Nanocomposites from PIB-Based Polyurethane and Clay

Title: POLYISOBUTYLENE-BASED POLYURETHANES CONTAINING ORGANICALLY MODIFIED MONTMORILLONITE

 Number/Link: WO/2014/018509

Applicant/Assignee: UNIVERSITY OF AKRON

Publication date: 30-01-2014

Gist”: A small amount of montmorillonite, modified with a quaternary ammonium compound containing an amine group, is incorporated in a polyisobutylene-based TPU.

Why it is interesting: Montmorillonite-type clay is “exfoliated” using a quat. ammonium compound which has an alkyl subsituent containing a primary amine group. The salt group will electrostatically interact with the clay while the amine group will react with isocyanate when used in a polyurethane formulation, thus incorporating the clay into the polymer structure. In an example a (T)PU is made from HMDI, 1,6-hexanediol and a mixture of a 4000MW polyisobutylene diol and a 1000MW PTMO diol. A montmorillonite was exfoliated using trimethyl-1-propylamine ammonium iodide (I¯N+(CH3)3CH2CH2CH2-NH2)  and incorporated in the PU to make the nanocomposite. In an amount of 0.5% (w/w) the clay increases stiffness, mechanical- and creep properties of the PU.  However at higher amounts (2%,5%..) these properties actually deteriorate.

Polymer morphology model according to the invention.  (omMMT = organically modified montmorrilonite)

Polymer morphology model according to the invention. (omMMT = organically modified montmorillonite)

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)

Expandable Polyurethane Particles for Insulation Panels

Title: POLYURETHANE-BASED EXPANDABLE POLYMER PARTICLES

 Number/Link: WO2014/006182  (German)

Applicant/Assignee: BASF

Publication date: 9-01-2014

Gist”: Microgranules of TPU/PS copolymer containing pentane can be expanded into insulation panels using standard EPS equipment.

Why it is interesting: Contrary to polystyrene, thermoplastic polyurethane cannot be ‘imbued’ with a physical blowing agent like pentane to make steam-expandable particles. This is due a.o. to the high diffusion rate of pentane (e.g.) in TPU.  BASF have now found that by using a TPU/PS copolymer, expandable particles can be prepared which can be used in standard EPS (expandable polystyrene) equipment to make insulation panels. The TPU used is based on 4,4′-MDI, polyTHF and butanediol such that the vicat softening point is below 80°C.   The TPU, in the form of microgranules (0.5-2mm), is swollen in styrene containing dicumylperoxide, dispersed in water and heated to polymerisation.  A blowing agent like (pref) pentane is added to the dispersion as well. The resulting particles are expandable and can be used to make insulation panels of 50-150 kg/m³.

Expandable Polystyrene.

Expandable Polystyrene.

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