Photocrosslinkable Polyurethane Coatings and Adhesives


 Number/Link: WO2018/039453

Applicant/Assignee:  Univ of Akron

Publication date: 1-March-2018

Gist”: PU coatings or adhesives with built-in coumarin or phenacyl groups 

Why it is interesting: According to this invention, polyurethane coating- and adhesive systems with two ‘levels of strength’ can be made by incorporating photoresponsive groups like coumarin into the PU backbone.  The coumarin groups will dimerize when irradiated with UV light of about 340nm and can be cleaved again with light of about 250nm. Alkoxyphenacyl groups can also be built into the PU backbone, allowing photocleavage with UV light of 250-350nm. The use of coumarin in (self-healing) coatings is not new and has been discussed before in this blog, so I doubt that this is patentable.

coumarin monomer

Hydroxy functional coumarin monomer

Hydrolysable Ureas


Number/Link: WO2017/155958

Applicant/Assignee: Univ. Illinois

Publication Date: 14 September 2017

“Gist”: Hindered urea bonds with fast hydrolysis kinetics are prepared from aromatic-sbstituted diamines and diisocyanates

Why it is interesting: Polyurethanes containing thermally reversible hindered urea bonds (HUBs) have been discussed before in this blog. In the current case the HUBs are prepared from aromatic (e.g aryl-) substituted amines and are said to show fast, pH-independent, hydrolysis kinetics. The HUBs can be built into linear or crosslinked polyurethanes or other polymers like polyamides, polycarbonates etc.  The resulting materials are useful for medical applications like drug delivery, water-degradable packaging, self-healing materials and the like.

HUB hysdrolysis

Hydrolysis reaction of phenyl-N-tetrabutyl-N-ethyl urea


Matte, Self-Healing Polyurethane Powder Coatings


Number/Link: WO2017/074835

Applicant/Assignee: Valspar

Publication Date: 4 May 2017

“Gist”: Coating composition comprising isocyanate and two polyester polyols having a similar Tg but a widely different equivalent weight.

Why it is interesting: Conventionally low gloss or “matte” coatings are the result of a microtextured surface achieved by certain fillers or by incompatible polymers and the like. According to this invention “ultra matte” finishes can also -surprisingly- be achieved from a (powder) coating composition comprising a (blocked) isocyanate and a mixture of two polyester polyols. Both polyols have a Tg between 40 and 60ºC prefereably differing not more than 5 to 8ºC, while the OHv of the first polyol is between 150 and 325 and that of the second between 15 and 35.  The ratio between first and second polyol is from about 1:1 to 1:3 w/w. Also surprisingly, the resulting coatings are said to show self-healing properties. An interesting composition but no examples of the polyesters or isocyanates used are given.

Car with matte finish

Self-Healing Polyurethane Elastomers


 Number/Link: W02016185172

Applicant/Assignee: Croda

Publication date: 24-11-2016

Gist”: PU from polyols which contain both a fatty dimer residue and an H-bonding group, show self-healing properties

Why it is interesting: Polyurethane elastomers with ‘intrinsic’ self-healing properties (i.e. without the need for external chemicals like encapsulated monomers) can be prepared by reacting isocyanates with polyols that have at least one urethane, amide or carbonate group and at least one fatty dimer residue. It is theorized that the fatty dimer allows the soft-phase of the polymer to flow and H-bonds to form, thus restoring most of the properties after damage.  In the examples polyols with internal urethane groups were prepared by reacting C36 dimer diol with HDI, which were then reacted with MDI and BDO. Samples of the resulting elastomers were cut in half, and manually stuck together again under mild heating (60°C), thus recovering most of their tensile and elongation properties.

A dimer diol

A dimer diol

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.