Fiber Reinforced TPU Composites

Patent Title: THERMOPLASTIC POLYURETHANE MATRIX RESIN

 Number/Link: WO 2018/104145

Applicant/Assignee:  Henkel

Publication date: 14 June 2018

Gist”: TPU based on a vicinal alkane diol together with an alkoxylated aromatic diol can be used as matrix material in a fiber composite

Why it is interesting: According to this invention a thermoplastic polyurethane with a high Tg (pref. >80°C) and a high stiffness (>1GPa) can be prepared from a short chain, sterically hindered, vicinal diol (e.g. 1,2-propanediol or 2,3-butanediol), an alkoxylated aromatic diol (e.g. alkoxylated bisphenol A or F) and an aromatic diisocyanate (e.g. 4,4’MDI) pref. mixed with some high functionality isocyanate (e.g. polymeric MDI) to control branching an molecular weight. The TPU composition can be used to make a fiber reinforced composite in an RTM-type process. The cured thermoplastic matrix has high mechanical properties but still allows for post-cure modification of the moulded part.

EtoxBisF

Ethoxylated Bisphenol F

Steam-Treated Polyisocyanurate: Take Two

Title: PROCESS FOR MAKING URETHANE-ISOCYANURATES

 Number/Link:WO2015/006391

Applicant/Assignee: Dow

Publication date: 15-01-2015

Gist”: Treating PUR-PIR with hot water at superatmospheric pressure results in a Tg increase.

Why it is interesting: This is exactly the same invention as discussed a while ago on this blog: WO2014/160616 . But, apart from the title, the application has been completely re-written by another agent and filed less then 4 months  after the first one. The only difference in the claims appears to be that the temperature and index ranges are taken a bit wider and that filled polyols and polyester polyols are claimed separately.  Very strange.  Is it possible that they forgot they already filed this?

Isocyanurate group

Isocyanurate group

Steam-Treated Polyisocyanurate

Title: PROCESS FOR MAKING URETHANE-ISOCYANURATES

 Number/Link: WO2014/160616

Applicant/Assignee: Dow

Publication date: 2-10-2014

Gist”: Treating PUR-PIR with hot water at superatmospheric pressure results in a Tg increase.

Why it is interesting: Fiber-reinforced phenol-formaldehyde composites are used to make pipes among other things.  They are however not completely stable in hot humid conditions so that they are less well suited for off-shore piping systems for example. According to this patent application, polyisocyanurate (PIR) or polyurethane-polyisocyanurate (PUR-PIR) systems are more suitable materials for such applications because properties of these materials remain stable and -surprisingly- glass transition temperature increases when subjected to high pressure water or steam. In the examples PUR-PIR systems based on polymeric MDI submerged in water at 120°C and 3500 kPa for 7 days show indeed an increase in Tg.  In my opinion it would be interesting to repeat the experiment with 4,4′-MDI based PUR/PIR.  Because 4,4′ MDI will show a higher conversion rate to PIR the ‘steam effect’ may well dissapear.

Isocyanurate group

Isocyanurate group