Non-Isocyanate Polyurethanes from Thiocarbonates

Patent Title: PROCESS FOR THE MANUFACTURING OF A POLYMER WITH URETHANE GROUPS

Number/Link: WO2019/034470 and WO2019/034473

Applicant/Assignee: BASF

Publication Date: 21 February 2019

“Gist”:  A cyclic thiocarbonate is reacted with a diamine and then with a diacrylate

Why it is interesting: NIPU is prepared by reacting a five-ring monothiocarbonate with di- (or poly-) amine and then with a compound having at least two thiol-reactive functional groups like e.g. ethylenically unsaturated groups. The reaction has advantages over conventional PU chemistry like being isocyanate-free, less moisture sensitive and running at moderate temperatures. In an example methyl monothiocarbonate is reacted with 1,5-pentanediamine and 1,4-butandioldimethacrylate, resulting in a colourless, transparent polymer with a high thermal stability.
An interesting take on hybrid non-isocyanate polyurethanes.

scheme1

Reaction scheme according to the invention

Novel Chain Extenders

Patent Title: METHOD OF PRODUCING FIVE-CARBON RING-CONTAINING COMPOUND AND FIVE-CARBON RING DERIVATIVE-CONTAINING POLYURETHANE, AND FIVE-CARBON RING DERIVATIVE-CONTAINING POLYURETHANE

Number/Link: US2019/0048123

Applicant/Assignee: CHUNG SHAN INSTITUTE OF SCIENCE AND TECHNOLOGY

Publication Date: 14-February 2019

Gist”: Novel chain extenders are derived from dicyclopentadiene (DCPD)

Why it is interesting: DCPD is a by-product of ethylene production by steam cracking of naphta.  It is produced in large quantities and it makes sense to search for new applications.  According to this invention, the compound shown below can be prepared by first ‘degrading’ DCPD to cyclopentadiene, followed by reaction with phenol to produce 4-(cyclopent-2-enyl)phenol which is then converted to 4-cyclopentenylphenol (translocation of the double bond).  The cyclopentenylphenol is then reacted with phenol followed by reaction with ethylene carbonate to produce the chain extender. In an example the chain extender is reacted with a 4,4′-MDI prepolymer in solvent.
Clever chemistry and an interesting compound, but its usefulness remains to be shown.

extender

Chain extender according to the invention

Thermoplastic PU-PDMS Copolymer

Patent Title: THERMOPLASTIC POLYURETHANE

Number/Link: WO2019/016313 (German)

Applicant/Assignee: BASF

Publication Date: 24 January 2019

“Gist”:  Thermoplastic polyurethane comprising OH-ended poly(dimethylsiloxane).

Why it is interesting: The invention relates to thermoplastic polyurethanes prepared from diisocyanate, polyether or polyester diol and a difunctional isocyanate-reactive polysiloxane.  The materials are said to have improved “haptic”-, hydrophobicity- and tensile properties while retaining the processibility of TPU and are useful for ‘on-body’ applications like wristbands. In the examples both 4,4′-MDI and HDI are used together with chain extenders, polyTHF, BDO-HDO adipate and EO capped PDMS to prepare TPUs ranging from 55 to 95 Shore A.

pdms-eo

EO-capped PDMS