Accelerating the Curing of Hybrid Poly(Hydroxy Urethane)-Epoxy Adhesives by the Thiol-Epoxy Chemistry.

The polyaddition between dicyclic carbonates and diamines leading to poly(hydroxy urethane)s (PHUs) has emerged as the preferred method for the synthesis of green, non-isocyanate polyurethanes. However, when proposed for use as structural adhesives, the long times for completion of aminolysis of the 5-membered cyclic carbonates under ambient conditions force the use of complementary chemistries to accelerate the curing process. In this work, a system that combines an amino-terminated PHU (NH2-PHU-NH2), an epoxy resin, and a thiol compound was employed to develop high-shear strength PHU-epoxy hybrid adhesives able to cure at room temperature in short times. A NH2-PHU-NH2 prepolymer synthesized by using a sub-stoichiometric quantity of dicyclic carbonates was mixed with a bisphenol A-based epoxy resin for the preparation of the structural adhesive. While this adhesive showed good lap-shear strength and shear resistance under static load and temperature, the curing process was slow. In order to speed up the curing process, a thiol (trimethylolpropane tris(3-mercapto propionate)) was added and its impact on the curing process as well as on the adhesive properties was evaluated. The trifunctional thiol additive allowed for faster curing in the presence of the 1,1,3,3-tetramethylguanidine basic catalyst. Moreover, a combination of NH2-PHU-NH2 and the thiol as curing agents for the epoxy resin resulted in adhesives with superior toughness, without any deterioration of the ultimate lap-shear strength or shear resistance under load and temperature, making these adhesives suitable for high-demand applications in the automotive industry.

Enhanced and Reusable Poly(hydroxy urethane)-Based Low Temperature Hot-Melt Adhesives.

Poly(hydroxy urethane)s (PHUs) based on 5-membered cyclic carbonates have emerged as sustainable alternatives to conventional isocyanate-based polyurethanes. However, while from the point of view of sustainability they represent an improvement, their properties are still not competitive with conventional polyurethanes. In this work, the potential of PHUs as reversible hot-melt adhesives is discussed. We found that with a judicious choice of reagents (i.e., the dicyclic carbonate and diamine), the detrimental hydrogen bonding between the soft segment of the chains and the pendant hydroxyl groups was partially avoided, thus imparting PHUs with hot-melt adhesion properties (i.e., adhesion at elevated temperatures and cohesiveness at a temperature lower than T g/T m). The importance of a balanced hard to soft segment ratio, along with the relevance of the chain extender in the final properties, is highlighted. Addition of aliphatic diamines (HMDA, 1,12-DAD) resulted in rubbery materials, while the employment of cycloaliphatic (CBMA) or aromatic ones (MXDA, PXDA) led to materials with hot-melt adhesive properties. The thermoreversibility of all compositions was assessed by rebonding specimens after lap-shear tests. Lap-shear strength values that were comparable to the virgin adhesives were observed. The breaking and reformation of hydrogen bonding interactions was demonstrated by FTIR measurements at different temperatures, as well as by rheological frequency sweep experiments. In order to mitigate the negative impact of the low molar mass PHUs and to enhance the service temperature of the adhesives, a hybrid PHU was prepared by adding a small amount of an epoxy resin, which acts as a cross-linker. These hybrid PHUs maintain the thermoreversibility displayed by thermoplastic PHUs while providing better adhesion at elevated temperatures. We believe that this work provides some important insights into the design of PHU-based hot-melt adhesives.

Trends in non-isocyanate polyurethane (NIPU) development.

The transition towards safer and more sustainable production of polymers has led to a growing body of academic research into non-isocyanate polyurethanes (NIPUs) as potential replacements for conventional, isocyanate-based polyurethane materials. This perspective article focuses on the opportunities and current limitations of NIPUs produced by the reaction between biobased cyclic carbonates with amines, which offers an interesting pathway to renewable NIPUs. While it was initially thought that due to the similarities in the chemical structure, NIPUs could be used to directly replace conventional polyurethanes (PU), this has proven to be more challenging to achieve in practice. As a result, and in spite of the vast amount of academic research into this topic, the market size of NIPUs remains negligible. In this perspective, we will emphasize the main limitations of NIPUs in comparison to conventional PUs and the most significant advances made by others and us to overcome these limitations. Finally, we provide our personal view of where research should be directed to promote the transition from the academic to the industrial sector.

Poly(hydroxyurethane) Adhesives and Coatings: State-of-the-Art and Future Directions.

Polyurethane (PU) adhesives and coatings are widely used to fabricate high-quality materials due to their excellent properties and their versatile nature, which stems from the wide range of commercially available polyisocyanate and polyol precursors. This polymer family has traditionally been used in a wide range of adhesive applications including the bonding of footwear soles, bonding of wood (flooring) to concrete (subflooring), in the automotive industry for adhering different car parts, and in rotor blades, in which large surfaces are required to be adhered. Moreover, PUs are also frequently applied as coatings/paints for automotive finishes and can be applied over a wide range of substrates such as wood, metal, plastic, and textiles. One of the major drawbacks of this polymer family lies in the use of toxic isocyanate-based starting materials. In the context of the REACH regulation, which places restrictions on the use of substances containing free isocyanates, it is now urgent to find greener routes to PUs. While non-isocyanate polyurethanes (NIPUs) based on the polyaddition of poly(cyclic carbonate)s to polyamines have emerged in the past decade as greener alternatives to conventional PUs, their industrial implementation is at an early stage of development. In this review article, recent advances in the application of NIPUs in the field of adhesives and coatings are summarized. The article also draws attention to the opportunities and challenges of implementing NIPUs at the industrial scale.

Synergetic Effect of Dopamine and Alkoxysilanes in Sustainable Non-Isocyanate Polyurethane Adhesives.

The preparation of non-isocyanate polyurethanes (NIPUs) by polyaddition of (poly)cyclic carbonates to (poly)amines represents one of the most optimistic alternatives for replacing conventional polyurethanes prepared by the toxic isocyanate chemistry. However, the limited reactivity of conventional five membered cyclic carbonates even in the presence of catalysts restricts their industrial implementation. One way to mitigate this lack of reactivity is to combine with other chemistries to create hybrid-NIPUs with superior performance. In this article the combination of the adhesive promoter, dopamine, and the fast-curing promoter, an aminopropyl trimethoxysilane, is found to create a synergetic effect on the rheological and adhesive properties of NIPUs. After demonstrating the importance of adjusting soft/hard ratios to obtain lap-shear strength adhesion values up to 21 MPa on stainless steel, these values are retained when adding dopamine and silane compounds. Importantly, the adhesive properties of NIPU are preserved at high temperature (T > 200 °C) for optimal compositions. Finally, adhesion tests on various substrates (polyamide, high density polyethylene, poly(methyl methacrylate), oak wood, and aluminum) show best performances on polar substrates confirming the strong interactions of hydroxyl groups of NIPU and dopamine.