Oxidation-Proof TPU

Patent Title: POLYURETHANE, METHOD OF PREPARATION, AND ARTICLE COMPRISING THE POLYURETHANE

 Number/Link:  WO2018/057488

Applicant/Assignee:  THE UNIVERSITY OF MASSACHUSETTS

Publication date:  29 March 2018

Gist”:  TPU based on hydrogenated diene diols

Why it is interesting: TPUs based on polyether- or polydiene-diols are prone to oxidative degradation and therefore less useful for e.g. medical applications.  According to this invention, oxidation-stable TPUs can be prepared from hydrogenated polydiene diols with an Mn of 500 to 2000, combined with 5-25% (w/w) polyether diols, chain extender and diisocyanate.  In an example a hydogenated polybutadienediol with Mn of 2000 Da was reacted with 4,4′-MDI together with PTMEG 1000 and BDO in toluene.  At a hardblock content of 35% the TPU showed a Shore hardness of 80A, 250MPa tensile strength and an elongation at break of 520%.

PIB

Hydrogenated (1,2) polybutadiene

 

TPU for RTM

Patent Title: THERMOPLASTIC PUR WITH HIGH TG FOR REACTION TRANSFER MOLDING (RTM)

 Number/Link: WO2018/050433

Applicant/Assignee:  Henkel

Publication date: 22 march 2018

Gist”:  High Tg TPU from polycyclic diols

Why it is interesting: The invention is about thermoplastic polyurethanes with high Tg and high stiffness that are useful for fiber-reinforced composites made by (reactive) resin transfer moulding.  The TPU is prepared from an isocyanate, a conventional diol chain extender and at least 25% (w/w) of a bridged- fused- or spiro- polycyclic diol. In the examples MDI is reacted with 1,2-propanediol or 2,3-butandiol and 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane. The resulting TPUs show a Tg of more than 135°C.

tricylodecane

4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane

Thermoplastic Polythiourethanes for 3D Printing

Patent Title: THIOURETHANE POLYMERS, METHOD OF SYNTHESIS THEREOF AND USE IN FUSED FILAMENT FABRICATION PRINTING

 Number/Link:  WO2018/035102

Applicant/Assignee:  University of Texas

Publication date: 22 February 2018

Gist”: Polythiourethanes from diisocyanates and dithiols are used in FFF printing

Why it is interesting: Fused Filament Fabrication (FFF), which is actually the same thing as  Fused Deposition Modeling (FDM) is a popular and cheap additive manufacturing technology in which a thermoplastic filament is molten and ‘printed’ in layers. Many off-the-shelf thermoplastics can be used in FFF but these often do not have the correct melt characteristics resulting in printed objects of poor quality. According to this invention FFF-optimized thermoplastics can be prepared by reacting dithiols with diisocyanates into polythiourethanes.  The reaction is carried out in an aprotic solvent and catalysed by a non-nucleophilic base. In an example 2,2′-(ethylenedioxy)diethanethiol is reacted with HDI in DMF and catalysed by triethylamine. FFF printed parts of this polymer are said to show high toughness and less water uptake compared to TPU and polyamides.

polythiourethane

Polythiourethane according to the invention

 

Polyurethanes from Alpha Glucan

Patent Title: POLYURETHANE POLYMERS COMPRISING POLYSACCHARIDES

 Number/Link: WO2018/017789

Applicant/Assignee:  Du Pont

Publication date: 25 january 2018

Gist”: Polyurethanes containing poly alpha 1,3-glucan

Why it is interesting: The invention is related to the preparation of different types of polyurethanes comprising poly alpha 1,3-glucan, which is a polymeric D-glucose having alpha 1,3 glycosidic bonds (as opposed to most natural glucose polymers which show α or β 1,4 glycoside linkages). Alpha 1,3 glucan can be prepared by enzymatic polymerization using sucrose and a glycosyltransferase. The glucan can be mixed with polyols and reacted with isocyanates to prepare polyurethanes.  Many examples are given ranging from PUDs, films, flexible foams to TPUs.

glucan

Poly alpha 1,3-glucan

 

Fluorinated Thermoplastic Polyurethanes

Patent Title: SHOE UPPERS & CASE FOR PORTABLE DEVICES

 Number/Link: WO2018/007359  WO2018007360

Applicant/Assignee:  Solvay

Publication date:  11 January 2018

Gist”:  F-TPUs are prepared by incorporating perfluoro diols

Why it is interesting: The current inventions are about fluorinated TPU and its applications. The F-TPUs are prepared by replacing part of the polyol with hydroxyl-ended fluorinated polyethers. In the examples fluorinated polyether diols are used in different ratios to conventional polyester-, PTMEG-, CAPA- and polycarbonate diols and reacted with MDI or HDI and BDO or HDO as chain extenders. The F-TPUs can be used as uppers for footwear and as cases for smartphones and are said to have improved stain resistance and – surprisingly- a soft feel to the touch.

case

F-TPU smartphone case