Classic PU Patent of the Month: Otto Bayer’s Invention of Polyurethane and Polyurea (1937)

Title: Verfahren zur Herstellung von Polyurethanen bzw. Polyharnstoffen

Number/Link: DE728981  (German)

Applicant/Assignee: I.G.Farbenindustrie

Publication date: 12-11-1942

Gist”: Production of polyurethanes by reacting diisocyanates and compounds containing at least two hydroxyl and/or amine groups.

Why it is interesting: This is the patent that marked the start of the polyurethane industry.   It covers both aromatic and aliphatic diisocyanates, notably NDI, MDI, TDI, HDI etc. The examples cover polyurethane and polyurea fibers and films. It is said that Bayer was trying to copy Nylon 6,6, the structure of which is very similar to a PU based on 1,6 hexanediol and 1,6 hexanediisocyanate.  The patent has only one claim:

“PATENTANSPRUCH:
Verfahren zur Herstellung von Polyurethanen bzw. Polyharnstoffen, dadurch gekennzeichnet, daβ man organische Diisocyanate mit solchen organischen Verbindungen
zur Reaktion bringt, die mindestens 2 Hydroxyl- oder Aminogruppen mit austauschbaren Wasserstoffatomen oder mindestens eine Hydroxylgruppe und mindestens eine Aminogruppe ,der genannten Art enthalten.”

Dr. Otto Bayer (1902-1982)

Dr. Otto Bayer (1902-1982)

Polyurea ‘Nano’-Particles to Improve Properties of Polyurethane Flexible Foams and Elastomers

Title: USE OF POLYUREA NANOPARTICLES AS PERFORMANCE MODIFIERS IN POLYURETHANE MATERIALS

 Number/Link: WO2014/012769

Applicant/Assignee: Huntsman

Publication date: 23-01-2014

Gist”: A dispersion of polyurea particles prepared from 4,4′ MDI, diamine chain extender and a high mole weight monoamine is used to improve mechanical properties of flex foam.

Why it is interesting: Dispersions of polyurea particles with an average diameter of a few hundred nanometer and a Tg>150°C (pref.) can be produced by first reacting a relatively high MW polyether monoamine and a di-isocyanate (optionally dispersed in e.g. polyol) and subsequently adding a diamine chain extender. The dispersion is then used in a flexible foam or elastomer formulation, such that the amount of particles in the material is about 1-5% (w/w). In an example a 2000MW EO/PO monoamine was used together with 4,4′-MDI and a diamine chain extender to produce a particle dispersion in polyol, which was then used in polyurethane formulations. The particles do seem to have a positive effect on mechanical properties, however, the results for flex foam are clouded because of a sharp increase in material density compared to the reference. This density increase may well be due to a cellopening effect as described in WO2007/104623  in which a similar particle dispersion is used.

Polyethermonoamine as used in the invention.

Polyethermonoamine as used in the invention.

Thermoplastic Polyurea Elastomers

Title: MELT PROCESSIBLE POLYUREAS AND POLYUREA-URETHANES, METHOD FOR THE PRODUCTION THEREOF AND PRODUCTS MADE THEREFROM

 Number/Link: US2013/0331538

Applicant/Assignee: University of Akron

Publication date: 12-12-2013 (priority PCT)

Gist”: Polyurea is made melt-processable by incorporating hydrogen-bond accepting chain extenders (HACE)

Why it is interesting: It is well known that polyurea elastomers with a decent hardblock content (of e.g. 30-35%) are not melt-processable. Because of very strong (bi-dentate) H-bond formation in the hard domains the material will degrade sooner than flow when heated. In this invention it is proposed to incorporate a relatively small amount of HACE to disrupt the hard domain structure and reduce flow temperature.  In an example a few parts of OH-ended pentamethylenepolycarbonate with a MW of 500 to 800 was used next to the conventional 1,6-hexamethylene chain extender to drop the flow temperature by 50°C while not affecting the tensile strength. (I suppose a NH2-ended polycarbonate could have been used as well to make an all-polyurea material).

Bi-dentate H-bonds between polurea molecules (left) disrupted by a polycarbonate group (right)

Bi-dentate H-bonds between polurea molecules (left) dusrupted by a carbonate group (right)

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