DE1545121C - Process for the production of polyurethanes or polyurethane foams - Google Patents

Description

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The German patent specification 1033 891 describes acid, fumaric acid, phthalic acid, isophthalic acid, hexaein Process for the production of flame-retardant hydrophthalic acid and its anhydrides. Example rigid Foams made from saturated polyesters and wise can per mole of the polyhalo-polyhydroaromatic Diisocyanates in which one methanonaphthalenedicarboxylic acid is 2 moles of the other liquid polyesters of hexachloroendomethylene 5 dicarboxylic acid can be used. By Mitvertetrahydrophthalic acid, an aliphatic dicarboxylic expression of such other dicarboxylic acids achieves acid with 5 to 10 carbon atoms and one still has an improved heat resistance, cons-triol with 5 to 10 carbon atoms with an acid resistance to inflammation and color number between 25 and 60 with an aromatic persistence.

Diisocyanate converts in a ratio that the io As organic polyhydroxy compounds can Foam at least 12 percent by weight chlorine aliphatic or aromatic can be used, such as contains. The foams obtained in this way have, for example, glycol, hydroquinone. Catechol however, a relatively dark color and show un- or bisphenol, being such amounts of the organic desired signs of aging, which are used in the form of polyhydroxy compounds that the darkening and brittleness of the upper hydroxyl groups in a stoichiometric surface to express. In addition, the USA. Patent describes "shot against the carboxyl groups of the acids writing 3105 087 the production of polyesters with or their anhydrides are present. The implementation fire retardant Properties through implementation conditions of the organic polyhydroxy compounds Polyhalo-polyhydromethanonaphthalenedicar- ding with polyhalo-polyhydromethanonaphthabonic acid or its anhydride with di- or more-lindicarboxylic acid and optionally another valuable organic hydroxy compounds. These dicarboxylic acids are in the usual ranges, where However, polyesters are usually reaction temperatures in the range of not further processed into polyurethanes. 50 to 300? C.

The object of the invention was to overcome the disadvantages of the organic diisocyanates as can, for example

known polyurethanes and polyurethane foam 25 toluene diisocyanate, diphenylmethane diisocyanate or

avoid substances and use fire retardant and aging polymethylene polyphenyl diisocyanate,

Resistant, especially colourfast, polyurethanes The foams are obtained by adding a

or polyurethane foams. This own foaming agent to the mixture of the hydroxyl

properties are particularly important in materials that contain group-containing polyesters and the organic di-

z. B. for building cladding, sockets and 30 isocyanate. Examples of such foaming agents are

Ashtrays and for paints, varnishes, varnishes or water, tertiary alcohols such as tertiary butyl alcohol

other protective coatings and films containing high or tertiary amyl alcohol, acids such as formic acid,

Exposed to temperatures, uses polymethylolphenols and ureas, polycarbonate

will. acids, monocarboxylic acids and their anhydrides.

According to the invention, one obtains excellent old- 35 It is expedient to use one such

stable and color-fast products, whatever the amount of hydroxyl-containing polyester

is particularly surprising because it is known that the reaction with the organic diisocyanate,

lated cyclohexanes under the action of air - that the component 'of the polyhalogen polyhydro-

Oxygen is easily subject to auto-oxidation. methanonaphthalenedicarboxylic acid or _v of its other

The invention relates to a method for producing 40 hydride in the finished polyurethane 5 to 50 weight

of polyurethanes or polyurethane foams. percent makes up.

Implementation of a hydroxyl group-containing polyester The following example serves to explain further

with an organic diisocyanate, which thereby according to the invention,

is indicated by a hydroxyl group example

containing polyester, which was obtained by implementation 45

an excess of an organic polyhydroxy polyester was made from

compound with a Polyhalogenpolyhydromethano- a mixture of 38.8 g (0.266 MoI) adipic acid,

naphthalenedicarboxylic acid, optionally in a mixture 57.4 g (0.135 mol) 5,6,7,8, .9,9-HeXaChIOr-I ^ jSjMa, - ·

with another dicarboxylic acid, or its an- 5,8,8 a -octahydro -5,8- methylene naphthalene -2,3- di-

hydriden has been produced. "5 ° carboxylic anhydride and 69.8 g (0.533 mol) 1,2,6-He-

The Polyhalogenpolyhydromethanonaphthalindicar- xantriol in a three-necked alkylation flask, the

Bonic acids or their anhydrides can, for example, with a stirrer, a nitrogen inlet tube, a

wise by Diels-Alder reaction of a conjugated short column for water removal and a condenser

aliphatic diene with an olefinic dicarbonic ² ; equipped with a generator. The mixture

acid or its anhydride and additional Diels-Alder 55 was left on for about 3.25 hours under nitrogen

Reaction of the reaction product obtained in this way is heated to a temperature of 155 to 173 ° C. To

A conjugated halocyclic alkadiene produced by this time had approximately 5 cm ^{3 of} water

will. Examples of polyhalopolyhydromethano- developed that has been removed. The obtained poly-

Naphthalenedicarboxylic acids are preferably 5,6,7,8,9; esters consisted of a yellow, viscous liquid

9- ^ x3 ^ 10 ^ 1,2,3,4,43,5,8,83-0 ^ 1 ^^ - 5,8-111611 ^ - ⁶ ° and had a final acid number of 43.

len-naphthalene-2,3-dicarboxylic acid, 5,6,7,8,9,9-hexa- 30 g of the hydroxyl-containing polyester

brom-l ^^^ aAS.Sa-octahydro-S ^ -methylene-naph- with 13 g of toluene-2,4-diisocyanate in a second

thalin-2,3-dicarboxylic acid and its anhydrides. Flask mixed. After about 5 minutes the

If necessary, the mixture according to the invention can be homogeneous and heat developed, and

Process Polyesters can be used which began to be produced approximately 10 minutes after blending

position other dicarboxylic acids or their anhydrides cause foam formation. The sample was then 1 hour

were also used. Examples of such other di- long hardened at a temperature of about 95 ° C,

carboxylic acids are adipic acid, sebacic acid, maleic The resulting polyurethane foam was a rigid,

white mass which, when removed from direct contact with a flame, extinguished itself.

Comparative experiment

For comparison, a polyurethane foam was prepared using 1,4,5,6,7,7-HeXaChIo ^ iCyClo- [2.2, l] -5-hepten-2,3-dicarboxylic anhydride instead of 5,6,7,8,9,9-hexachloro -1,2,3,4,4a, 6,8,8a-octahydro-5,8-methylene-naphthalene-2,3-dicarboxylic acid anhydride produced according to the procedure described above. The foam obtained was also rigid and self-extinguished when removed from exposure to direct flame, but it was from considerably darker in color than the first foam. Furthermore, using the chlorinated Acyclic anhydride produced foam after aging in direct sunlight for two Weeks even darker, and at the same time the surface of the foam became brittle. In contrast to this end, a corresponding aging of the foam produced according to the invention showed a considerably less darkening.

Claims (1)

Claim: Process for the production of polyurethanes or polyurethane foams by reacting a hydroxyl-containing polyester with a organic diisocyanate, characterized in that that one uses a hydroxyl-containing polyester, which by reacting an excess of an organic Polyhydroxy compound with a polyhalogen polyhydromethanonaphthalenedicarboxylic acid, optionally prepared as a mixture with another dicarboxylic acid or its anhydrides has been.