Classic PU Patent of the Month: ICI on Non-Isocyanate Polyurethanes (1961)

Title: Polyurethanes

 Number/Link: GB944310

Applicant/Assignee: Imperial Chemical Industries

Publication date: 11-12-1963

Gist”: Non-isocyanate polyurethanes by transurethanization of bis-carbamates and polyols.

Why it is interesting: Because of the growing concern over isocyanate toxicity and related changes in legislation, research and development of non-isocyanate polyurethane (NIPU) systems has increased sharply over the last few years. The idea, and most of the chemistry of NIPU is by no means new. In this patent, filed by ICI in 1961, NIPU is prepared by transesterification of bis-carbamates and polyols with a functionality of 2 or more. The materials are said to be especially useful for coatings and as TPU for fiber production. According to the patent, the advantages of this reaction system over the use of isocyanates are the reduction of the toxicity hazard, less moisture sensitivity and no need to carefully control reaction conditions and reactant proportions.  In an example N,N’-methylene-bis-urethane was reacted with 1,4-butanediol catalyzed by DBTDL resulting in a TPU which could be melt-drawn into fibers.  (Note that, in this case, ‘urethane’ is the common name for ethylcarbamate).

ICI logo anno 1961.

ICI logo anno 1961

Non-Isocyanate Polyurethane Using Thiol-Ene “Click Chemistry”

Title: POLY(HYDROXYL URETHANE) COMPOSITIONS AND METHODS OF MAKING AND USING THE SAME

 Number/Link: US20140182784

Applicant/Assignee:  Inventors but with US goverment interest

Publication date: 3-07-2014

Gist”: Crosslinked poly(hydroxyurethanes) are prepared by reacting a cyclic carbonate comprising a carbon-carbon double bond, a di-thiol and a polyamine.

Why it is interesting: According to this invention hydroxyurethanes are produced by first reacting a cyclic carbonate which has a double bond (e.g. 4-vinyl-1,3-dioxolan-2-one) with a dithiol (e.g. 1,6-hexanedithiol) using UV radiation and a UV initiator. The resulting di-carbonate is then reacted with a polyamine (e.g. diethylene triamine) resulting in a crosslinked poly(hydroxyurethane). Alternatively the carbonate-amine reaction can happen before the thiol-ene ‘click’ reaction. The materials can be used for binders and adhesives a.o.  The reactions have the advantage of being solvent-, catalyst- and isocyanate-free and having a high yield.

Thiol-ene reaction followed by carbonate-amine reaction

Thiol-ene reaction followed by carbonate-amine reaction

More Non-Isocyanate Polyurethanes

Title:  METHOD FOR PREPARING POLY(CARBONATE-URETHANE) OR POLY(ESTER-URETHANE)

 Number/Link: US20130144027

Applicant/Assignee: CENTRE NAT RECH SCIENT; TOTAL RES & TECHNOLOGY

Publication date: 6-06-2013 (priority PCT/EP)

Gist”: Non-isocyanate polycarbonate- or polyester- polyurethane with very high softblock molecular weight produced by “immortal” ring opening polymerization.

Why it is interesting: Non-isocyanate PU systems appear to become a growing trend – at least in scientific and patent literature. In addition to not using phosgene or isocyanates, advantages quoted are improved biodegradability and recyclability.  The current invention teaches the use of “immortal” ringopening polymerization to polymerize 5,6 or 7 membered cyclic carbonates or cyclic esters. This type of ROP is highly efficient and is described in e.g. US2011092664.  The resulting polymer is subsequently modified with anhydrides to a polymer with carboxylic end-groups, which are then reacted with cyclic carbonates bearing hydroxyl groups.  The resulting polymer has a MW of (preferably) 50,000 to 100,000 and can be reacted with polyamines to produce the polyurethanes. See the reaction scheme below.

Reaction sequence according to the invention

Reaction sequence according to the invention

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