Self-Healing Polyurethanes

Title: SELF-HEALING POLYURETHANES

 Number/Link: WO2015/067833 (Spanish)

Applicant/Assignee: Fundacion Gaiker

Publication date: 14-05-2015

Gist”: Self-healing polyurethanes coatings can be prepared using dihydroxy coumarin derivatives

Why it is interesting: Self-healing polymers have been made before using e.g. microencapsulated ‘healing agents’ or supramolecular chemistry such as hydrogen-bond formation.  This patent application relates to polyurethanes having photochemical self-healing properties, which, in contrast to previous systems, have the advantage of allowing for multiple recoveries and for (potentially) being transparent. The self-repairing PU systems are based on the photodimerization and photocleavage reactions of coumarine-derivatives as shown in the scheme below.  Dihydroxy derivatives of coumarine can be built into PU coatings sytems. Damaged coatings can then be radiated with light of a wavelength of (pref.) 254nm to cleave coumarin dimers present, followed by radiation of about 340nm to (re-)form the dimers and repair the coating.

Photodimerization and -cleavage of coumarine derivatives

Photodimerization and -cleavage of coumarine derivatives

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

 

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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