Non-Isocyanate Polyurethanes from Thiocarbonates

Patent Title: PROCESS FOR THE MANUFACTURING OF A POLYMER WITH URETHANE GROUPS

Number/Link: WO2019/034470 and WO2019/034473

Applicant/Assignee: BASF

Publication Date: 21 February 2019

“Gist”:  A cyclic thiocarbonate is reacted with a diamine and then with a diacrylate

Why it is interesting: NIPU is prepared by reacting a five-ring monothiocarbonate with di- (or poly-) amine and then with a compound having at least two thiol-reactive functional groups like e.g. ethylenically unsaturated groups. The reaction has advantages over conventional PU chemistry like being isocyanate-free, less moisture sensitive and running at moderate temperatures. In an example methyl monothiocarbonate is reacted with 1,5-pentanediamine and 1,4-butandioldimethacrylate, resulting in a colourless, transparent polymer with a high thermal stability.
An interesting take on hybrid non-isocyanate polyurethanes.

scheme1

Reaction scheme according to the invention

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Thiol-Crosslinked Poly(hydroxyurethanes)

Title: METHOD FOR PRODUCING OR CURING POLYMERS USING THIOL-ENE POLYADDITION REACTIONS

Number/Link: W2017/081120

Applicant/Assignee:  Henkel

Publication Date: 18-05-2017

“Gist”: Unsaturated PHU are crosslinked using polythiols

Why it is interesting: The invention is about poly(hydroxyurethanes) (PHU) containing alkylene groups that are crosslinked using thiol-ene ‘click’ polyaddition reactions. The unsaturated PHU are first prepared by aminolysis of cyclocarbonates using unsaturated amines. In an example di-trimethylolpropane is converted to di-trimethylolpropanedicarbonate using ethylchloroformiate.  The di-TMPDC is then reacted with 3-aminopropylvinylether to prepare the PHU, which is then crosslinked using pentaerithritol-tetra(3-mecaptopropionate) in the presence of a photoinitiator and UV light.  The invention is said to be useful for isocyanate-free adhesive- and coating systems.

Di-trimethylolpropanedicarbonate

Dispersions of Comb-Structured Polyurethanes

Patent Title: POLYURETHANE-BASED BINDER DISPERSION

 Number/Link: WO2016122569

Applicant/Assignee: Hewlett-Packard

Publication date: 4-08-2016

Gist”:  Aqueous dispersions of “1,2”-dihydroxypolyacrylate -based polyurethanes

Why it is interesting: According to this invention aqueous dispersions can be made of “comb -structured” polyurethanes which are based on polyols having two hydroxyl groups at one end of the chain.  The “1,2”-diols are made by copolymerizing (e.g.) methylmethacrylate and n-butylmethacrylate together with thioglycerol up to a Mw of about 2000. The polyols can then be reacted with isocyanate and dimethylolpropionic acid for dispersion in water. The dispersions are said to have a small average particle size (10-100 nm) and be especially useful as binders for inkjet-ink.

Thioglycerol

Thioglycerol