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

TPU from Oleic Acid

Title: RENEWABLY DERIVED THERMOPLASTIC POLYESTER-BASED URETHANES AND METHODS OF MAKING AND USING THE SAME

Number/Link: US2017/0145145

Applicant/Assignee: Trent University

Publication Date: 25-may-2017

“Gist”: Thermoplastic polyurethane made entirely from C9 monomers derived from oleic acid.

Why it is interesting: Azaleic acid can be prepared by oxidative cleavage of the oleic acid double bond.  Azaleic acid in turn can be converted to 1,9-nonanediol and to 1,7-heptamethyldiisocyanate via azides and Curtius rearrangment (see previous blog post). In this invention a polyester diol is prepared from azaleic acid and nonanediol and is then reacted with 1,7-heptamethylenediisocyanate together with nonanediol as chain extender, resulting in a phase-separated TPU. Best properties are obtained when the nonanediol is first prepolymerized with the diisocyanate. The TPU is said to degrade without cytotoxic degradation products, and is therefore useful for medical applications such as resorbable implants and scaffolds.
Related case: US2017/0145146.

Oleic Acid

 

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

Polyurethane for Filament Winding

Patent Title: FILAMENT WINDING PROCESSES USING POLYURETHANE RESINS AND SYSTEMS FOR MAKING COMPOSITES

 Number/Link: W2016183073

Applicant/Assignee: Covestro

Publication date: 17-11-2016

Gist”: Compositions comprising polymeric MDI, amine-initated polyethers and natural oil polyols are useful for filament winding

Why it is interesting: Filament winding is a process for the production of hollow composite structures whereby resin-impregnated fibers are wound on a mandrel and then cured. Typically the fibers are impregnated with polyesters or epoxies.  Polyurethane compositions are difficult to use in this process because of reactivity and moisture sensitivity. According to this invention an isocyanate reactive composition comprising at least 50% high functionality amine-initiated polyether polyols and up to 50% of a hydrophobic OH-functional vegetable oil, can be advantageously used for PU filament winding. In the examples blends of 3 and 4-functional amine-initated polyether polyols with mole weight of about 250, castor oil, or OH-functional soy-oil, are used together with a high 2,4′ polymeric MDI.

Filanent winding process

Filanent winding process

PET-Lignin Polyols

Patent Title: HIGH RECYCLE CONTENT POLYOLS FROM THERMOPLASTIC POLYESTERS AND LIGNIN OR TANNIN

 Number/Link: WO2016/118411

Applicant/Assignee: Resinate Materials Group

Publication date: 28-07-2016

Gist”: PET is glycolized and then reacted with lignin or tannin

Why it is interesting: This application is about ‘sustainable’ aromatic polyester polyols partly based on recycled materials and partly on biorenewable materials. According to the invention the polyols can be prepared by first glycolizing (waste) PET and subsequently reacting the mixture with lignin at 110-210°C while removing volatile condensation products.  The resulting polyols (pref) show a OH value between 40 and 400 mg KOH/g, a fn of 2-2.2 and a viscosity at 25°C of 500 to 3000 cP. In the examples polyols with up to 25 wt% lignin are shown. The polyols are said to be useful e.g. in 2K PU coating compositions.

Part of a lignin structure

Part of a lignin structure