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

 

Matte, Self-Healing Polyurethane Powder Coatings

Title: POLYURETHANE COATING COMPOSITION

Number/Link: WO2017/074835

Applicant/Assignee: Valspar

Publication Date: 4 May 2017

“Gist”: Coating composition comprising isocyanate and two polyester polyols having a similar Tg but a widely different equivalent weight.

Why it is interesting: Conventionally low gloss or “matte” coatings are the result of a microtextured surface achieved by certain fillers or by incompatible polymers and the like. According to this invention “ultra matte” finishes can also -surprisingly- be achieved from a (powder) coating composition comprising a (blocked) isocyanate and a mixture of two polyester polyols. Both polyols have a Tg between 40 and 60ºC prefereably differing not more than 5 to 8ºC, while the OHv of the first polyol is between 150 and 325 and that of the second between 15 and 35.  The ratio between first and second polyol is from about 1:1 to 1:3 w/w. Also surprisingly, the resulting coatings are said to show self-healing properties. An interesting composition but no examples of the polyesters or isocyanates used are given.

Car with matte finish

TPU with Reduced Blooming

Patent Title: POLYOLS WITH REDUCED CYCLIC OLIGOMER CONTENT AND THERMOPLASTIC POLYURETHANE COMPOSITIONS THEREOF

 Number/Link: WO2017040505

Applicant/Assignee: Lubrizol

Publication date: 9-mar-2017

Gist”: Enzymes are used to remove cyclo-oligomers from polyster polyols

Why it is interesting: It is known that the “blooming” of polyester TPUs (i.e. the fomation of a white surface haze) is caused by the migration of cyclic polyester oligomers to the surface of the TPU. Conventionally these unreactive cyclo-oligomers are removed by e.g extraction, or their formation is prevented by careful choice of diol and diacid as mentioned before in this blog. According to this invention the cyclic polyesters can be removed by treating the polyol with an enzyme. Enzymes of the lipase or cutinase type are immobilized by attachement to an inert and insoluble material and then heated together with the polyol at 70 to 90ºC to ‘cut’ the polyester rings. After treatment of the polyol the immobilized enzyme can be filtrated.

A cyclic diester

Hydrolysis Resistant Polyester Urethane

Patent Title: HIGHLY DURABLE POLYESTER POLYOL

 Number/Link: US2017/0022143

Applicant/Assignee: Kuraray

Publication date: 26-jan-2017

Gist”: PU from polyester polyol with bulky side groups

Why it is interesting: The invention is about polyester polyols prepared from a dibasic acid (e.g adipic acid) and a mixture of two diols: 3-methyl-1,5-pentanediol and cyclohexane-1,1-dimethanol. The diols are used in a molar ratio of about 1:1 (25-75 to 75-25 pref.). Polyurethanes prepared with these polysters are said to be highly hydrolysis resistant in both acidic and basic environments.

Cyclohexane-1,1-dimethanol

Cyclohexane-1,1-dimethanol

Self-Healing Polyurethane Elastomers

Patent Title: POLYURETHANE

 Number/Link: W02016185172

Applicant/Assignee: Croda

Publication date: 24-11-2016

Gist”: PU from polyols which contain both a fatty dimer residue and an H-bonding group, show self-healing properties

Why it is interesting: Polyurethane elastomers with ‘intrinsic’ self-healing properties (i.e. without the need for external chemicals like encapsulated monomers) can be prepared by reacting isocyanates with polyols that have at least one urethane, amide or carbonate group and at least one fatty dimer residue. It is theorized that the fatty dimer allows the soft-phase of the polymer to flow and H-bonds to form, thus restoring most of the properties after damage.  In the examples polyols with internal urethane groups were prepared by reacting C36 dimer diol with HDI, which were then reacted with MDI and BDO. Samples of the resulting elastomers were cut in half, and manually stuck together again under mild heating (60°C), thus recovering most of their tensile and elongation properties.

A dimer diol

A dimer diol