Open Microcellular Rigid Foams

Patent Title: POLYURETHANE FOAM AND PROCESS FOR PRODUCING SAME

 Number/Link: WO 2018/162372 (German)

Applicant/Assignee:  Covestro

Publication date: 13 September 2018

Gist”: Rigid foam formulation is blown with supercritical carbondioxide

Why it is interesting: Open-celled rigid polyurethane foams are well known and used in vacuum insulation panels. Theoretically the best thermal insulation is obtained with the smallest cell size. According to this invention microcellular rigid foams with a homogeneous cell structure, more than 90% open cells and an average cell diameter of less than 50μm can be prepared by using a rigid foam formulation containing a cellopener and supercritical carbondioxide and allowing it to react and expand in a closed mould. In an example a rigid foam is produced with a density of 67kg/m³, open cell content of 95% and average cell diameter of 17μm.

CO2_phase_diagram

Carbon dioxide (P,T) phase diagram (Wikipedia)

 

Aerogels from Isocyanates and Epoxies

Patent Title: ORGANIC AEROGELS BASED ON ISOCYANATE AND CYCLIC ETHER POLYMER NETWORKS

 Number/Link: WO2017016755

Applicant/Assignee: Henkel

Publication date: 2-feb-2017

Gist”: Isocyanate and epoxy are reacted in solvent and supercritically dried

Why it is interesting: While most ‘conventional’ aerogels are based on silica, organic aerogels, especially isocyanate-based aerogels, are also well known: polyurethane-, polyurea-, polyamide-, polyimide-, polycarbodiimide- and polyisocyanurate aerogels have all been reported. This invention adds another type of aerogel based on the reaction of isocyanates and cyclic ethers, esp. oxetanes and oxiranes. The isocyanate with a functionality of (pref.) 2 to 3, (e.g. 4,4′-MDI or methylidynetri-p-phenyletriisocyanate) is reacted with a cyclic ether  of (pref.) functionality of 2 to 3, (e.g. N,N-diglycidyl-4-glycidyloxianiline) in a suitable solvent (e.g. DMAc). After washing, the gel is dried with supercritical carbon dioxide. The materials are useful for thermal insulation and are said to have better mechanical properties compared to other organic aerogels.

N,N-Diglycidyl-4-glycidyloxyaniline

N,N-Diglycidyl-4-glycidyloxyaniline

 

 

Insulating Wood-Aerogel Composites

Title: REINFORCED ORGANIC NATURAL FIBER COMPOSITES

 Number/Link: WO2015/144267

Applicant/Assignee: Huntsman

Publication date: 1-10-2015

Gist”: Aerogel particles are incorporated in composite wood boards

Why it is interesting: Composite wood products (OSB, MDF..) are  well known and popular construction materials which are produced by compressing wood fibers (or flakes and the like) together with a binder like e.g. a polymeric MDI. Typically these materials show thermal conductivity values of about 50 mW/m.K at densities of around 200 kg/m³.  According to this invention these insulation values can be significantly improved by incorporating (a large amount of) hydrophobic nanoporous particles and binding the composite with an in-water emulsified isocyanate. In the examples silica aerogel particles and wood fibers are mixed an bonded with an emulsifiable MDI. The amount of particles ranges from about 25 to 50% (w/w) resulting in composites with densities below 200 kg/m³ and insulation values of about 20 to 30 mW/mK.

Medium density fibreboard (MDF).

Medium density fibreboard (MDF).

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

PU Rigid Foams with very Small Cell Size

Title: RIGID POLYURETHANE FOAM HAVING A SMALL CELL SIZE

 Number/Link: WO2015/109488

Applicant/Assignee: Dow

Publication date: 30-07-2015

Gist”: Rigid foams are blown with CO2 under pressure

Why it is interesting: It is known that the thermal conductivity of conventional rigid polyurethane foams can be most efficiently improved by reducing the conductivity contribution of the gas present in the foam cells. This, in turn, can be achieved by reducing the gas pressure, by using ‘heavy’ blowing agents or by reducing the average cell size.  The current application discloses rigid PU foams having cell sizes small enough to achieve a thermal conductivity of less than 16 mW/m.K without the need for a strong vacuum or special blowing agents. This is achieved by first saturating the polyol formulation with CO2 under pressure, then adding the isocyanate and increasing the pressure for a set amount of time and finally releasing the pressure to allow the material to expand. Examples are given using a pressure of 7 MPa at 40°C for 30 minutes to saturate the polyol, and a pressure of 10 MPa for up to about 10 minutes after addition of the isocyanate.  Foams with average cell sizes of 8 to 70 μm and porosities of up to 90% are obtained at densities of about 250 to about 300 kg/m³.  Oddly enough no thermal conductivity (λ) values are given.

Rigid polyurethane insulation foams (Wikimedia)

Rigid polyurethane insulation foams (Wikimedia)