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


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

TPU from Gem-Dialkyl Cyclooctene

Patent Title: TELECHELIC PREPOLYMERS AND REACTION PRODUCTS THEREOF

 Number/Link: WO 2017/023506

Applicant/Assignee: University of Minnesota

Publication date: 9-feb-2017

Gist”:  Diols are made by ROM polymerization of gem-dialkyl cyclooctene together with a symmetrical diol as chain transfer agent

Why it is interesting: According to this application, thermoplastic polyurethanes containing geminal dialkyl groups have far superior thermal stability, oxidative-, hydrolytic- and barrier properties as compared to TPUs containing conventional soft segments. Diols containing gem-dialkyl groups are prepared by ring-opening metathesis polymerization (ROMP) of a gem-dialkyl cyclooctene with a suitable catalyst and in the presence of a symmetrical aliphatic olefin chain transfer agent having functional end groups. Examples are 5,5-dimethylcyclooct-1-ene and 1,8-oct-4-ene diol as the chain transfer agent.  The resulting diol is then reacted with (e.g.) 4.4′-MDI to prepare the TPU.

5,5-dimethylcyclooct-1-ene

5,5-dimethylcyclooct-1-ene

Natural Oil Polyols Using Metathesis Chemistry

Patent Title: METATHESIZED TRIACYLGLYCEROL POLYOLS FOR USE IN POLYURETHANE APPLICATIONS AND THEIR RELATED PROPERTIES

 Number/Link: US2015/0337073

Applicant/Assignee: Trent University

Publication date: 26-11-2015

Gist”: Palm oil is metathesized before hydroxylation.

Why it is interesting: Natural-oil based polyols (NOPs) prepared from unsaturated plant oils are well known in the PU industry. In this case however, the oil is first modified into a ‘metathesized triacylglycerol’ by cross-metathesis using (e.g.) 1,2-butene and an appropriate catalyst. The result is a complex mixture of triglycerids, the unsaturations of which are then epoxidized and hydrolyzed into the final polyol.  In the examples palm-oil metathezised triacylglycerol (PMTAG) is compared to a commercially available soy-oil polyol when used to perpare both flexible and rigid foams. While the chemistry is interesting there does not appear to be much advantage to this type of NOP.

Metathesis reaction of triolein with butene

Metathesis reaction of triolein with butene

Polyurethane-Polyamides from Dimer Diacids

Title: A POLYOL BASED ON DIMER FATTY ACID RESIDUES AND THE CORRESPONDING POLYURETHANES

 Number/Link:WO2015/097433

Applicant/Assignee: Croda

Publication date: 2-07-2015

Gist”: Polyurethane/polyamide elastomers based on dimer diacids and long chain dicarboxylic acids

Why it is interesting: Polyurethane elastomers (and thermoplastic elastomers) based on dimer diacids or dimer diols are very hydrophobic and hydrolysis resistant but are relatively soft with lowish mechanical properties. According to this invention, using a blend of a dimer diacid (or -diol) and a (semi-) crystalline C17 to C32 dicarboxilic acid (or -diol) results in elastomers with greatly improved hardness and tensile strength while retaining flexibility and hydrolysis resistance. The C17 to C32 dicarboxylic acids can be prepared by a self-metathesis reaction of unsaturated fatty acid esters.  In the examples a C36 dimer diacid is used together with 1,18-octadodecanoic acid (prepared by metathesis from methyl oleate).  This is reacted ‘one shot’ with 4,4′ MDI and hexanediol or DEG, resulting in 85 shore A elastomers with high elongation and hydrolysis resistance.

A C36 dimer diacid

A C36 dimer diacid