TPU from HDI and H12MDI

Patent Title: NON-SOFTENING RESILIENT THERMOPLASTIC POLYURETHANES

 Number/Link: WO2016/054320

Applicant/Assignee: Lubrizol

Publication date: 7-04-1016

Gist”: TPU from a blend of HDI and H12MDI has improved creep and wet modulus

Why it is interesting: Polymeric materials used for in vivo medical applications like catheters, need to be hydrolytically stable and retain physical properties like stiffness, resilience, flexibility etc. in wet conditions.  It is known that conventional TPUs based on aromatic or cyclo-aliphatic isocyanates tend to show some softening in aqueous environments. For this reason copolyamides (COPAs) and polyether-block-polyamides (PEBAs) are often preferred over TPU for use in medical devices.  According to this invention, TPUs that can replace COPA and PEBA in medical applications can be produced using a blend of 1,6-hexanediisocyanate (HDA) and H12MDI. In the examples polyether TPUs, prepared from 2000MW polytetramethyleneether diol, butanediol and a 19:1 HDI:H12MDI isocyanate blend at harblock contents ranging from 15 to 50%, convincingly show improved creep properties and wet modulus when compared to conventional TPU and a commercial PEBA material.

H12MDI

H12MDI

TPU from Biorenewable Isocyanate

Patent Title: BIO-BASED DIISOCYANATE AND CHAIN EXTENDERS IN CRYSTALLINE SEGMENTED THERMOPLASTIC POLYESTER URETHANES

 Number/Link: WO2016041076

Applicant/Assignee: Trent University

Publication date: 24-03-2016

Gist”:  TPU with highly crystalline hard segment is based on 1,7 heptamethylenediisocyanate

Why it is interesting: According to this application, polyester TPUs with crystalline hard segments can be produced using 1,7-heptamethylenediisocyanate. The HPMDI is reacted with a 2000MW poly(ethyleneadipate) diol and a short chain diol as chain extender. The  TPUs show a high hard-segment crystallinity, resulting in improved phase separation and in a (semi-)crystalline softphase which has a significant reinforcement effect. The TPUs are thermally stable up to 250°C and show a toughness and strength comparable to conventional TPUs. HPMDI can reportedly be made from natural oils using the Curtius rearrangement – but no reference is given.

Curtius Rearrangment

Curtius Rearrangment

Polyurethane Elastomers from Modified Polybutadienols

Patent Title: POLYESTER-MODIFIED POLYBUTADIENOLS FOR PRODUCING POLYURETHANE ELASTOMERS AND THERMOPLASTIC POLYURETHANES

 Number/Link: WO2016/026807  (German)

Applicant/Assignee: BASF

Publication date: 25-02-2016

Gist”: Polybutadiene polyols are capped with caprolactone

Why it is interesting: Liquid hydroxy-terminated polybutadienes have been available for quite a while and their use in polyurethane elastomers and TPUs is known.  However, because of their immiscibility with isocyanates, polyols and most chain extenders they are notoriously difficult to process, resulting in elastomers that often show poor or inconsistent properties. According to this invention the problem can be solved by capping the polybutadienols with a few moles of cyclic ester, preferably with ε-caprolactone. The capped polyols are miscible with e.g. MDI and butanediol and the resulting elastomers show much improved properties compared to both polybutanedienol- and polycaprolactone- based elastomers.

Caprolactone

Epsilon-caprolactone

ε

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