Influence of Hard Segment Content and Diisocyanate Structure on the Transparency and Mechanical Properties of Poly(dimethylsiloxane)-Based Urea Elastomers for Biomedical Applications

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.

Application of polyurethane in the production of shoe soles

Good footwear should be comfortable, long-lasting and fit for purpose, polyurethanes allow designers to meet all of these objectives. Polyurethanes are used in the footwear industry to make insoles and shoe soles.There are two types of PU soles a polyether and polyester based PU sole. Polyether based PU soles have a high resistance against hydrolysis and low oil resistance while polyester based PU soles have a low resistance against hydrolysis and high oil resistance. In this work thermal and mechanical properties of PU elastomers with polyether and polyester polols with different hard segment content were investigated. Differential scanning calorimetry (DSC) indicated partial crystalinity structure of the PU elastomers. PU elastomers based on polyether type polyol show the higher degree of crystalization. Based on DMAresults , Tgvalues of the PU increases and broadened with increasing hard segment content in the PU elastomers based on polyester polyol, due to the interaction between the urethane groups and the ester carbonyl groups. Mechanical studies indicated that the tensile strength of PU elastomers increased with hard segment.

Effect of diacylhydrazine as chain extender on microphase separation and performance of energetic polyurethane elastomer

It is low cost and feasible to improve the mechanical properties of polyurethane by using the chain extender with hydrogen bonding function to improve the degree of microphase separation. In this article, hydrazine hydrate was used to react with ethylene carbonate and propylene carbonate, respectively, to synthesize diacylhydrazines as the polyurethane chain extender with amide bonds, which were characterized by 1H nuclear magnetic resonance. Polyurethane with different contents of hard segment were prepared from poly-3,3-bis(azidomethyl)oxetane-tetrahydrofuran as the polyol and 4,4′-diphenylmethane diisocyanate as the isocyanate components. Fourier transform infrared spectroscopy showed that with the increase of the hard segment content, the proportion of hydrogen-bonded ordered carbonyl group increased to 94%, proving that diacylhydrazines could improve the degree of ordered hydrogen bonding, which led to clear microphase separation observed by field emission scanning electron microscopy and higher storage modulus of the polyurethane. Differential scanning calorimetry and dynamic mechanical analysis showed that polyurethane with higher hard segment content is likely to exhibit multiple thermal transitions caused by microphase separation. When the hard segment content was 40%, compared with polyurethane with 1,4-butanediol as the chain extender, the tensile strengths of polyurethanes with diacylhydrazines also improved by 30% and 76%, respectively.

Investigating the Properties and Structure of Polyurethane Elastomers with Monoethylene Glycol Chain Extender

The effect of monoethylene glycol (mEG) acting as chain extender in polypropylene glycol (PPG-4000) and 4,4ʹ-diphenylmethane diisocyanate (MDI) reaction was investigated. Polyurethane elastomers (PUR) were changed from flexible to rigid materials by varying the mEG content. Results show that Shore A and D hardness values trend to increase with increasing mEG content. It appears that increasing the chain extender content increases the hard segment content in the polyurethane structure. Moreover, increasing the mEG content increases Young’s modulus and the tensile strength of PUR, while elongation at break decreases. The chemical structure of the hard segment of PUR was characterized by Infrared (IR) spectroscopy. IR spectra exhibited the bands typical for PUR consisting of –NH, CH2– and C=O groups. The spectra reveal a few interactions between the polymeric chains that appear to be responsible for the shift of transmittance peak and decrease of some peak intensity. This may be due to the hard segment aggregating more to form domains in the PUR when mEG content was increased.