Reactive TPU for AM

Patent Title: REACTIVE THERMOPLASTIC POLYURETHANE BASED ON BLOCKED ISOCYANATES

 Number/Link: WO2018/149977

Applicant/Assignee:  BASF

Publication date: 23 August 2018

Gist”: Low molecular weight TPU with blocked isocyanate groups is useful for 3D printing

Why it is interesting: The invention is related to relatively low MW ( up to 40,000Da) thermoplastic polyurethanes with thermolabile end groups and a melting point of about 100ºC (pref).  The TPU has a low melt viscosity and after de-blocking (at pref. about 150ºC) the isocyanate groups can react with chain extender present, resulting in increased MW and related properties. The TPU can be prepared by partially blocking diisocyanates (with e.g. caprolactam) and then reacting in one shot or prepolymer system with polyols and chain extenders. In powder form the TPUs are said to be useful in additive manufacturing (AM) processes.

caprolactam

Caprolactam

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

 

Breathable TPU Membranes

Patent Title: POROUS THERMOPLASTIC MEMBRANES

 Number/Link: WO2017/178482

Applicant/Assignee:  BASF

Publication date: 19-october-2017

Gist”: Semi-permeable membranes are made by phase inversion of all-hardblock TPU solutions

Why it is interesting: ‘Breathable” membranes show a high resistance to liquid water permeation (LEP) combined with a high water vapour permeability (WDD). According to this invention breathable polyurethane membranes can be prepared by dissolving an all-hardblock thermoplastic polyurethane in a polar, aprotic solvent (like N-methyl pyrrolidone) together with a water soluble compound, casting a film and coagulating the film with water. In the examples diisocyanates (MDI, TDI and HDI) are stoichiometrically reacted with chain extenders (MEG, BDO and HDO).  The resulting materials were schredded and dissolved in NMP together with some glycerol. 150 μm thick films were cast on glass and coagulated in water, resulting in membranes with an average pore size ranging between 4 and 500 nm.  The membranes are said to be useful to make breathable fabrics for outdoor wear e.g. (“Gore Tex” (TM) – type materials)

N-methyl-2-pyrrolidone

 

 

 

 

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.