Classic PU Patent of the Month: Non-Isocyanate Polyhydroxyurethanes by Dow (1957)

Title: Polyhydroxyurethanes

 Number/Link: US3084140

Applicant/Assignee: Dow

Publication date: 2-04-1963

Gist”: bis-cyclocarbonates are reacted with aliphatic polyamines

Why it is interesting: Non-isocyanate polyurethanes (NIPU) are still gaining in popularity – at least in the patent and science literature. The chemistries to make NIPU are far from new as discussed in a previous ‘classic patent of the month’ on this blog.  The most common route to NIPU is by reacting cyclocarbonates with amines resulting in hydroxyurethanes, as was first dicussed in this patent. The intent of the invention was, actually, not to avoid the use of isocyanates but to make hydroxy-group containing polyurethanes which were said to be ‘highly desirable’:  the OH groups can act as points for crosslinking, make the resin more hydrophilic and compatible with certain materials etc.

Preparation of polyhydroxyurethanes according to the invention

Preparation of polyhydroxyurethanes according to the invention

Hybrid Hotmelt Adhesive with Low Free Isocyanate

Title: POLYURETHANE HOT-MELT ADHESIVE HAVING A LOW CONTENT OF DIISOCYANATE MONOMERS AND GOOD CROSS-LINKING SPEED

 Number/Link: WO2015/135833 (German)

Applicant/Assignee: Sika

Publication date: 17-09-2015

Gist”: Use of mercaptosilane to reduce free monomeric diisocyanate

Why it is interesting: Reduction of the amount of free monomeric diisocyanate in adhesives, coatings, OCF systems etc. remains a hot topic in industrial polyurethane research, mostly because of changing legislation. For example, in the EU the amount of free MDI needs to be below 1% in order to avoid “R-40” (suspect carcinogen) labeling. A number of strategies to reduce free isocyanate have been tried in the past (and mentioned in this blog). Examples are distillation, the use of asymmetric diisocyanates and the use of monols. According to this invention the amount of free monomeric isocyanate in a hotmelt formulation can be reduced by adding a mercaptosilane like e.g. mercaptopropyltrimethoxysilane.  The mercaptosilane is said to react preferentially with the monomeric isocyanate.  Only a relatively small amount of mercaptosilane is used such that the main curing mechanism is still the isocyanate-water reaction.

Mercaptopropyltrimethoxysilane

Mercaptopropyltrimethoxysilane

 

PU Sealants using Michael Addition Chemistry

Title: MICHAEL ACCEPTOR-TERMINATED URETHANE-CONTAINING FUEL RESISTANT PREPOLYMERS AND COMPOSITIONS THEREOF

 Number/Link: US2015/0252232

Applicant/Assignee: PRC-DeSoto

Publication date: 10-09-2015

Gist”: A PU prepolymer is capped with Michael accepting groups and then cured with a dithiol

Why it is interesting: This invention is about sulphur containing PU sealants with properties acceptable for the aerospace industry. A bis(vinylsulfonyl)- terminated urethane-polythioether prepolymer is prepared according to the scheme below. The prepolymer can then be cured with a dithiol-ended polyether, catalysed by a tertiary amine.  The compositions have an extended pot life and the curing rate can be controlled by using an encapsulated tert-amine as a controlled-release catalyst.

Michael acceptor-terminated prepolymer preparation according to the invention

Michael acceptor-terminated prepolymer preparation according to the invention

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