Crystalline High-Hardblock TPU

Title: CRYSTALLINE HIGH MODULUS THERMOPLASTIC POLYURETHANE

Number/LinkWO2017079101  WO2017079188

Applicant/Assignee: Lubrizol

Publication Date: 11 May 2017

“Gist”: High-hardblock TPU using ‘stacking’ chain extenders and MDI

Why it is interesting: Thermoplastic polyurethanes with hardblock levels of 75% and higher were first patented by Upjohn in 1981 in a “classic” patent which has been discussed before in this blog. These materials – often marketed under the ‘ISOPLAST’ tradename- are usually produced from a diol, 4,4′-MDI and a (mixture of) chain extender(s) comprising a ‘non-stacking’ chain extender like cyclohexanedimethylol, neopentylglycol, MPdiol etc. to control crystallinity. In the current invention only ‘stacking’ chain extenders are used in an otherwise identical composition, resulting -unsurprisingly- in a more crystalline material with a higher modulus and melting temperature. It is also said that these materials are easier to compound with e.g. fire retardants.
Even if this idea were formally ‘new’ I doubt its inventiveness and therefore its patentability.

The famous ISOPLAST(TM) nail

Triptycene Chain Extenders

Title: TRIPTYCENE MONOMER AND TRIPTYCENE CONTAINING POLYESTERS AND POLYURETHANES

 Number/Link: US20150191408

Applicant/Assignee: not yet recorded. Research supported by US Army

Publication date: 9-07-2015

Gist”: A novel primary diol derived from triptycene is useful as chain extender for polyurethanes and polyesters.

Why it is interesting: Polymers with increased mechanical properties and stiffness can be obtained by incorporating rigid structures in the polymer chain.  This however also results in increased glass transition temperature and reduced ductility because of reduced chain flexiblity and entanglements.  According to this invention polyurethanes (and copolyesters) with high modulus and good ductility at low temperatures can obtained by using triptycene-1,4-hydroquinone-bis(2-hydroxyethyl ether) or TD. In and example TD capped with PEG400 is reacted with a 4,4’MDI- PTMEG1000 prepolymer.  The resulting material indeed has a very low softblock Tg of  -65ºC and a much higher Y modulus compared to a PU made with HQEE as chain extender. According to the inventors the PU is highly suitable as a matrix material in KEVLAR or UHMWPE fiber composites.
In my opinion this is a very interesting chain extender as it appears to prevent H-bond formation and increase molar volume thereby substantially decreasing Tg. However lack of availability, and (most probably) price, will prevent this from becoming mainstream anytime soon.

Tryptycene-1,4-hydroquinone-bis(2-hydroxyethyl ether)

Triptycene-1,4-hydroquinone-bis(2-hydroxyethyl ether)

 

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