Polyurethanes from Alpha Glucan

Patent Title: POLYURETHANE POLYMERS COMPRISING POLYSACCHARIDES

 Number/Link: WO2018/017789

Applicant/Assignee:  Du Pont

Publication date: 25 january 2018

Gist”: Polyurethanes containing poly alpha 1,3-glucan

Why it is interesting: The invention is related to the preparation of different types of polyurethanes comprising poly alpha 1,3-glucan, which is a polymeric D-glucose having alpha 1,3 glycosidic bonds (as opposed to most natural glucose polymers which show α or β 1,4 glycoside linkages). Alpha 1,3 glucan can be prepared by enzymatic polymerization using sucrose and a glycosyltransferase. The glucan can be mixed with polyols and reacted with isocyanates to prepare polyurethanes.  Many examples are given ranging from PUDs, films, flexible foams to TPUs.

glucan

Poly alpha 1,3-glucan

 

Fluorinated Thermoplastic Polyurethanes

Patent Title: SHOE UPPERS & CASE FOR PORTABLE DEVICES

 Number/Link: WO2018/007359  WO2018007360

Applicant/Assignee:  Solvay

Publication date:  11 January 2018

Gist”:  F-TPUs are prepared by incorporating perfluoro diols

Why it is interesting: The current inventions are about fluorinated TPU and its applications. The F-TPUs are prepared by replacing part of the polyol with hydroxyl-ended fluorinated polyethers. In the examples fluorinated polyether diols are used in different ratios to conventional polyester-, PTMEG-, CAPA- and polycarbonate diols and reacted with MDI or HDI and BDO or HDO as chain extenders. The F-TPUs can be used as uppers for footwear and as cases for smartphones and are said to have improved stain resistance and – surprisingly- a soft feel to the touch.

case

F-TPU smartphone case

 

Breathable TPU Membranes

Patent Title: POROUS THERMOPLASTIC MEMBRANES

 Number/Link: WO2017/178482

Applicant/Assignee:  BASF

Publication date: 19-october-2017

Gist”: Semi-permeable membranes are made by phase inversion of all-hardblock TPU solutions

Why it is interesting: ‘Breathable” membranes show a high resistance to liquid water permeation (LEP) combined with a high water vapour permeability (WDD). According to this invention breathable polyurethane membranes can be prepared by dissolving an all-hardblock thermoplastic polyurethane in a polar, aprotic solvent (like N-methyl pyrrolidone) together with a water soluble compound, casting a film and coagulating the film with water. In the examples diisocyanates (MDI, TDI and HDI) are stoichiometrically reacted with chain extenders (MEG, BDO and HDO).  The resulting materials were schredded and dissolved in NMP together with some glycerol. 150 μm thick films were cast on glass and coagulated in water, resulting in membranes with an average pore size ranging between 4 and 500 nm.  The membranes are said to be useful to make breathable fabrics for outdoor wear e.g. (“Gore Tex” (TM) – type materials)

N-methyl-2-pyrrolidone

 

 

 

 

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

 

Rigid Thermoplastic Polyurethanes

Patent Title: ISOCYANATE-MODIFIED RIGID THERMOPLASTIC POLYMER COMPOSITIONS

 Number/Link: WO2017/146948  WO2017/146949

Applicant/Assignee: Eastman Chemical

Publication date: 31 august 2017

Gist”: A “rigid”, high Tg polyester diol is extended with 4,4′ MDI

Why it is interesting: Rigid, high modulus TPUs have been known for a long time – see e.g. Upjohn’s classic patent on ‘Isoplast’ from 1981. These materials are high hardblock TPUs made from diisocyanates, chain extenders with only a small amount of high molecular weight diol as an impact modifier. According to the current invention however, rigid TPUs can be made using less than 40% (w/w) of diisocyanate, a high Tg polyester diol and optionally some chain extender.  The polyester is prepared from ‘rigid’ diols like isosorbide or 1,4-cyclohexanedimethanol together with a ‘rigid’ diacid like terephthalic acid, such that the diol has a MW of more than 400 Dalton and a Tg of more than 40°C. The diisocyanate is pref. 4,4-MDI. The rigid TPUs have a Tg of more than 145°C and a tensile modulus of 1 GPa or higher. They are said to be less moisture sensitive than conventional rigid TPUs.

1,4-cyclohexanedimethanol