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The chemical synthesis of polysiloxanes from monomeric starting materials involves a series of hydrolysis, condensation and modification reactions with complex monomeric and oligomeric reaction mixtures. Real-time monitoring and precise process control of the synthesis process is of great importance to ensure reproducible intermediates and products and can readily be performed by optical spectroscopy. In chemical reactions involving rapid and simultaneous functional group transformations and complex reaction mixtures, however, the spectroscopic signals are often ambiguous due to overlapping bands, shifting peaks and changing baselines. The univariate analysis of individual absorbance signals is hence often only of limited use. In contrast, batch modelling based on the multivariate analysis of the time course of principal components (PCs) derived from the reaction spectra provides a more efficient tool for real time monitoring. In batch modelling, not only single absorbance bands are used but information over a broad range of wavelengths is extracted from the evolving spectral fingerprints and used for analysis. Thereby, process control can be based on numerous chemical and morphological changes taking place during synthesis. “Bad” (or abnormal) batches can quickly be distinguished from “normal” ones by comparing the respective reaction trajectories in real time. In this work, FTIR spectroscopy was combined with multivariate data analysis for the in-line process characterization and batch modelling of polysiloxane formation. The synthesis was conducted under different starting conditions using various reactant concentrations. The complex spectral information was evaluated using chemometrics (principal component analysis, PCA). Specific spectral features at different stages of the reaction were assigned to the corresponding reaction steps. Reaction trajectories were derived based on batch modelling using a wide range of wavelengths. Subsequently, complexity was reduced again to the most relevant absorbance signals in order to derive a concept for a low-cost process spectroscopic set-up which could be used for real-time process monitoring and reaction control.
An apparatus and method for analyzing a flow of material having an inlet region, a measurement range and an outlet region, and having a first diverter and a second diverter, and a deflection area, wherein in a first state of operation, the two diverters form a continuous first material flow space from the inlet region via the first diverter through the measurement range, via the second diverter to the outlet region, and in a second state of operation, form a continuous second material flow space from the inlet region via the first diverter through the deflection area, via the second diverter to the outlet region.
Film formation of self synthesized Polymer EPM–g–VTMDS (ethylene–propylene rubber, EPM, grafted with vinyltetramethyldisiloxane, VTMDS) was studied regarding bonding to adhesion promoter vinyltrimethoxysilane (VTMS) on oxidized 18/10 chromium/nickel–steel (V2A) stainless steel surfaces. Polymer films of different mixed solutions including commercial siloxane and silicone, dimethyl, vinyl group terminated crosslinker (HANSA SFA 42100, CAS# 68083-19-2, 0.35 mmol Vinyl/g) and platinum, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex Karstedt's catalyst (ALPA–KAT 1, CAS# 68478-92-2) were spin coated on V2A stainless steel surfaces with adsorbed VTMS thin layers in order to analyze film formation of EPM–g–VTMDS at early stages. Surface topography and chemical bonding of the high performance polymers on different oxidized V2A surfaces were investigated with X–ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and surface enhanced Raman spectroscopy (SERS). AFM and SEM as well as XPS results indicated that the formation of the polymer film proceeds via growth of polymer islands. Chemical signatures of the essential polymer contributions, linker and polymer backbones, could be identified using XPS core level peak shape analysis and also SERS. The appearance of signals which are related to Si–O–Si can be seen as a clear indication of lateral crosslinking and silica network formation in the films on the V2A surface.
Polyurethane thermosets have a wide range of applications. In this study, alternative raw materials were used to enhance sustainability. In two newly developed biobased polyurethanes (PUs), the cross-linker content was varied, which caused phase separation and therefore affected the turbidity. To investigate this phenomenon, UV–Vis–NIR spectroscopy was utilized. Spectra were recorded from 200 to 2500 nm in transmittance mode, and multivariate data analysis was applied to the three UV, Vis, and NIR sections separately. For the two different PU classes, each with five different cross-linker contents, classification by principal component analysis combined with linear or quadratic discriminant analysis was possible with an accuracy between 93% and nearly 100%. The best separation was achieved in the NIR range. Partial least-squares regression models were determined to predict the cross-linker content. As mentioned, the model for the NIR range is the most suitable, with the highest R2 (validation) of 0.99 for PU1 and 0.98 for PU2. The corresponding root-mean-square error of prediction values of the external validation was the lowest, with 0.82% (PU1) and 1.25% (PU2). Therefore, UV–Vis–NIR absorbance spectroscopy, especially NIR, is a suitable tool for monitoring the appropriate material composition of turbid PU thermosets in line.
Die kontinuierliche Erfassung von Qualitätsparametern ist eine zunehmende Anforderung in der Polymerextrusion. Die optische Spektroskopie kann diese Anforderung erfüllen, da sie neben der Farbe weitere Parameter wie beispielsweise chemische Eigenschaften, Trübungsgrad oder Partikelgröße erfasst. Dabei werden für Inline-Messungen im Extruder optische Sonden eingesetzt. Im laufenden Betrieb bilden sich Ablagerungen auf den Sondenfenstern. Dieser Beitrag präsentiert ein neues Cleaning in Place Konzept, mit dessen Hilfe die Fenster auch während der Produktion ohne Unterbrechung gereinigt werden können. Auch die Kalibrierung der Messtechnik ist dabei möglich. Das verhindert Rüstzeiten und sichert eine kontinuierliche Inline-Messung.
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.
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.
Here, we report the continuous peroxide-initiated grafting of vinyltrimethoxysilane (VTMS) onto a standard polyolefin by means of reactive extrusion to produce a functionalized liquid ethylene propylene copolymer (EPM). The effects of the process parameters governing the grafting reaction and their synergistic interactions are identified, quantified and used in a mathematical model of the extrusion process. As process variables the VTMS and peroxide concentrations and the extruder temperature setting were systematically studied for their influence on the grafting and the relative grafting degree using a face-centered central composite design (FCD). The grafting degree was quantified by 1H NMR spectroscopy. Response surface methodology (RSM) was used to calculate the most efficient grafting process in terms of chemical usage and graft yield. With the defined processing window, it was possible to make precise predictions about the grafting degree with at the same time highest possible relative degree of grafting.
Polyurethane-bases block copolymers (TPCUs) are block-copolymers with systematically varied soft and hard segments. They have been suggested to serve as material for chondral implants in joint regeneration. Such applications may require the adhesion of chondrocytes to the implant surface, facilitating cell growth while keeping their phenotype. Thus, aims of this work were (1) to modify the surface of soft biostable polyurethane-based model implants (TPCU and TSiPCU) with high-molecular weight hyaluronic acid (HA) using an optimized multistep strategy of immobilization, and (2) to evaluate bioactivity of the modified TPCUs in vitro. Our results show no cytotoxic potential of the TPCUs. HAbioactive molecules (Mw =700kDa) were immobilized onto the polyurethane surface via polyethylenimine (PEI) spacers, and modifications were confirmed by several characterization methods. Tests with porcine chondrocytes indicated the potential of the TPCU-HA for inducing enhanced cell proliferation.
Appropriate mechanical properties and fast endothelialization of synthetic grafts are key to ensure long-term functionality of implants. We used a newly developed biostable polyurethane elastomer (TPCU) to engineer electrospun vascular scaffolds with promising mechanical properties (E-modulus: 4.8 ± 0.6 MPa, burst pressure: 3326 ± 78 mmHg), which were biofunctionalized with fibronectin (FN) and decorin (DCN). Neither uncoated nor biofunctionalized TPCU scaffolds induced major adverse immune responses except for minor signs of polymorph nuclear cell activation. The in vivo endothelial progenitor cell homing potential of the biofunctionalized scaffolds was simulated in vitro by attracting endothelial colony-forming cells (ECFCs). Although DCN coating did attract ECFCs in combination with FN (FN + DCN), DCN-coated TPCU scaffolds showed a cell-repellent effect in the absence of FN. In a tissue-engineering approach, the electrospun and biofunctionalized tubular grafts were cultured with primary-isolated vascular endothelial cells in a custom-made bioreactor under dynamic conditions with the aim to engineer an advanced therapy medicinal product. Both FN and FN + DCN functionalization supported the formation of a confluent and functional endothelial layer.