Polyurethane/Polyurea Elastomers from 2,4′-MDI and MDA

Title: MOLDED POLYURETHANE ELASTOMER PARTS MADE OF DIPHENYLMETHANE DIISOCYANATE-BASED NCO PREPOLYMERS AND METAL SALT COMPLEXES, AND A METHOD FOR PRODUCING SAME

 Number/Link: US2013267655

Applicant/Assignee: Bayer

Publication date: 10-10-2013 (priority PCT/DE)

Gist”: Molded PU/PUA elastomers are prepared from a 2,4′-MDI based prepolymer cured with blocked MDA

Why it is interesting: A prepolymer with an NCO content between 3 to 7% is prepared from MDI containing more than 97% of the  2,4′ isomer together with a diol with an OH value of about 100.  (e.g a PTMEG or a polycaprolacton).  The prepolymer is then cured with a salt-complexed diphenylmethanediamine (“blocked MDA”). Because of it’s relatively low viscosity and long potlife the system allows for the production of thick-walled, bubble-free molded elastomers.  Probably because there is less premature polyurea phase separation (due the 2,4′-MDI) the system cures homogeneously.

4,4'-MDA

4,4′-MDA

Brominated Polyurethane Oligomers

Title: FLAME-RETARDING OLIGOMERIC BROMINATED URETHANE COMPOSITIONS

 Number/Link: US2013/0217286

Applicant/Assignee: Lubrizol

Publication date: 22-08-2013 (priority PCT)

Gist”: Use of highly brominated isocyanate-reactive monomers to prepare brominated PU oligmers useful as non-leaching fire retardants.

Why it is interesting: Brominated fire retardants are highly effective in polyurethanes but their use is being phased-out because of environmental issues and the production of some of them will be discontinued in the near future. Brominated PU oligomers can be used as fire retardants with less environmental problems as they are not fugitive and will leach less.  The oligomers can be produced using monofunctional highly brominated isocyanate-reactive monomers like tribromoneopentanol or pentabromophenol. Difunctional brominated monomers can also be using together with monofunctional isocyanates to control the molecular weight which is preferably between 800 and 20,000 (claimed).  The oligomers can be used as fire retardants in PU dispersions (claimed) and in other polyurethane compositions e.g. in TPUs.

pentabromophenol

pentabromophenol

Yet Another Way to Make Isocyanate Prepolymers with Low Free Monomeric Isocyanate

Title: LOW-VISCOSITY REACTIVE POLYURETHANE COMPOUNDS

 Number/Link: WO2013092564 (in German)

Applicant/Assignee: Bayer

Publication date: 27-06-2013

Gist”: A prepolymer with very low free diisocyanate content and relatively low viscosity can be prepared by reacting MDI having a high 2,4′ isomer content with a low MW diol in a first step and adding a high MW polyol in a second step.

Why it is interesting: The use of asymmetric diisocyanates (having isocyanate groups with different reactivities) to prepare prepolymers with low free monomers is well known.  Prepolymers prepared using diisocyanates with high levels of 2,4′-MDI, 2,4-TDI, IPDI etc. will however still show a very high viscosity at low isocyanate content. Bayer has now found that prepolymers with lower free monomer and lower viscosity can be prepared by using two polyols reacted in seperate stages. In a first step an MDI with >95% 2,4′ isomer is reacted with a (pref) diol with a molecular weight between 60 and 700 to produce a prepolymer with an NCO content of more than 15%. In a second step this prepolymer is then further reacted with a ‘conventional’polyol to obtain the final prepolymer.  In an example a prepolymer with less than 0.1% free MDI and a viscosity of 25 Pa.s at 40°C was prepared.

2,4'-MDI

2,4′-MDI

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