DE2545118A1 - CATALYST AND METHOD FOR MANUFACTURING HARD, POLYURETHANE-MODIFIED POLYISOCYANURATE FOAM - Google Patents

Description

Folder 2? 833 - Dr. K / by
M&T Case 1123

M&T CHEMICALS INC. Greenwich, Connecticut, U.S.A.

Catalyst and process for the production of rigid, polyurethane-modified polyisocyanurate foams

Priority: 9-4-1975 - U.S.A.

The invention relates to rigid foams and more particularly on hard, polyurethane-modified polyisocyanurate foams. The invention further relates to a process for the production of hard, urethane-modified polyisocyanurate foams, in which a catalysis with a synergistic combination of isocyanurate trimerization catalysts is used.

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on the trimerization of isocyanates into isocyanurates ^ under Use of triethy! Phosphine was the first to be used by Hofmann reported. Since then, many other catalysts for the trimerization of isocyanates have become known. the Use of amines is described in U3-PSs 2 993 870 and 2 979 485, the contents of which are included in the present Registration should apply included. Additional basic nitrogen compounds, such as triazines and their derivatives, are described in U.S. Patent 3,804,782, the contents of which are also disclosed to be considered included in the present application. Weak acid salts such as calcium acetate (described by Frentzel) and potassium acetate and sodium carbonate (described by Hofmann) were also used. The use of potassium octanoate (potassium 2-ethyl-hexoate) is described in JA-PS 7Ί 4-2 386, its content as well to be considered included in the present application. The manufacture of rigid polyisocyanurate foams or poly (urethane isocyanurate) foams are usually made by reacting a polyether or polyester polyol, an organic polyisocyanate, a surface active one Agent, a propellant and a catalyst. In the production of these foams, there is a puncture of the catalyst in accelerating the formation of a cellular product, making the process economical and efficient can be designed. Amine catalysts, such as 2,4,6- (N, N-dimethylaminomethyl) phenol, and hexahydrotriazines are true effective, but they are poisonous and, moreover, they must be used in very large amounts. So it exists a need in the manufacture of these foams to reduce the toxicity hazards associated with handling the ingredients and maximize their efficiency to take full advantage of these foams. The invention relates now on such an efficient catalyst with reduced toxicity.

According to the invention, hard, polyurethane-modified

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Polyisocyanurate-based foams produced by reacting an organic compound which has at least two active hydrogen atoms with an organic polyisocyanate using a large excess of the polyisocyanate, which occurs simultaneously with the polyurethane formation
is trimerized in isocyanurate, the trimerization
or polymerization of the isocyanate with the active hydrogen-containing compound is catalyzed by a synergistic combination of an alkaline soap and a tertiary amine. By using this unique
Catalyst combination creates a balanced urethane formation
and isocyanurate formation, the cost of the catalyst being exceptionally low. The reaction of the active hydrogen compound with part of the polyisocyanate proceeds due to the low amount of the
Combination of alkaline soap and tertiary amine in good balance with the polyisocyanate trimerization reaction. By using this class of catalyst combination for. Promotion of the urethane and isocyanurate reaction
Isocyanate indices up to 1000 can be used in making these foams. Because of the high isocyanate index that can be used and because of the very small amount of catalyst combination required, polyurethane-modified polyisocyanurate foams can be produced economically. Polyisocyanurate foams of this type are very desirable because of their reduced tendency to burn, because of the necessity
the addition of other agents to achieve flame retardancy is omitted. These and other advantages of polyurethane-modified polyisocyanate foams have been described in the literature by Frisch et al. discussed.

It has surprisingly been found that by using
a certain combination of isocyanurate trimerization catalysts in the production of polyurethane-modified isocyanurate foams is an economically advantageous

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ter synergism occurs. Through the resulting low catalyst concentrations will not only result in faster and more economical manufacture of polyurethane foam products allows, but it will also drastically reduce the required amounts of toxic, irritant and expensive tertiary amines. All of these advantages are direct from using the catalyst combinations described herein attributable to.

The invention further relates to a method for producing hard urethane foams, which is carried out thereby is that a polyalkylene polyol having at least two reactive 'hydrogen atoms and at least an organic polyisocyanate is reacted with one another, a combination being used as the trimerization and polymerization catalyst from 0.01 to 5 parts of a 1,3,5-tris (N, N-dialkylaminoalkyl) hexahydrotriazine or a 2,4,6-tris (N, N-dialkylaminoalkyl) phenol or an adduct of one of the two compounds with alkylene oxide and water and from 0.01 to 5 Parts of an alkali metal salt of a carboxylic acid having 2 to 19 carbon atoms per 100 parts of organic polyisocyanate used.

The preferred isocyanate trimerization urethane polymerization catalyst consists of a 1,3 »5-tris- (N, N-dialkylaminoalkyl) hexahydrotriazine or an addition product of this compound with alkylene oxide and · water and of one Alkali metal hydroxide neutralization product of a carboxylic acid such as potassium 2-ethylhexoate.

1,3i5-tris (N, N-dialkylaminoalkyl) hexahydrotriazines are generally prepared by reacting equimolar amounts of a dialkylaminoalkylamine and a 37% aqueous solution of formaldehyde at a temperature in the range of about -20 to +20 ⁰ C and reacts at atmospheric pressure. In particular, the amine and the formaldehyde are ^{mixed at about 0} ° C. with moderate stirring. Thereupon the

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allowed to warm to room temperature with continued moderate stirring. The hexahydrotriazine compound is then obtained by first salting out the hexahydrotriazine from the reaction mixture with a strong base such as potassium hydroxide and then purifying the product by distillation. These hexahydrotriazine compounds and their preparation have been particularly described by Nicholas et al., Journal of Cellular Plastics, ± (1), 85 (1965) and Graymore, Journal of the Chemical Society, 1493 (1931).

Examples of 1,3,5-l ¹ ris- (N, N-dialkylaminoalkyl) hexahyärotriazines, which can be used in the process according to the invention, are 1,3 »5-tris- (N, N-dimethyl-2-aminoethyl) - shexahydrotriazine, 1,3,5-tris (N, N-dimethyl-2-a: ninopropyl) hexahydrotriazine, and the like; 1,3,5-T2? Is- (N, N-diethyl-2- aminoethyl) -s-hexahydrotriazine; 1,3,5-tris (N, N-diethyl-3-aminoethyl) -s-hexahydrotriazine and the like; 1,3,5-TrIS- (N, N-dipropyl-2-air.inoethyl) -s-hexahydrotriazine and the like; etc. The preferred compound is 1,3,5-fris- (li, N-dimethyl-3-aminopropyl) -shexahyd.rotriazine, which is also known as 1,3,5-0? ris- (3-dimethylaminopropyl) -s -hexahydrotriazine can be called. Related preferred isocyanurate Triiaerisationskatalysatorkomponenten are, as already mentioned, the alkylene oxide and the above-described Wasseraddukte 1.3 _i 5-tris (N, N-diäthylaminoalkyl) -shexahydrotriazine. These compounds are believed to be quaternary ammonium hydroxides with the following structure:

"-N-R'-N N-R'-NR ₂ " OH

R-CH-CH-OH

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wherein Ii, each for hydrogen or lower alkyl, such as z.3. Methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl and pentyl; R "represents lower alkyl as indicated above for H; and R 'represents alkylene, such as ethylene, Propylene and butylene are available as they are derived from the hexahydrotriazines which can be used and the preferred hexahydrotriazines in this case being the same are as defined above.

In view of the above structure, it should be noted that there are 6 nitrogen atoms which lead to the formation of quaternary ammonium hydroxide may be capable, which is why the above structure is to be understood as an illustration only. It should also be pointed out that the hydroxyl group can be either primary or secondary in nature.

The alkylene oxides used to make the adducts are preferably linear alkylene oxides such as e.g. Ethylene oxide and propylene oxide, the butylene oxides and the pentylene oxides. Also, although not preferred, any cyclic oxide such as cyclopentylene oxide can be used and cyclohexylene oxide. Finally, can also be substituted Alkylene oxides such as styrene oxides can be used. The preferred alkylene oxide is propylene oxide.

If 1,3 »5-Ti * is- (3-dimethylaminopropyl) -s-hexahydrotriazine, Propylene oxide and water are used to make the preferred adduct then presumably own the product the structure:

H
(CH ₂ ) 3 "N-

- (CH ₂ ) ₃ -N

ΐ »

N (CH ₂ J ₃ -N- (CH ₃ )

CH ₀ -CH-OH

² i

CH ^

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These alkylene oxide and water adducts are generally prepared by adding substantially equimolar amounts of hexahydrotriazine, alkylene oxide and water at a temperature of about 10 to 80 G for a period of about 5 minutes to 2 hours and at a pressure of about atronic pressure to 3 » 5 atü implements. Any convenient reaction procedure can be used, such as:

(1) Reaction of the hexahydrotriazine and alkylene oxide at atmospheric pressure or elevated pressure for a period of about 15-60 minutes, preferably 15-30 minutes, and at a temperature of about 10 to 35 ° C, preferably 20 to 50 ° C, and thereafter addition of and reaction with V / ater min at a temperature of about 25 to 80 ⁰ G, preferably 40 to 60 ° G, and for a period of about 10 to 60, preferably 15 to 40 min;

(2) Adding water to the hexahydrotriazine and then adding the alkylene oxide, this procedure under the same heaction conditions as above are carried out; or

Simultaneous (3) but separate addition and reaction of the alkylene oxide and water with the hexahydrotriazine at a temperature of about 10 to 8O ⁰ C, preferably 20 to 60 min to 60 ⁰ C, and for a period of about 5, preferably from 15 to 40 min.

The products obtained are highly viscous products that are considered to be Solutions can be used to facilitate their handling.

The preferred 2,4,6-TriS- (BT, N-dialkylaminoalkyl) phenol is 2,4,6-tris (dimethylaminomethyl) phenol.

Examples of alkaline soaps or alkali metal hydroxide neutralization products of carboxylic acids are the lithium, sodium and potassium hydroxide reaction products of acetic acid,

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Propionic acid, butyric acid, valeric acid, kexanoic acid, heptanoic acid up to C ^ -carboxylic acids, whereby the latter need not necessarily be the limit. Unsaturated carboxylic acids derived from tall oils or animal fats, such as oleic acid or linoleic acid, or mixtures thereof can also be used. The use of aromatic carboxylic acids, such as, for example, benzoic acid and benzoic acid derivatives, salicylic acid and naphthenic acids, is also possible. Any suitable polycarboxylic acid can also be used, such as, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, α-hydroxymuconic acid, κ-butyl β-hydroxyl -ot-ethyl-glutaric acid, α, ß-diethy! succinic acid, isophthalic acid, terephthalic acid, hemimellitic acid and 1,4-cyclohexanedicarboxylic acid.

The alkaline soap is made by neutralizing the carboxylic acid with an aqueous solution of the alkali metal hydroxide produced with stirring. Careful control of the exothermic heat of reaction of the neutralization is required, to obtain a non-discolored product. The water the solution and neutralization is then removed under vacuum and with stirring.

In an optional method, a diluent is used as a viscosity depressant and / or a solvent for the reactants and products used. In this process, the carboxylic acid is first dissolved in the diluent and then neutralized with the aid of the aqueous alkaline solution. The water is removed in a similar manner. Suitable diluents are alcohols such as methanol, ethanol, propanol, butanol and the like; Glycols, such as ethylene glycol, Diethylene glycol, poly (äthy1englyko1), propylene glycol, Dipropylene glycol and poly (propylene glycol) and the like.

During the production of a foam in the presence of this

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Catalyst combinations can be used with significantly reduced amounts of total catalysts, particularly with regard to the hexahydrotriazine, which, on a weight basis, is less effective than the alkali soaps such as potassium 2-ethylhexoate. Although up to 12 parts of hexahydrotriazine per 100 parts of polyisocyanate or 3 to 2 parts of a 65% solution of potassium 2-ethylhexoate in poly (propylene glycol) per 100 parts of polyisocyanate can be used as the sole catalyst, but only 1 part per 100 parts (i.e. a total of 2 parts per 100 parts of polyisocyanate) has a more effective catalyst effect than if only one of the components is used in the specified amounts.

The polyurethane-modified polyisocyanurate foams according to the invention consist in general of the reaction product of an isocyanate with itself, whereby a poly (isocyanurate) arises, which is caused by the simultaneous reaction product part of the polyisocyanate with an organic Compound with at least 2 active hydrogen atoms, such as a hydroxy-terminated polyester, polyesteramine, Polyesteramide or polyether.

In general, any organic compound that contains at least 2 active hydrogen atoms can react with the Polyisocyanate used v / earth to make the necessary urethane modification of the foam. Examples of suitable organic compounds with at least 2 active hydrogen Atoms are hicinus oil, hydroxyl-containing polyesters, polyalkylene polyether polyols, hydroxy-terminated polyurethane polymers, polyhydroxy polyethioethers, alkylene oxide adducts of Phosphorus acids, polyacetals, aliphatic polyols, simple, oligomeric and polymeric glycols such as ethylene glycol, Propylene glycol, butylene glycol, poly (ethylene glycol), Poly (propylene glycol) and poly (butylene glycol).

Ingeniously with the above mentioned organic compounds, which have at least 2 active hydrogen atoms, each

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the appropriate polyisocyanate can be used, such as polymethylene polyphenylene polyisocyanate (crude MDI). These polyols generally have an average molecular weight of about 31 for ethylene glycol to 2000 for ioxyoxypropylene adducts of glycerol. It is also possible to use polyols, such as, for example, a mixture of high molecular weight polyether polyols with low molecular weight polyether polyols or monomeric polyols.

The organic polyisocyanates which can advantageously be used in accordance with the invention have the general principles Formula:

R (RCO)

Zr

where B stands for a polyvalent organic sadical that is selected from aliphatic, aromatic arylalkyl and alkaryl radicals; and ζ for an integer stein; which is the Equals valence of H and is at least 2. Examples of organic polyisocyanates which can be used according to the invention are aromatic diisocyanates such as 2,4-Tcluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2, F) -Toluene diisocyanate, crude toluene diisocyanate, Kethylene-diphenyl-diisocyanate, crude methylene diphenyl diisocyanate and the like; aromatic triisocyanates such as tris (4-isocyanatophenyl) methane and 2,4,6-toluene triisocyanate; aromatic tetraisocyanates, such as 4,4'-dimethyldiphenylmethane-2,2 ', 5', 5'-tetraisocyanate, and the like; Alkylary polyisocyanates such as xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate, Lysine diisocyanate methyl ester and the like; as Mixtures of these. Other organic polyisocyanates are e.g. polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 3j3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl-diiso-

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/ Tv

cyanate and 5 »3 '-dimethyldiphenylmethane-V-diisocyanate.

These polyisocyanates are obtained by conventional methods such as those in the art for the phosgenation of the
corresponding organic amines are known.

Further classes of organic polyisocyanates according to
The so-called "^ uasiprepolymers" can be used in the invention. These quasi-prepolymers are prepared by using an excess of an organic polyisocyanate or polyisocyanate mixture with a smaller amount
an active hydrogen containing compound as determined by the well-known Zerewitinoff test
k & nn, as reported by Kohler in Journal of American Chemical
Society, 4-9, 3181 (1927). These
Compounds and their methods of preparation are well known in the art. The use of a special compound with active hydrogen is not required there
namely, any such compound can be used to produce a quasi-prepolymer. In general, the quasi-prepolymers are prepared by reacting an organic polyisocyanate in less than the stoichiometric amount, based on the weight of the polyisocyanate, of the compound with active hydrogen. Suitable active hydrogen containing compounds are the same as described above.

According to the invention, the preferred isocyanate is polymethylene polyphenylene polyisocyanate. This polyisocyanate having an isocyanate index of about 200 to 1000, preferably about 300 to 500, is used. The term "isocyanate index" as used herein means the amount actually used
Isocyanate divided by the theoretical stoichiometric
required amount of isocyanate, multiplied by 100. See
Berder, Handbook of Foam Plastics, Lake Publishing Corporation, Libertyville, Illinois (1965).

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In addition to the components defined above, others also know ingredients useful for the production of foams are used, such as surfactants, fillers, Pigments and propellants. Surfactants that can be used are conventional surfactants Agents used in the manufacture of urethanes, such as the polysiloxanes or the alkylene oxide adducts of organic compounds with active hydrogen atoms. The surfactant is preferably used in an amount in the range from 0.01 to 5 parts by weight per 100 parts by weight of FoIyisoeyanat used.

The expansion into a foam takes place through use a propellant. Volatile organic solvents that evaporate during the exothermic reaction can can be used, such as methylene chloride, ethylene chloride, Triclilorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane, Tetrachloromethane, difluorotetrachloroethane and the like. The preferred propellant is trichlorofluoromethane. Vsser can be used as a propellant supplement to the halogenated hydrocarbons. The use of water as a propellant in urethane chemistry is from Saunders and Frisch, Advances in Polyurethane Chemistry, Vol. 1, pp. 7 & 7.

In addition to the components already mentioned, you can still other ingredients can be used in the manufacture of the foams, such as fillers, pigments, and the like are conventional Fillers are for example aluminum silicate, calcium silicate, Magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, carbon black and silicon dioxide. The filler is usually in an amount of about 5 to 50 parts by weight 100 parts by weight of the total foam present.

The pigments used in the process according to the invention can be selected from the conventional pigments, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, sienna iron blue and molybdate orange.

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Organic figs can also be used, e.g. Parrot, Benzidine Yellow, Toluidine Red, Toners and Phthalocyanines.

In the manufacture of rigid foams according to the invention any conventional method for making urethane foams can be used. Generally werder. in such a process the appropriate ingredients are mixed with stirring. The responding Ilasse is then in transferred to a suitable container before expansion begins.

The invention will now be explained in more detail by the following examples. All parts are parts by weight, unless otherwise is specified. The rise profiles of the foams were determined in the manner customary in the industry.

EXAMPLE 1

A mixture of 275 parts of Pluracol P-4-10 (poly (oxypropylene) with a hydroxyl number) was placed in a 1 liter glass container from 4-25 »supplied by BASF Wyandotte), 276 parts Trichlorofluoroniethan and 30 parts of NiäX-Silicone-L-534-O (PcIyoxyaikylen-polysiloxan, supplied by Union Carbide Corporation) stirred at 1000 rpm for 5 minutes. The mixture became overnight left to stand and formed a clear solution.

EXAMPLE 2

50 parts of the basic mixture, the preparation of which is described in Example 1, were poured into a 250 g containing plastic lined paper cups weighed. Then 4-.0 parts of Folycat 41 (1,3,5-'lFis- (dimethylaminopropyl) hexahydrotriazine, supplied by Abbott Laboratories). The mixture was stirred at 500 rpm for 2 minutes and weighed. The loss of propellant due to its volatility was then compensated for by the subsequent addition of fluorocarbon from a Wash bottle supplemented. 100 parts PAPI (polymethylene-polypheny-

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len polyisocyanate supplied by Upjohn Company) were then used added all at once and mixed in with 2000 U / rain for 10 seconds. This material was then put into a cardboard box with the dimensions 20.3 x 20.3 x Ί5- »2 cm poured in and expand freely calmly. The cream, rise, gel and tack-free times were 20, 76, 127 and 4-00 seconds, respectively. The foam had one dark colour. *

EXAMPLE 3

The procedure of Example 2 was repeated except that 8 parts of 1,3,5-tris (dimethylaminopropyl) hexahydrotriazine each 100 parts of polyisocyanate were used. The cream, climbing, Gel and tack-free times were 20, 53 »97 and 215 seconds, respectively. Of the Foam was dark in color.

EXAMPLE 4

The procedure of Example 2 was repeated using 12.0 parts of 1,3,5-tris (dimethylaminopropyl) hexahydrotriazine per 100 parts Polyisocyanate were used. The cream, rise, gel and tack-free times were 16, 4-7, 102 and 200 seconds, respectively. It is possible that with this system compared to Examples 2 and 3, an activity plateau was reached, because the increase the amount of catalyst only a slight increase in activity was obtained.

EXAMPLE 5

The procedure of Example 2 was repeated, using 1.0 part of a 65% solution of potassium 2-ethylhexoate in poly (o>: ypropylene) with a hydroxyl number of 4-25 as the only catalyst was used. No reaction could be observed.

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GAME 6

The procedure of Example 2 was repeated using 2.0 parts of a 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) having a hydroxyl number of 425.
The cream, rise, gel, and tack-free times were 17, 35, 55
or 70 sec. The foam was brightly colored.

EXAMPLE 7

The procedure of Example 2 was repeated using 4.0 parts of 1,3,5-tris (dimethylaminopropyl) hexahydrotriazine and 1.0
Part of a 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) with a hydroxyl number of 425 was used as a synergistic catalyst combination. 60 sec. Of the
Foam was light in color.

EXAMPLE 8

The procedure of Example 2 was repeated, 1.0 part of 1,3,5-Ti "is- (dimethylaminopropyl) hexahydrotriazine and 1.0 part of a 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) with a Hydroxyl number of 425 were used as a synergistic catalyst combination.
Gel and tack-free times were 14, 28, 45 and 125 seconds, respectively.

From the above examples it can be seen that the addition of only 1.0 part of a 65% solution of potassium 2-ethylhexoate
in poly (oxypropylene) with a hydroxyl number of 425 per 100
Parts of polyisocyanate to a 1,3 »5-tris (dimethylaminopropyl) hexahydrotriazine catalyzed system gives a synergistic increase in activity, since 1.0 part of a 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) with a The hydroxyl number of 425 alone is not an effective catalyst.
Higher concentrations of the 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) with a hydroxyl number of 425

■ - 15 ■ 6 O 9 8 4 3/1 OC 2

successfully catalyze foam formation. However is the use of such a detention is undesirable because the obtained Foam product only has a low level of strength :;t.

EXAMPLE 9

The basic mixture of Example 1 was made up again, but with an equal weight of poly (ethylene glycol) of poly (propylene glycol) was used.

EXAMPLE 10

50 parts of the basic mixture described in Example 9 were placed in a 250 g plastic-lined paper cup weighed in. 1.0 part 1,315-tris (dimethylaminopropyl) hexahydrotriazine and 1.0 part of a 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) having a hydroxyl number from 4-25 were weighed into the beaker. Then was Stirred for 2 min at 500 rpm, after which the volatilized fluorocarbon was replenished. Then 100 parts were made of polymethylene polyphenylene polyisocyanate admitted at once. The reacting mixture was mixed at 2000 rpm for 10 seconds. the The resulting mass was then placed in a cardboard box with the dimensions 20.3 x 20.3 x 15 »2 cm and rose freely calmly. The cream, rise, gel and tack-free times were 14, 27, 46 and 120 seconds, respectively.

EXAMPLE 11 '

The procedure of Example 10 was repeated, the 1.0 part of the 65% solution of potassium 2-ethylhexoate in poly (oxypropylene) having a hydroxyl number of 425 through 0.90 g a 65% solution of sodium - ^ - äthylhexoat in PolyCoxypropylene) with a hydroxyl number of 425 was replaced. The cream, rise, gel and tack-free times were 14, 21, 47 and 125 seconds, respectively.

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12th

D. 1.5 The procedure of Example 10 was repeated, with 1.0 part of the 65% iE solution of potassium 2-ethylhexoate in poly (oxypropylene) having a hydroxyl number of 42? ig by 1.8 parts of a 65% solution of i ^e * was Kaliuaioleat in poly (oxypropylene) replaced with a hydroxyl number of 425th The cream, rise, gel and tack-free times were 15, 30, 49 and 130 seconds, respectively.

The purpose of the above examples was to show that when the potassium 2-ethyl-hexoate is replaced by similar ones alkaline soaps in equimolar amounts achieve a similar behavior.

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BATH ORIGINAL

Claims (10)

ΡΛ'ΓΞΝϊ A.N3PRÜ GHE: Λ. ι Catalyst for the production of hard polyisocyanurate foams modified by polyra ret ho, characterized in that it consists essentially of a combination of a tertiary amine and an alkali metal neutralization product of a carboxylic acid. 2. Catalyst according to claim 1, characterized in that the tertiary amine consists of a hexahydrotriazine. 3- catalyst according to claim 1, characterized in that the tertiary areas of 1,3 »5-tris (N, N-dialkylaminoalkyl) hexahydrotriazine consists. 4. Catalyst according to claim 1, characterized in that the tertiary amine from the alkylene oxide or water adduct of 1,3,5-tris (N, N-dialkylaminoalkyl) hexahydrotriazine
consists. 5. Catalyst according to claim 1, characterized in that the alkaline soap consists of the lithium, sodium or potassium hydroxide neutralization product of a carboxylic acid. 6. Catalyst according to claim 1, characterized in that the alkaline soap made from Kaliuta-2-ethylhexoate or one Solution of the same in an active hydrogen-containing diluent. ?. Catalyst according to claim 1, characterized in that the tertiary amine and the alkaline soap from the alkylene oxide or water adduct of 1,3,5- ^ ris- (H ", N-dialkylartinoalkyl) hexahydrotriazine and from a 65% solution of
Potassium 2-ethylhexoate consists. 8. Catalyst according to claim 1, characterized in that the tertiary amine from 1, Ji ^ -T'rishexahydrotriazine consists. - 18 609843/1002 BATH ORIGINAL 9. Method of making a rigid polyurethane foam by reacting a polyalkylene polyol which has at least two hydrogen atoms with an organic polyfunctional isocyanate, characterized in that the reaction in the presence of at least a compound from the group: 1,3,5-Tris- (N,! i-dialkylaminoalkyl) hexahydrotriazines, 2,4-, 6-TrIs- (Ii, N-dialkylaminoalkyl) phenols and their adducts with alkylene oxide; and at least one compound from the group: carboxylic acids having 2 to 19 carbon atoms and their alkali metal salts; is performed. 10. Process for the simultaneous trimerization of a polyisocyanate and producing a rigid polyurethane foam by converting a mixture of one Polyaikylenpolyol, which at least two reactive hydrogen has atoms, and at least one organic polyisocyanate, characterized in that the trimerization and polymerization catalyst combination 0.01 to 5 parts of at least one compound from the group: 1,3,5-tris- (N, N-dialkylaminoalkyl) hexahydrotriazine, 2,4,6-Tris- (N, N-dialkylaminoalkyl) phenols and their adducts with alkylene oxide and water; and 0.01 to 5 parts of at least one compound from the group: alkali metal salts from carboxylic acids having 2 to 19 carbon atoms; used per 100 parts of organic polyisocyanate will. • MÜ. R PNCKE, DlPL-If: *. H. S6f # NKiN &. S. - 19 - .609-843 / 1002