Hydrophobic and Clear Thermoplastic Polyurethane

Title: CLEAR HYDROPHOBIC TPU

 Number/Link: WO2014/121174

Applicant/Assignee: Lubrizol

Publication date: 7-08-2014

Gist”: A hydrophobic, clear and low density TPU is prepared from 4,4’MDI, a dimer acid-based polyol and a mixture of “non-stacking” chain extenders.

Why it is interesting: Most commercial TPUs are hydrophilic to a certain extend and because of phase separation and partial crystallization are often transparent but not clear. The current invention teaches a highly hydrophobic and clear TPU made form 4,4′ MDI, a polyester polyol produced by reacting a C36 dimerized fatty acid (“dimer acid”) with 1,6-hexanediol and a chain extender mixture consisting of 1,12-dodecanediol and 2-butyl,2-ethyl propanediol or  1,4-cyclohexanedimethanol (all preferred). Hardblock content in the examples is between 25 and about 45% resulting in a shore A hardness range of about 75 to 95. No thermal data are given.
While this is no doubt an interesting material, I expect this to be a single phase glass with a relatively low Tg and therefore less useful for structural applications.

Example of a C36 dimer acid

Example of a C36 dimer acid

 

Hydrolysis Resistant Polyester Polyurethane

Title: A POLYESTER POLYURETHANE MATERIAL WITH LONG TERM HYDROLYSIS RESISTANCE

 Number/Link: WO2014114614

Applicant/Assignee: Bayer

Publication date: 31-07-2014

Gist”: Hydrolysis resistant polyurethane elastomers can be prepared from sterically hindered polyester polyols together with a perchlorate salt.

Why it is interesting: Because of their high mechanical properties and abrasion resistance, polyester-based polyurethane elastomers are a material of choice in e.g. the footwear and automotive industries. Main drawback however is their susceptibility to hydrolysis which causes loss of physical properties in moist environments.  According to the current invention, hydrolysis resistance can be greatly improved by using a specific polyester polyol together with a perchlorate salt (e.g. 0.3% sodium perchlorate on the total composition). The polyester polyol is based on a diacid (e.g. adipic acid) and a mixture of diols one of which contains alkyl side groups (e.g. a mixture of butanediol and neopentylglycol).
The invention is actually a combination of two known ‘tricks’:  the neopentyl glycol will introduce some hydrophobicity and steric hindrance into the polyester backbone, and the perchlorate may have a weak coordination with the hydrolysable ester bonds thus forming a steric protection layer (at least according to Bayer’s own WO2013/030147). Because both effects are known and published I doubt that this is patentable.

Neopentylglycol

Neopentylglycol

Classic PU Patent of the Month: The First SMPUs (1988)

Title: Shape memory polymer foam.  – and – Shape memory polyurethane elastomer molded article.

 Number/Link: EP0361418 and EP0361419

Applicant/Assignee: Mitsubishi Heavy Industries

Publication date: 27-09-1989

Gist”: The first shape memory polyurethane foams and elastomers

Why it is interesting: Shape memory polymers are so-called “smart materials” that remain in a deformed shape until a trigger (usually an increase in temperature) makes them return to their original  (“memorized”) shape. In the 1980s these materials were more of a curiosity, only used in some niche applications such as heat shrinkable tubing. Currently however a lot of academic and industrial research is done on these materials, mostly driven by medical applications (e.g. stents, orthopedic casts, self-tightening sutures etc). And not surprisingly a lot of current SMPs are based on polyurethanes (SMPUs).  Interest in shape memory materials was stimulated significantly by the invention of the first SMPUs by Mitsubishi H.I. Ltd. They filed two patents covering both shape memory foams and elastomers. The first SMPUs were based on a di-isocyanate like 4,4′-MDI, a diol like PPG700 and a chain extender like bisphenol-A, and were formulated over a range of Tg’s. The foamed materials were blown with a physical blowing agent (i.e. not water) so that all materials can be considered thermoplastics.

SMP transition from temporary shape (spiral) to permanent shape (rod).  (Angew. Chem. Int. Ed. 2002, 41, 2034 ± 2057)

SMP transition from temporary shape (spiral) to permanent shape (rod). (Angew. Chem. Int. Ed. 2002, 41, 2034 ± 2057)

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