Non-Isocyanate Polyurethanes from Thiocarbonates

Patent Title: PROCESS FOR THE MANUFACTURING OF A POLYMER WITH URETHANE GROUPS

Number/Link: WO2019/034470 and WO2019/034473

Applicant/Assignee: BASF

Publication Date: 21 February 2019

“Gist”:  A cyclic thiocarbonate is reacted with a diamine and then with a diacrylate

Why it is interesting: NIPU is prepared by reacting a five-ring monothiocarbonate with di- (or poly-) amine and then with a compound having at least two thiol-reactive functional groups like e.g. ethylenically unsaturated groups. The reaction has advantages over conventional PU chemistry like being isocyanate-free, less moisture sensitive and running at moderate temperatures. In an example methyl monothiocarbonate is reacted with 1,5-pentanediamine and 1,4-butandioldimethacrylate, resulting in a colourless, transparent polymer with a high thermal stability.
An interesting take on hybrid non-isocyanate polyurethanes.

scheme1

Reaction scheme according to the invention

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PU Elastomers from SGO Polymerized Acrylic Polyols

Patent Title: PHYSICAL PROPERTY IMPROVEMENT OF POLYURETHANES

 Number/Link: WO2018/132648

Applicant/Assignee:  BASF

Publication date: 19 July 2018

Gist”: Solvent-free acrylate polyols are reacted together with polyether polyols and diisocyanates

Why it is interesting: In this invention a solvent-free (“100% solids” in the patent’s terminology) acrylic polyol is blended with a conventional polyether polyol and reacted with an aliphatic or aromatic diisocyanate.  The acrylic polyol is prepared by co-polymerizing (e.g.)  ethyl- or butyl (meth)acrylates, styrene and a hydroxyl functional acrylate like 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate, using BASF’s “solid grade oligomer” (SGO) polymerization process. The SGO process is a high temperature and high pressure continuous process allowing for the production of low-solvent acrylic resins. The polyurethanes are said to have increased physical properties, esp. tear- and tensile strength properties.

HBA

Hydroxybutylacrylate

Aerogels from Urethane-Acrylate Star Monomers

Title: FLEXIBLE TO RIGID NANOPOROUS POLYURETHANE-ACRYLATE (PUAC) TYPE MATERIALS FOR STRUCTURAL AND THERMAL INSULATION APPLICATIONS

 Number/Link:US2015/0266983

Applicant/Assignee: University of Missouri

Publication date: 24-09-2015

Gist”: A trifunctional acrylate-ended urethane monomer is polymerized in solvent and supercritically dried

Why it is interesting: Research related to nanoporous materials has been gaining significant momentum in recent years and both inorganic (usually silica-based) and organic (e.g resorcinol-formaldehyde or polyurethane -based) aerogels are increasingly being used especially for thermal insulation applications. The current invention relates to hybrid PU-AC aerogels prepared from acrylate functional “star” monomers. The monomers are made by reacting a tris(isocyanatoaryl)methane with one or more hydroxyacrylates in a suitable solvent.  The monomer is then radically polymerized and the resulting ‘wet’ gel is supercritically dried into an aerogel. In the examples tris(4-isocyanatophenyl)methane is reacted with 2-hydroxyethylacrylate in ethyl acetate. The monomer solution is polymerized by heating with a radical initiator and the resulting gel is then dried using acetone and supercritical CO2.  The resulting aerogels have a density ranging from about 135 to 650 kg/m³ with a porosity bewteen 90 and 50% (v/v).  The lower density aerogels are flexible and have a thermal conductivity of about 40 mW/m.K.

Star monomer according to the invention

Star monomer according to the invention

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