Rigid Thermoplastic Polyurethanes

Patent Title: ISOCYANATE-MODIFIED RIGID THERMOPLASTIC POLYMER COMPOSITIONS

 Number/Link: WO2017/146948  WO2017/146949

Applicant/Assignee: Eastman Chemical

Publication date: 31 august 2017

Gist”: A “rigid”, high Tg polyester diol is extended with 4,4′ MDI

Why it is interesting: Rigid, high modulus TPUs have been known for a long time – see e.g. Upjohn’s classic patent on ‘Isoplast’ from 1981. These materials are high hardblock TPUs made from diisocyanates, chain extenders with only a small amount of high molecular weight diol as an impact modifier. According to the current invention however, rigid TPUs can be made using less than 40% (w/w) of diisocyanate, a high Tg polyester diol and optionally some chain extender.  The polyester is prepared from ‘rigid’ diols like isosorbide or 1,4-cyclohexanedimethanol together with a ‘rigid’ diacid like terephthalic acid, such that the diol has a MW of more than 400 Dalton and a Tg of more than 40°C. The diisocyanate is pref. 4,4-MDI. The rigid TPUs have a Tg of more than 145°C and a tensile modulus of 1 GPa or higher. They are said to be less moisture sensitive than conventional rigid TPUs.

1,4-cyclohexanedimethanol

TPU Aerosol

Title: POLYURETHANE AEROSOL COMPOSITIONS, ARTICLES, AND RELATED METHODS

Number/Link: US20170198150

Applicant/Assignee: 3M

Publication Date: 13-july-2017  (priority PCT)

“Gist”: Aqueous dispersion of a hydrazide-extended  TPU can be sprayed as aerosol to make protective films

Why it is interesting: An aqueous thermoplastic polyurethane dispersion is prepared from a non-yellowing diisocyanate, e.g. bis(4-isocyanatocyclohexyl), a diol (e.g. PPG2000), a difunctional hydrazine or hydrazide chain extender (e.g. 1,3-diaminourea) and a water solubilizing compound (e.g. dimethylolpropionic acid).  Together with a propellant the, composition is shelf-stable and can be aerosol-sprayed to form clear, non-yellowing protective films.

3M’s aerosol-sprayed protective film.

TPU Shrink Wrap

Title: TPU SHRINK MATERIAL

Number/Link: WO2017/108920

Applicant/Assignee: BASF

Publication Date: 29-jun-2017

“Gist”: Shape memory TPU is used as shrink wrap

Why it is interesting: A thermoplastic polyurethane with a shape-memory is prepared from a diisocyanate, a chain extender and a polyol comprising an ‘aromatic polyester block’, especially a polyethylenetherephthalate block. The composition is chosen such that the TPU has a melting point between 160 and 230ºC and another phase transition between 30 and 80ºC (the “switching temperature”). Films of this material are then stretched at a temperature higher than the switching temperature but below melt temperature and then cooled in stretched state. The stretched films are said to be useful as shrink wrap, especially for foodstuffs. No examples are given.
A surprising application for TPU but hardly a surprising TPU invention i.m.o.

Shrink-wrapped Helicopters (Wikipedia)

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