Preventing Ostwald Ripening in Rigid PU Foams

Title: PRODUCTION OF FINE CELL FOAMS USING A CELL AGING INHIBITOR

Number/Link: WO2017093058  (German)

Applicant/Assignee: Evonik

Publication Date: 8 June 2017

“Gist”: Perfluorinated hydrocabons reduce Ostwald ripnening in PU foam formulations

Why it is interesting: Polymeric foams form by nucleation and growth of gass bubbles in the reacting mixture followed by (or simultaneous with) ageing of the bubbles through coalesence and Ostwald ripening, i.e. the growth of larger bubbles at the expense of smaller bubbles. Ostwald ripening ultimately results in fewer and larger cells, which has a negative effect on the thermal insulation properties of rigid foams. According to this invention the ripening effect can be prevented or reduced by incorporating in the foam formulation an “Ostwald hydrophobe”, i.e. a highly hydrophobic liquid which is largely immiscible with the reacting mixture. Examples of such liquids are perfluorinated hydrocabons with a boiling point of less than 150°C, e.g. perfluoropentane, perfluorocyclohexane and perfluoroisohexene (used in the examples).

Perfluorocyclohexane

 

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

 

 

Spray Foam with Increased Reactivity

Patent Title: POLYOL PREMIX COMPOSITION FOR RIGID POLYURETHANE FOAMS

 Number/Link: WO2016/162362

Applicant/Assignee: Covestro

Publication date: 13-10-2016

Gist”: Addition of dicarboxilic acid reduces cream time in amine catalyzed foams

Why it is interesting: A short cream time has advantages for rigid PU spray foam because it can reduce dripping of the material after application.  According to this invention the cream time of an amine-catalyzed, HFC-blown spray foam composition can -surprisingly-be reduced by addition of a dicarboxilic acid, preferably succinic or glutaric acid. The diacids are used in a ratio of about 2 equivalents acid to 1 equivalent of (free) amine. In the examples a clear reduction of cream time is shown compared to compositions with no diacid, a mono-acid or less than the required amount of diacid. However, all examples also contain some trimerization catalyst (2-hydroxypropyl trimethylammonium formate) next to the tert-amine catalyst (N,N-dimethylcyclohexylamine). It would be interesting to see an example without the trimerization catalyst i.m.o.

Succinic acid.

Succinic acid

 

Formic Acid Blown EPIC Foams

Patent Title: ISOCYANATE-BASED TEMPERATURE-RESISTANT FOAMS WITH HIGH FLAME RESISTANCE

 Number/Link: WO2016/131874

Applicant/Assignee: BASF, Covestro

Publication date: 25-08-2016

Gist”:  One shot rigid isocyanate-epoxy foams blown with formic acid

Why it is interesting: This is the first in a series of (at least) 3 patent applications apparently resulting from a cooperation between BASF and Covestro on epoxy-isocyanate (“EPIC”) foams.  The other applications are WO2016/131878 and WO2016/131880 published on the same date. More publications may follow.
The current invention is about temperature-resistant foams with reportedly very high mechanical properties prepared form a one-shot system comprising a (pref.) high functional MDI, a (pref.) bisphenol-A or bisphenol-F polyglycidylether, at least one reactive amine catalyst and a blowing agent comprising formic acid. The ratio of iso to epoxy groups is (pref.) 3:1 to 15:1. The resulting materials are post-cured at 200°C. The foams contain no, or very little, urethane or urea groups and are said to be especially useful in laminates a.o.  In the examples foams with densities of 25-35 kg/m³ with a thermal conductivity as low as 20 mW/mK are shown.

Bisphenol-F diglycidylether

Bisphenol-F diglycidylether

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).