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)

Classic PU Patent of the Month: Upjohn’s “Isoplast®” (1981)

Title: Polyurethane prepared by reaction of an organic polyisocyanate, a chain extender and an isocyanate-reactive material of m.w. 500-20,000 characterized by the use of only 2-25 percent by weight of the latter material

 Number/Link: US4376834

Applicant/Assignee: Upjohn

Publication date: 15-03-1983

Gist”: Very high hardblock TPU from MDI and chain extenders.

Why it is interesting: “Isoplast” is a so-called engineering thermoplastic useful in niche applications where high impact strength and high chemical resistance are required. The material can be clear or reinforced and can also be used in fiber-reinforced composites.  Currently the trademark is owned by Lubrizol who acquired it from Dow who in turn bought it from Upjohn in the 1980s.  Isoplast is made from 4,4′ MDI and a mixture of chain extenders selected from MEG,DEG, neopentyl glycol, 1,4-cyclohexanedimethanol etc. The choice of chain extenders controls the crystallinity/glassiness of the polymer.  A few percent of high mole weight polyol may be added to improve impact resistance. A very interesting material with interesting melt-flow characteristics because of its depolymerization and repolymerization behaviour during processing.

Screw from reinforced Isoplast

Screw from reinforced Isoplast

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