Natural Oil Polyols using Self-Metathesis

Patent Title: POLYOLS FORMED FROM SELF-METATHESIZED NATURAL OILS AND THEIR USE IN MAKING POLYURETHANE FOAMS

 Number/Link: US2017/0291983

Applicant/Assignee:  Trent Univ.

Publication date: 12 october 2017

Gist”: NOPs from self-metathesized soy oils

Why it is interesting: The use of metathesis chemistry to modify natural oils before converting them to polyols has been discussed before in this blog:  see e.g. US2015/0337073, to the same applicant, which relates to cross-metathesis of natural oils using (e.g.) 1-butene. The current case is about self-metathesis of unsaturated natural oils, resulting in ‘metathesis oligomers’ which are then (partially) epoxidated and hydroxylated to prepare the polyols. In the examples soybean oil is turned into polyols with OH values between about 100 and 250, which are used to make flexible foams with densities of more than 150 kg/m³.

Oligomer from self-metathesis of unsaturated triglycerid


Hydrolysable Ureas

Patent Title: DYNAMIC UREA BONDS WITH FAST HYDROLYTIC KINETICS FOR POLYMERS

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

 

PU Flexible Foams with Reduced Acetaldehyde Emissions

Title: METHOD FOR THE REDUCTION OF ALDEHYDE EMISSION IN POLYURETHANE FOAM

Number/Link: WO2017/134296

Applicant/Assignee: Huntsman

Publication Date: 10 August 2017

“Gist”: Cyanoacetamide is used as aldehyde scavenger

Why it is interesting: Reduction of aldehyde emissions from (especially flexible) polyurethane foams remains an important issue and has already been discussed a number of times on this blog. According to this case the use of (pref) 0.05 to 0.5 pbw of cyanoacetamide in a flexible foam formulation will reduce the emission of formaldehyde, acetaldehyde, propionaldehyde, and possibly of higher aldehydes as well.
While an interesting compound, the use of cyanoacetamide in polyurethanes is not new and the effect is hardly surprising.

Cyanoacetamide

 

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

Polyols from Natural Oils using the Alkyne Zipper Reaction

Title: POLYURETHANE MATERIALS FORMED FROM UNSATURATED PLANT OILS VIA AN ALKYNE ZIPPER REACTION

Number/Link: US2017/0166679 US2017/0166680

Applicant/Assignee: IBM

Publication Date: 15-june-2017

“Gist”: Oils are turned into alkyne alcohols, ‘zippered’ and oxidized to polyols

Why it is interesting: This is yet  another IBM patent application about interesting, albeit somewhat exotic, chemistry and featuring only “prophetic” examples. In this case unsaturated natural oils are first converted into unsaturated alcohols and then into alkynes by bromination and elimination.  The internal alkynes are then converted to terminal alkynes by an “alkyne zipper reaction” and then into hydroxyl groups by hydroboration and epoxidation/ring-opening. This series of reactions should result in polyols having two primary- and one or more secondary OH groups, useful, for example, for the preparation of sound absorbing foams.

Reaction sequence according to the invention