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 Polyurethane Flexible Foams

Title: NON ISOCYANATE POLYURETHANE FOAMS

Number/LinkUS2017/0218124

Applicant/Assignee: Faurecia

Publication Date: 3 august 2017

“Gist”: Flex foams from a blend of two polyfunctional cyclocarbonates, a polyamine and HFC blowing agent.

Why it is interesting: While non-isocyanate polyurethanes are well known by now, examples of NIPU foams, especially flexible foams are rare. According to this case NIPU foams ‘having good resilience and low density’ can be prepared by reacting two polyfunctional carbonates A and B with a polyamine in the presence of a blowing agent and a catalyst. Cyclocarbonate A is (pref) trimethylolpropaneglycidylether carbonate and B is a polyetherpolyol with the OH groups replaced by glycidylcarbonate groups, for example an alkoxyalated trimethylolpropaneglycidylether carbonate. The polyamine is e.g. 1,6 diaminohexane.  The ratio A:B is preferably about 60:40.  In the examples no value for the resilience is given (but my guess based on the Tg is that it is probably not very high) and the lowest moulded density achieved is 140 kg/m³. So still a long way to go..

Glycidylether carbonate of alkoxylkated trimethylolpropane

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