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)

 

Syntactic Polyurethane Elastomers

Title: SYNTACTIC POLYURETHANE ELASTOMERS FOR USE IN SUBSEA PIPELINE INSULATION

 Number/Link: WO2015065769 WO2015065770 WO2015065771 WO2015065772

Applicant/Assignee: Dow

Publication date: 7-05-2015

Gist”: Zn/Zr catalyzed syntactic elastomers for subsea pipeline insulation

Why it is interesting: Conventional polyurethane rigid foams cannot be used for the insulation of subsea pipelines because the foams would collapse under the pressure and they are too brittle to be bent.  For these reasons syntactic elastomers can be a better choice for this application. Syntactic polyurethane elastomers consist of a solid PU matrix containing up to 50% (wt/wt) of hollow glass microspheres. The catalyst of choice to produce these materials is phenylmercury neodecanoate.  However because of regulatory pressure other catalyst systems are now being used.  The gist of these four patent applications appears to be the use of a mixture of a zinc carboxylate with a small amount of zirconium carboxylate as a replacement for the organomercury catalyst, but this is not the main claim (probably because of non-patentability). Instead the WO..69 case is about the use of polymer polyols in these systems,  the WO..70 case is about the use of low unsat polyols, WO..71 is about a special type of morphology and WO..72 about the use of prepolymers.

Phenylmercury neodecanoate

Phenylmercury neodecanoate

Sound Absorbing PU-PA Foams

Title: THERMOFORMABLE RIGID POLYURETHANE-POLYAMIDE FOAM

 Number/Link: US2014/058005

Applicant/Assignee: BASF

Publication date: 27-2-2014

Gist”: Rigid, open-celled and thermoformable polyurethane-polyamide foams are produced using short chain di-acids as both chain extender and blowing agent.

Why it is interesting: The reaction of a carboxylic acid group with an isocyanate group results in a mixed anhydride, which after releasing carbon dioxide forms an amide. Because the reaction is relatively sluggish a  Lewis base catalyst is used, e.g. N-methylimidazole. In this case a rigid foam-forming formulation based on MDI and (pref.) polyether polyols is further reacted with short chain diacids like azelaic- or glutaric acid.  The examples show foam densities of less than 30 kg/m³ without the use of water.  The foams are open celled with high air flow and with a Tg of around 90°C, making them thermoformable.  This type of foams is used as acoustic bonnet- en roofliners in the automotive industry.

Azelaic Acid

Azelaic Acid

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