Thermoplastic PU-PS Graft Copolymers

Title: POLYURETHANE-BASED POLYMER COMPOSITION

 Number/Link: WO2014/147194

Applicant/Assignee: BASF

Publication date: 25-09-2014

Gist”: TPU microparticles react with styrene monomer resulting in a TPU-PS copolymer.

Why it is interesting: Blends of TPU with polystyrene are known, but compatibility is low and PS to TPU ratio therefore needs to be low as well  to prevent ‘delamination’ of injection moulded parts.  According to this patent application it is however possible to graft the PS onto TPU such that much higher PS/TPU ratio’s can be obtained. The TPU needs to be MDI-based and have a relatively low hardblock content and softening temperature. Apparently the PS grafts onto the MDI methylene groups which form radicals easily. In an example TPU micropellets are swollen in styrene monomer at low temperature together with dicumulperoxide as a radical initiator. The swollen particles are then dispersed in water together with an emulsifier and heated under pressure to form a 60-40 TPU-PS copolymer. A solvent-based process is also exemplified.  The resulting polymers are especially useful for injection moulded parts such as spring-aids.

MDI radical

MDI radical

Renewable Polyurea from Lysinol

Title: NEW POLYMERS DERIVED FROM RENEWABLY RESOURCED LYSINOL

 Number/Link: US2014/275311

Applicant/Assignee: Du Pont

Publication date: 18-09-2014

Gist”: Use of lysinol as renewable monomer for nitrogen-containing polymers including polyurea.

Why it is interesting: Lysinol or 2,5-diamino-1-hexanol is an amino alcohol derived from the amino acid lysine by  hydrogenation.  Lysine itself is produced by fermentation from sugars.  Annual production of lysine is apparently in excess of 1 million tonnes and its derivative lysinol is therefore considered as a potentially interesting biorenenawable monomer for a number of nitrogen-containing polymers. This patent application claims lysinol-based polyamides, polyimides, polyureas and “urethane crosslinked” polyureas including foams. In the examples urethane-polyureas are produced by reacting lysinol with hexamethylenediisocyanate using DABCO as catalyst.

Preparation of the two lysionol enantiomers from lysine.

Preparation of the two lysinol enantiomers from lysine.

Bio-Renewable Thermoplastic Polyurethanes

Title: HOMOGENEOUS EXTRUDED ARTICLES MADE FROM THERMOPLASTICALLY PROCESSABLE POLYURETHANES BASED ON POLYESTER DIOLS FORMED FROM SUCCINIC ACID AND 1,3-PROPANEDIOL

 Number/Link: US2014/0256902

Applicant/Assignee: Bayer

Publication date: 11-09-2014 (priority PCT)

Gist”: TPU based on polyester diols prepared from succinic acid and propandiol

Why it is interesting: The use of biorenewable raw materials is no longer a curiosity in polyurethane production. Especially natural oil-based polyols are currently fashionable in newly developed products.  These ‘NOPs’ are however not very suitable for the production of thermoplastic polyurethanes.  According to the current invention (partly) bio-renewable TPUs can be produced from polyester diols based on succinic acid and 1,3-propanediol. Both these monomers can be produced by fermentation of carbohydrates. 1,3-propanediol is produced on industrial scale by DuPont through fermentation of corn syrup using genetically modified E.Coli bacteria (“Bio-PDO”). In the examples PDO-succinate polyester diols with MW from 1000 to 2000 are used together with 4,4′-MDI and 1,4-butanediol to produce TPUs with shore hardness ranging from 85 to 94A and Tg’s from -18 to +11°C.

Succinic acid or butanedioic acid.

Succinic acid or butanedioic acid.

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