Self-Healing Polyurethane Coatings

Patent Title: Self-Repairing Polyurethane Networks

 Number/Link: US20160289495

Applicant/Assignee: Clemson University

Publication date: 6-10-2016

Gist”: Polyurethane networks with alkylated polysaccharide moiety show self-healing properties

Why it is interesting: Chitosan (pref.) is alkylated by reacting with dodecylaldehyde (in solvent) and reducing the resulting imine with sodium cyanoborohydride. The alkylated chitosan is then reacted with isocyanate and polyol.  When used as coating, the material is claimed to show self-healing properties when irradiated with UV light. Modifying the composition by incorporation of catechol, or by changing the saccharide allows for materials which ‘heal’ when exposed to ferric ions or carbon dioxide. No explanation for this behaviour is given and it is not immediately clear to me why this should work.

Self-healing network according to the invention. The isocyanate used was (E)-3,5-bis(6-isocyanatohexyl)- 6-( ( 6-isocyanatohexyl)imino )-1,3,5-oxadiazinane-2, 4-dione.

Self-healing network according to the invention. The isocyanate used was (E)-3,5-bis(6-isocyanatohexyl)-6-( ( 6-isocyanatohexyl)imino )-1,3,5-oxadiazinane-2,4-dione. ALK= alkyl, POL=polyol.

 

Polyurethane Prepolymer with Very Low Monomeric Isocyanate Content

Patent Title: ULTRALOW MONOMER POLYURETHANES

 Number/Link: WO 2016/142513

Applicant/Assignee: Henkel

Publication date: 15-09-2016

Gist”: An NCO-ended prepolymer is reacted with a bis(alkoxysilylalkyl)amine

Why it is interesting: This invention is about laminating adhesives with a ‘primary aromatic amine migration limit’ of less than 10ppb, in accordance with the EU regulation for food packaging laminates. The low monomeric content is achieved by first making a NCO-ended prepolymer, which is then reacted with an monofunctional ‘H-acidic’ compound, preferably a bis(alkoxysilylalkyl)amine.  In an example a mixture of diols (OHv 108 to 236) was  reacted with 2.4-TDI down to an NCO value of 3.85%. Then 4,4′ MDI, trimethylolpropane and a triiso based on TDI were added to an NCO value of 2.2%.  Finally the prepolymer was reacted with bis(3-(triethoxysilyl)proplyl)amine at an NCO/NH ratio of 7:1.  Final NCO value was 2% with 0.05% (w/w) free 2,4-TDI and less than 0.01% free 4,4′-MDI. The prepolymer is said to be useful in 1K and 2K adhesive compositions and is said to have better adhesion properties and reactivity compared to NCO-free adhesives like sile silane-terminated PU adhesives.

Bis(3-(triethoxysilyl)propyl)amine

Bis(3-(triethoxysilyl)propyl)amine

Polyurethane Tissue Adhesives

Patent Title: URETHANE DECOMPOSING METHOD AND URETHANE DECOMPOSING AGENT

 Number/Link:  US2016/0257800

Applicant/Assignee: Obihiro University

Publication date: 8-09-2016 (priority PCT/JP)

Gist”: Prepolymer from ether-ester polyol and aliphatic isocyanate

Why it is interesting: There is a growing trend in current surgerical practice to replace sutures and staples with adhesives. These tissue adhesives need to have a particular set of properties, like the correct viscosity, hardening speed, biodegradability and toxic and allergenic properties. Current surgical adhesives are often cyanoacrylates, which react very fast, are brittle and show poor biodegradability, or protein-based adhesives which are costly and form weak bonds. According to this invention an improved polyurethane tissue adhesive can be prepared from an isocyanate-ended prepolymer based on an aliphatic isocyanate and a polyol.  The polyol is prepared from a starter polyol or amine which is reacted with a mixture of an alkoxide and about 10-20% of a  lactide (or glycolide or cyclic acid anhydride).  The lactide is randomly copolymerized with the alkoxide using DMC catalysis. The polyol is then reacted with an aliphatic isocyanate, pref. HDI or IPDI in a NCO/OH ratio of about 8:1. After that monomeric isocyanate is removed by thin film distillation down to less than 1% free monomer.
The adhesives are said to be fast, non-toxic, non-allergenic and biodegradable.

L-Lactide

L-Lactide

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