Polythiourethanes for 3D Printing

Patent Title:  THIOURETHANE POLYMERS, METHOD OF SYNTHESIS THEREOF AND USE IN ADDITIVE MANUFACTURING TECHNOLOGIES

 Number/Link: WO2017/0267804

Applicant/Assignee:  Univ. Texas

Publication date: 21-September-2017

Gist”: Photolatent bases are used to catalyse the polythiol-polyisocyanate reaction

Why it is interesting: According to this invention reactive systems useful for additive manufacturing processes can be prepared from polythiols, diisocyanates and a photolatent base.  When irradiated the photolatent base will split off a non-nucleophilic base which will catalyse the thiol-isocyanate reaction. The systems can be prepared such that the resulting materials show improved mechanical properties over current 3D printed materials.  In an example 2,2′-(ethylenedioxy)diethanethiol and pentaerithritol tetrakis(3-mercaptopropionate) are reacted with HDI using 1,1-dimethyl-1-(2-hydroxypropyl)amine-p-nitrobenzimide (DANBA) as a photolatent base.

Example of pholatent base (DANBA)

Tack-Free Polythiourethane Gels

Patent Title: SOFT ISOCYANATE-CROSSLINKED POLYMER SUBSTANCE AND ASSOCIATED PRODUCTS

 Number/Link: WO2017/054797 (German)

Applicant/Assignee: Technogel

Publication date: 6-april-2017

Gist”: Tack-free polyurethane gels are made from polythiols

Why it is interesting: Very soft polyurethane elastomers or “gels” can be made using high functionality isocyanate and monols (as co-invented by myself – e.g. EP1389222 ) or by reacting a high functionality polyol/siocyanate system at low isocyanate-index (as invented by Bayer – later spun off as Technogel).  PU gels are useful as shock dampers, gaskets and cushions but are always tacky and need to be covered or wrapped, which changes their damping and hardness characteristics. According to this invention tack-free gels without the need for covering can be produced by using polythiols instead of polyols, resulting in poly(thiolurethanes) instead of polyurethanes. This is interesting and surprising and I wonder if it would work with the monol-gels as well.

thiolurethane

Thiolurethane linkage