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

Non-Isocyanate Poly(Amide-Hydroxyurethanes)

Patent Title: NON-ISOCYANATE POLYURETHANES AND METHODS OF MAKING AND USING THE SAME

 Number/Link: WO 2017/ 030880

Applicant/Assignee: ELEVANCE RENEWABLE SCIENCES

Publication date: 23-feb-2017

Gist”: Telechelic cyclocarbonate-alkylesters are reacted with diamines in the melt

Why it is interesting: According to this invention (ω-) unsaturated alkylesters can be converted to mono-cyclocarbonate alkylesters and then reacted with diamines to prepare thermoplastic poly(amide-hydroxyurethanes) (PAHU). For example methyl-9-decenoate was first epoxidized and then reacted with CO2 to produce 9,10-cyclic carbonate-methyl decanoate. After separation and washing the cyclocarbonate was reacted – in the melt- with a mixture of dodecane diamine and a PTMO diamine (Jeffamine THF-100). It is said that the unsaturated alkylesters can be prepared from natural oils using (cross- or self-) metathesis followed (or preceded) by transesterifaction with alkanols.

PAHU preparation scheme

PAHU preparation scheme

Non-Isocyanate Polyurethane Using Thiol-Ene “Click Chemistry”

Title: POLY(HYDROXYL URETHANE) COMPOSITIONS AND METHODS OF MAKING AND USING THE SAME

 Number/Link: US20140182784

Applicant/Assignee:  Inventors but with US goverment interest

Publication date: 3-07-2014

Gist”: Crosslinked poly(hydroxyurethanes) are prepared by reacting a cyclic carbonate comprising a carbon-carbon double bond, a di-thiol and a polyamine.

Why it is interesting: According to this invention hydroxyurethanes are produced by first reacting a cyclic carbonate which has a double bond (e.g. 4-vinyl-1,3-dioxolan-2-one) with a dithiol (e.g. 1,6-hexanedithiol) using UV radiation and a UV initiator. The resulting di-carbonate is then reacted with a polyamine (e.g. diethylene triamine) resulting in a crosslinked poly(hydroxyurethane). Alternatively the carbonate-amine reaction can happen before the thiol-ene ‘click’ reaction. The materials can be used for binders and adhesives a.o.  The reactions have the advantage of being solvent-, catalyst- and isocyanate-free and having a high yield.

Thiol-ene reaction followed by carbonate-amine reaction

Thiol-ene reaction followed by carbonate-amine reaction