Hydrophobic Thermoplastic Polyurethanes

Title: POLYURETHANE

 Number/Link: US2015/0119535

Applicant/Assignee: Nippon Soda

Publication date: 30-04-2015 (priority PCT/JP)

Gist”: TPU based on a ‘hybrid’ polybutadiene-polyester polyol and an asymmetric isocyanate

Why it is interesting: According to this invention, TPUs with excellent water-resistance can be prepared from a polyol which is made by reacting a polybutadiene diol with a mole weight of a few 1000 with a cyclic ester monomer, up to a mole weight of about 5000 to 15000 (preferred).  The resulting ‘hybdrid’  (polyester-polybutadiene-polyester) polyol is then prepolymerized with a surplus of an assymetric di-isocyanate. Finally the prepolymer is reacted with a chain extender to make the TPU. In the examples polybutadiene diols are reacted with ε-caprolactone and then with IPDI or 2,4-TDI.  The chain extender used is 1,4-butanediol. Interesting materials and (but) relatively soft as would be expected.

Caprolactone

Caprolactone

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

 

 

 

 

Particle-Reinforced Thermoplastic Polyurethane

Title: COMPOSITION AND ARTICLE COMPRISING THERMOPLASTIC POLYURETHANE AND PARTICULATE ENGINEERING POLYMER

 Number/Link: WO2015/031292

Applicant/Assignee: SABIC

Publication date: 5-03-2015

Gist”: TPU is reinforced with ultrafine particles made from engineering thermoplastics having a melting point of over 200°C.

Why it is interesting: Particulate polyarylsulfone, polyimide, poly(phenylene sulfide) or polyamide, with a melting point or glass transition higher than 200°C and average particle size between 5 and 200 μm, is melt-blended with TPU at a temperature below 200°C and in an amount of 10-30% (w/w).  Alternatively the particles could be mixed (“slurried”) with the polyol and/or isocyanate used to produce the TPU.  The resulting composite is said to have increased hardness, tensile strength and heat resistance.
Sabic is becoming quite active in polyurethane innovation and is apparently looking for synergies with its engineering thermoplastics business.

Poly (1,4-phenylene sulfide) (PPS)

Poly (1,4-phenylene sulfide) (PPS)

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