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We present the modification of ethylene-propylene rubber (EPM) with vinyltetra-methydisiloxane (VTMDS) via reactive extrusion to create a new silicone-based material with the potential for high-performance applications in the automotive, industrial and biomedical sectors. The radical-initiated modification is achieved with a peroxide catalyst starting the grafting reaction. The preparation process of the VTMDS-grafted EPM was systematically investigated using process analytical technology (in-line Raman spectroscopy) and the statistical design of experiments (DoE). By applying an orthogonal factorial array based on a face-centered central composite experimental design, the identification, quantification and mathematical modeling of the effects of the process factors on the grafting result were undertaken. Based on response surface models, process windows were defined that yield high grafting degrees and good grafting efficiency in terms of grafting agent utilization. To control the grafting process in terms of grafting degree and grafting efficiency, the chemical changes taking place during the modification procedure in the extruder were observed in real-time using a spectroscopic in-line Raman probe which was directly inserted into the extruder. Successful grafting of the EPM was validated in the final product by 1H-NMR and FTIR spectroscopy.
Thermoplastic polymers like ethylene-octene copolymer (EOC) may be grafted with silanes via reactive extrusion to enable subsequent crosslinking for advanced biomaterials manufacture. However, this reactive extrusion process is difficult to control and it is still challenging to reproducibly arrive at well-defined products. Moreover, high grafting degrees require a considerable excess of grafting reagent. A large proportion of the silane passes through the process without reacting and needs to be removed at great expense by subsequent purification. This results in unnecessarily high consumption of chemicals and a rather resource-inefficient process. It is thus desired to be able to define desired grafting degrees with optimum grafting efficiency by means of suitable process control. In this study, the continuous grafting of vinyltrimethoxysilane (VTMS) on ethylene-octene copolymer (EOC) via reactive extrusion was investigated. Successful grafting was verified and quantified by 1H-NMR spectroscopy. The effects of five process parameters and their synergistic interactions on grafting degree and grafting efficiency were determined using a face-centered experimental design (FCD). Response surface methodology (RSM) was applied to derive a causal process model and define process windows yielding arbitrary grafting degrees between <2 and >5% at a minimum waste of grafting agent. It was found that the reactive extrusion process was strongly influenced by several second-order interaction effects making this process difficult to control. Grafting efficiencies between 75 and 80% can be realized as long as grafting degrees <2% are admitted.
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.
It has been widely shown that biomaterial surface topography can modulate host immune response, but a fundamental understanding of how different topographies contribute to pro-inflammatory or anti-inflammatory responses is still lacking. To investigate the impact of surface topography on immune response, we undertook a systematic approach by analyzing immune response to eight grades of medical grade polyurethane of increasing surface roughness in three in vitro models of the human immune system. Polyurethane specimens were produced with defined roughness values by injection molding according to the VDI 3400 industrial standard. Specimens ranged from 0.1 μm to 18 μm in average roughness (Ra), which was confirmed by confocal scanning microscopy. Immunological responses were assessed with THP-1-derived macrophages, human peripheral blood mononuclear cells (PBMCs), and whole blood following culture on polyurethane specimens. As shown by the release of pro-inflammatory and anti-inflammatory cytokines in all three models, a mild immune response to polyurethane was observed, however, this was not associated with the degree of surface roughness. Likewise, the cell morphology (cell spreading, circularity, and elongation) in THP-1-derived macrophages and the expression of CD molecules in the PBMC model on T cells (HLA-DR and CD16), NK cells (HLA-DR), and monocytes (HLA-DR, CD16, CD86, and CD163) showed no influence of surface roughness. In summary, this study shows that modifying surface roughness in the micrometer range on polyurethane has no impact on the pro-inflammatory immune response. Therefore, we propose that such modifications do not affect the immunocompatibility of polyurethane, thereby supporting the notion of polyurethane as a biocompatible material.
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.
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.
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 effect of hard segment content and diisocyanate structure on the transparency and mechanical properties of soft poly(dimethylsiloxane) (PDMS)-based urea elastomers (PSUs) was investigated. A series of PSU elastomers were synthesized from an aminopropyl-terminated PDMS (M¯n: 16,300 g·mol−1), which was prepared by ring chain equilibration of the monomers octamethylcyclotetrasiloxane (D4) and 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS). The hard segments (HSs) comprised diisocyanates of different symmetry, i.e., 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI), 4,4′-methylenebis(phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI), and trans-1,4-cyclohexane diisocyanate (CHDI). The HS contents of the PSU elastomers based on H12MDI and IPDI were systematically varied between 5% and 20% by increasing the ratio of the diisocyanate and the chain extender APTMDS. PSU copolymers of very low urea HS contents (1.0–1.6%) were prepared without the chain extender. All PSU elastomers and copolymers exhibited good elastomeric properties and displayed elongation at break values between 600% and 1100%. The PSUs with HS contents below 10% were transparent and became increasingly translucent at HS contents of 15% and higher. The Young’s modulus (YM) and ultimate tensile strength values of the elastomers increased linearly with increasing HS content. The YM values differed significantly among the PSU copolymers depending on the symmetry of the diisocyanate. The softest elastomer was that based on the asymmetric IPDI. The elastomers synthesized from H12MDI and MDI both exhibited an intermediate YM, while the stiffest elastomer, i.e., that comprising the symmetric CHDI, had a YM three-times higher than that prepared with IPDI. The PSUs were subjected to load–unload cycles at 100% and 300% strain to study the influence of HS morphology on 10-cycle hysteresis behavior. At 100% strain, the first-cycle hysteresis values of the IPDI- and H12MDI-based elastomers first decreased to a minimum of approximately 9–10% at an HS content of 10% and increased again to 22–28% at an HS content of 20%. A similar, though less pronounced, trend was observed at 300% strain. First-cycle hysteresis among the PSU copolymers at 100% strain was lowest in the case of CHDI and highest in the IPDI-based elastomer. However, this effect was reversed at 300% strain, with CHDI displaying the highest hysteresis in the first cycle. In vitro cytotoxicity tests performed using HaCaT cells did not show any adverse effects, revealing their potential suitability for biomedical applications.
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.