Isocyanate-Free Polyurethanes Using Azide-Alkyne Click Chemistry

Title: SYNTHESIS OF POLYURETHANE POLYMERS VIA COPPER AZIDE-ALKYNE CLICK CHEMISTRY FOR COATINGS, ADHESIVES, SEALANTS AND ELASTOMER APPLICATIONS

 Number/Link: WO2014/122153

Applicant/Assignee: Sika

Publication date: 14-08-2014

Gist”: Polyurethane prepolymers capped with azides and alkynes are reacted using copper catalysis.

Why it is interesting: Because of safety, health and envriromental issues, isocyanate-free systems have clearly been gaining in importance the last few years.  Especially for coatings, adhesives and OCF applications, alternative curings systems are being developed. In the current invention an isocyanate-free system is based on the reaction between a prepolymer having at least two azide groups and a prepolymer having at least two alkyne groups. The reaction is copper catalyzed such that it can be performed at ambient temperature. The first prepolymer is (pref.)  prepared by reacting an isocyanate ended prepolymer with glycidol (2,3-epoxy-1-propanol) and subsequently with sodium azide. The second prepolymer is similarly prepared by reacting an isocyanate ended prepolymer with propargyl alcohol (2-propyn-1-ol).  The systems are said to be especially useful for roof coatings.

Example of an azide-alkyne reaction resulting in 1,4-disubstituded triazoles.

Example of an azide-alkyne reaction resulting in 1,4-disubstituded triazoles.

 

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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

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