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)

Hydrolysable Ureas

Patent Title: DYNAMIC UREA BONDS WITH FAST HYDROLYTIC KINETICS FOR POLYMERS

Number/Link: WO2017/155958

Applicant/Assignee: Univ. Illinois

Publication Date: 14 September 2017

“Gist”: Hindered urea bonds with fast hydrolysis kinetics are prepared from aromatic-sbstituted diamines and diisocyanates

Why it is interesting: Polyurethanes containing thermally reversible hindered urea bonds (HUBs) have been discussed before in this blog. In the current case the HUBs are prepared from aromatic (e.g aryl-) substituted amines and are said to show fast, pH-independent, hydrolysis kinetics. The HUBs can be built into linear or crosslinked polyurethanes or other polymers like polyamides, polycarbonates etc.  The resulting materials are useful for medical applications like drug delivery, water-degradable packaging, self-healing materials and the like.

HUB hysdrolysis

Hydrolysis reaction of phenyl-N-tetrabutyl-N-ethyl urea

 

Viscoelastic Polyurethane Elastomers

Title:  IMPACT PROTECTION FOAM

Number/Link: US2017/0233519

Applicant/Assignee: Dow

Publication Date: 17 august 2017

“Gist”: Viscoelastic foams are prepared from MDI, castor oil and a hydrophilic polyether polyol.

Why it is interesting: According to this invention energy absorbing foams with relatively low density and a low hardness and resilience in the temperature range from about -10 to +40°C, can be produced by reacting a blend of hydrophilic and hydrophobic polyols containing castor oil, about 0.5 pbw water and some catalyst and chain extender with MDI.  The examples show foams of about 500 kg/m³ with hardness below shore 50A and ball rebound below 15% at both -10 and +23°C. The foams are said to be useful for impact-protective garments.

Castor oil

Castor oil component

PCM Containing PU Gels

Title: Temperature Regulating Polyurethane Gels

Number/Link: US2017/0210961

Applicant/Assignee: Technogel

Publication Date: 27 july 2017

“Gist”: Fatty acid ester PCMs are incorporated into Technogel-type gels without encapsulation

Why it is interesting: Polyurethane gels have been discussed before in this blog. The current invention is about “Technogel-type”  gels, made at low NCO-index and high functionality, that contain phase change materials (PCMs). The PCMs are esters of fatty acids that can be blended in molten state with the low EO polyol to form a clear solution, which is then reacted with isocyanate to form the gel. Despite not being encapsulated or forming a separate phase, the PCMs can reversibly melt and crsytallize while in the fluid phase of the gel. In the examples blends of lauryl laurate (C12-C12) and myristyl myristate (C14-C14) are used as PCM such that the phase change temperature is about 22-38°C.  The gels are said to be useful for ‘close to body’ comfort applications especially for use in matresses to improve sleeping comfort.

Lauryl laurate

 

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