Polythionourethane Thermoset Synthesis via Activation of Elemental Sulfur in an Efficient Multicomponent Reaction Approach

• For the transition toward a safer and more sustainable production of polymeric materials, new synthetic concepts need to be developed. Herein, we describe a catalytic, solvent-free synthesis approach for novel thionourethane thermoset materials, in which the diisothiocyanate reactant is generated in situ via a sulfurization of isocyanides with elemental sulfur, preventing the exposure and handling of the diisothiocyanate. In this one-pot procedure, castor oil fulfills a dual role: (i) acting as the solvent for the in situ diisothiocyanate synthesis in the first step and (ii) reacting as the polyol component in the subsequent thionourethane thermoset formation. The kinetics of the consecutive two steps were studied in detail via real-time IR measurements, and the thermoset crosslinking step was found to be thermally triggerable after the diisothiocyanate reactant is quantitatively formed, enabling high control over the curing process of the system. Differential scanning calorimetry, thermogravimetric analysis, and rheological measurements were performed to investigate the thermal and mechanical properties of the novel thionourethane thermosets and then compared to analogous polyurethane materials. Our results demonstrate an unprecedented approach for thermoset synthesis via an in situ reagent synthesis, i.e., the generation of isothiocyanates from isocyanides by catalytic activation of elemental sulfur, and subsequent thermally triggerable thermosetting with a polyol, resulting in materials with appealing properties.

Subject headings

NATURVETENSKAP  -- Kemi -- Polymerkemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Polymer Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Keyword

castor oil

DBU

isocyanide

isothiocyanate

multicomponent reaction

organocatalysis

sulfur

thermoset

thiourethane

Publication and Content Type

ref (subject category)

art (subject category)