Soft, High Resilience Polyurethane Elastomers

Title: URETHANE FOAM RUBBER AND COMPOSITION FOR FORMING URETHANE FOAM RUBBER

 Number/Link: US20150105485

Applicant/Assignee: Yamaha

Publication date: 16-04-2015

Gist”: Use of carbodiimide-MDI to make soft high resilience elastomers

Why it is interesting: According to this patent application, soft, high-resilient PU elastomers with a density higher than 300 kg/m³ can be prepared from a diisocyanate, a polyether polyol with a molecular weight of about 1000 to 4000 together with some polymeric MDI. The invention being, that the diisocyanate needs to have an “atom number minimum bond path” between the two NCO groups of at least 11.  Examples of such diisocyanates would be α,ω-undecane- (or dodecane- or tridecane- etc.) diisocyanates, propylene-1,3-di(1,4-cyclohexylene diisocyanate) but also carbodiimide modified MDI which is preferred. Examples are given of 440 kg/m³ elastomers with a ball rebound of 81 and an Asker C hardness of 44 at temperatures ranging from -20°C to 50°C,  based on a polyTHF diol with a MW of 2000 and a carbodiimide modified MDI.  No other isocyanates are used in the examples, so it appears to me that the “atom number minimum bond path” is just an attempt to make this case new and patentable. Not very convincing. I would like to see an example with tridecanediisocyanate.

Carbodiimide modified MDI

Carbodiimide modified MDI species

 

 

 

 

Supercritically Foamed Thermoplastic Polyurethane

Title: LOW DENSITY FOAM, MIDSOLE, FOOTWEAR, AND METHODS FOR MAKING LOW DENSITY FOAM

 Number/Link: WO2015/017088

Applicant/Assignee: Nike

Publication date: 5-02-2015

Gist”: TPU blown with supercritical CO2 and/or N2

Why it is interesting: This case relates to foamed TPU (or EVA) with densities down to 150 kg/m³. The low density is accomplished by the combination of a conventional physical blowing agent and a supercritical fluid, specifically supercritical CO2 or N2 or a combination of these. The conventional blowing agent is incorporated into the polymer pellets before these are added to the extruder while the supercritical fluid is added to the molten polymer through a port in the extruder barrel.  The material is then extruded or injection moulded. Nike have filed two more patents on this technology: WO2015/017089 and WO2015/017090.

Nike shoe with EVA midsole

Nike shoe with foamed thermoplastic midsole

Ionic Liquids for Improved Hydrolysis Resistance of Polyester Polyurethanes

Title: HYDROLYSIS-RESISTANT POLYURETHANE MOULDED ARTICLES MADE OF POLYESTER POLYURETHANE

 Number/Link: WO2014/095438  (German)

Applicant/Assignee: BASF

Publication date: 26-06-2014

Gist”: Polyester polyurethane elastomers containing carbodiimides, together with an ionic liquid and an amine catalyst in a specific ratio, show improved hydrolysis resistance.

Why it is interesting: Polyester PU elastomers show higher mechanical properties compared to polyether elastomers but have have a much worse hydrolysis resistance.  It is well known that the hydrolysis resistance can be improved by using sterically hindered carbodiimides (commercially known e.g. as Stabaxol®).  This invention shows that hydrolysis resistance can be even more improved by using a specific molecular ratio (pref. 0.5 : 1 to 2 : 1)  of  ionic liquid to amine catalyst in combination with the carbodiimides. The effect is apparent from the examples where 1-ethyl-3-methylimidazolium ethylsulfate was used as ionic liquid together with ethylenediamine as catalyst.  No theory or explanation for the effect is given and it is not immediately clear to me how this interesting synergy works.

Ionic liquid as used in the invention

Ionic liquid as used in the invention

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