetic design as well as to the specific techniques used for specimen preparation, namely: (1) the annealing for reducing residual polymer surface stress and preventing IES, (2) stabilization of the morphology by long time storage of the specimens after processing before being immersed in the test liquids, (3) purification by extraction to remove the shot chain oligomers which are the most susceptible to degradation. All mechanical tests were performed on cylindrical and circular disc specimens for modelling the thickness of the meniscus implants under application-relevant stress conditions.
This article contains data on the synthesis and mechanical characterization of polysiloxane-based urea-elastomers (PSUs) and is related to the research article entitled “Influence of PDMS molecular weight on transparency and mechanical properties of soft polysiloxane-urea-elastomers for intraocular lens application” (Riehle et al., 2018) [1]. These elastomers were prepared by a two-step polyaddition using the aliphatic diisocyanate 4,4′-Methylenbis(cyclohexylisocyanate) (H12MDI), a siloxane-based chain extender 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (APTMDS) and amino-terminated polydimethylsiloxanes (PDMS) or polydimethyl-methyl-phenyl-siloxane-copolymers (PDMS-Me,Ph), respectively. (More details about the synthesis procedure and the reaction scheme can be found in the related research article (Riehle et al., 2018) [1]).
Amino-terminated polydimethylsiloxanes with varying molecular weights and PDMS-Me,Ph-copolymers were prepared prior by a base-catalyzed ring-chain equilibration of a cyclic siloxane and the endblocker APTMDS. This DiB article contains a procedure for the synthesis of the base catalyst tetramethylammonium-3-aminopropyl-dimethylsilanolate and a generic synthesis procedure for the preparation of a PDMS having a targeted number average molecular weight of 3000 g mol−1. Molecular weights and the amount of methyl-phenyl-siloxane within the polysiloxane-copolymers were determined by 1H NMR and 29Si NMR spectroscopy. The corresponding NMR spectra and data are described in this article.
Additionally, this DiB article contains processed data on in line and off line FTIR-ATR spectroscopy, which was used to follow the reaction progress of the polyaddition by showing the conversion of the diisocyanate. All relevant IR band assignments of a polydimethylsiloxane-urea spectrum are described in this article.
Finally, data on the tensile properties and the mechanical hysteresis-behaviour at 100% elongation of PDMS-based polyurea-elastomers are shown in dependence to the PDMS molecular weight.
Soft thermoplastic polysiloxane-urea-elastomers (PSUs) were prepared for the application as a biomaterial to replace the human natural lens after cataract surgery. PSUs were synthesized from amino-terminated polydimethylsiloxanes (PDMS), 4,4′-Methylenebis(cyclohexylisocyanate) (H12MDI) and 1,3–Bis(3-aminopropyl)-1,1,3,3–tetramethyldisiloxane (APTMDS) by a two-step polyaddition route. Such a material has to be highly transparent and must exhibit a low Young’s Modulus and excellent dimensional stability. Polydimethylsiloxanes in the range of 3000–33,000 g·mol−1 were therefore prepared by ring-chain-equilibration of octamethylcyclotetrasiloxane (D4) and APTMDS in order to study the influence of the soft segment molecular weight on the mechanical properties and the transparency of the PSU-elastomers. 2,4,6,8-Tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (D4Me,Ph) was co-polymerized with D4 in order to adjust the refractive index of the polydimethyl-methyl-phenyl-siloxane-copolymers to a value equivalent to a young human natural lens. Very elastic PSUs with Elongation at Break values higher than 700% were prepared. PSU-elastomers, synthesized from PDMS of molecular weights up to 18,000 g·mol−1, showed transmittance values of over 90% within the visible spectrum range. The soft segment refractive index was increased through the incorporation of 14 mol % of methyl-phenyl-siloxane from 1.4011 to 1.4346 (37 °C). Young’s Moduli of PSU-elastomers were around 1 MPa and lower at PDMS molecular weights up to 15,000 g·mol−1. 10-cycle hysteresis measurements were applied to evaluate the mechanical stability of the PSUs at repeated stress. Hysteresis values at 100% strain decreased from 32 to 2% (10th cycle) with increasing PDMS molecular weight. Furthermore, hysteresis at 5% strain was only detected in PSU-elastomers with low PDMS molecular weights. Finally, preliminary results of in vitro cytotoxicity tests on a PSU-elastomer showed no toxic effects on HaCaT-cells.