DE2357859A1 - Catalysts for epoxy resin and polyurethane prodn. - consisting of tert. amine salts of substd. carboxylic acids - Google Patents

Abstract

A catalyst for the polymn. of polyurethanes (and epoxy resin) precursors contains salts of amines with 1 or more tert. N atoms and carboxylic acids with an alpha-substit., which causes irreversible thermal decompsn. to the catalytically amine and CO2 to take place at 70-200 degrees. The salts are of formula: AH + OCO-CRR1 -nX (in which A is an amine; m is 1 or 2; R and R1 are hydrogen, (m)ethyl or aryl; n is 1 or 2, and X is -CN, -NO2, -COO, or -COCH3 if n = 1, or -SO-, -SO2- or -CO- if n = 2, in alpha-posn.). The catalysts give compsns. which have prolonged storage stability at room temp. but react on heating, due to quick and irreversible decompsn. of the salts, releasing the active amine.

Description

AIR PRODUCTS AND CHEMICALS, IFC. P, O. Box 538, Allentown, Pennsylvania I8105, U.S.A.

Catalyst mass

The invention relates to a catalyst composition with a content on an acid salt of a tertiary amine, which is "an essential" when used in a polyurethane precursor composition increased activity in polyurethane formation catalysis has a temperature significantly above room temperature.

Urethane and epoxy resin reactions are known to require the Catalysis, especially the formation of such polymers in the form of cellular polyurethanes, polyurethane coatings and Epoxy moldings and foils *

509822/1057

In certain applications of polyurethanes and epoxy resins it proves desirable to produce a mass which contains practically all components in a practically stable source at a comparatively low temperature, and to cause a rapid polymerization reaction at a time when the composition is at activation temperature is heated. When trying for such heat-activated Difficulties are encountered in using bulk amines as catalysts because the amine tends to start the polymerization already to promote considerably at room temperature. A delayed-action catalysis has so far been achieved by that an acid salt of a tertiary amine was used. So was z. B. a delayed onset of catalysis through use a benzoate salt or acetate salt of a tertiary amine. Such salts, however, tend to both to partially dissociate at room temperature as well as at elevated temperature when used as a catalyst with a polymer precursor system be incorporated. Partial dissociation occurs at room temperature and leads to premature one Amine catalysis, so that the applicable storage stability of the component composition is shortened in a disadvantageous manner. At elevated temperatures, some of the amines turn out to be useless for catalysis, since their dissociation is reversible.

When it comes to the balanced catalysis of polyurethane compounds, it has Proven to be advantageous to use a mixture of amine catalyst and tin catalyst. Because of the intolerance between the benzoate salts of tertiary amines and tin catalysts, however, the use of such Do not enforce catalyst masses. Despite the continuing need for heat activated catalysis for polyurethane precursors The previous efforts brought the salts of tertiary amines as catalysts with delayed action use, significant disadvantages.

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It has now been found that, according to the present invention, the catalysis of polyurethane and epoxy resin reactions can be brought about with the aid of a catalyst composition which has a tertiary amine which is irreversibly released at elevated temperature from the salt of the tertiary amine and an acid, the acid thereby is characterized 'that it is a carboxylic acid which is substituted in the w-position with a group which promotes ^{thermal decomposition at a temperature below 200 0 O.}

Salts of this type correspond to the general formula

0 R
φ θ II I

R ¹
where mean:

A is an amine with at least one tertiary nitrogen atom,

R and R ¹ independently of one another are a hydrogen atom, an alkyl radical with 1 or 2 carbon atoms or an aryl radical,

X is a remainder of the formulas CN, SO, SO ₂ , CO, NO ₂ , COCH ₃ and CO ^ that promotes decomposition,

m = 1 or 2,

η = 1 if X is a radical of the formulas CN, NO ₂ , GO0 _t or COCH-. means and ■

η = 2, if X denotes a radical of the formulas CO, SO or SO _2.

Typical compounds suitable as catalysts for polyurethane formation which can be used according to the invention,

509822/1057

-A-

are z. B,

TEDA-bis-cyanoacetate of the formula 0 > 0

NCH ₀ CCO HN / \ / NH 0-C-CH ₂ CN

Bis-TEDA acetone dicarboxylate of the formula

ο ο ° η ffi

0-C-OH ₂ -S-CH ₂ CO ΗΝ / Λ / Ν

_22nd

DMEA-oyanoacetate of the formula OH,

HOOH ₂ -CH ₂ -NH 0 -C _{-CH 2 -CN}

Bis-DMEA acetone dicarboxylate of the formula

i ³ e £ g · 2 θ

HIGH ₀ CH ₀ -NH 0-CCH ₀ -C-CH ₀ CO

OH.

CH.

HN-CH ₀ CH ₀ OH ® \

2.2 ^f -oxybis (dimethylethylamino) sulfonyl diacetate of the formula

• ^0H

OH ₀ -N-CH ₀ CH ₀ -O-CH ₀ CH ₀ N ^{3 2}

3 θ

O-CH ₂ O-SO ₂ -H ₂ CCO

B09822 / 1057

_ 5 - bis (dimethylcycloh.exylamine) -tliionyldiaoetat of the formula '

/ ³ © 2- S 2 θ ® / ³ / - \

/ VIH ⁰ OC-GH ₂ -S-CH ₂ -OO HN: (\

^ CH

N-ethylmorpholine cyanoacetate of the formula

ti rt nrj θ »t

3 ι 2 0-C-CH ₀ -CN

NfN-dimethylisopropanol-amine-acetoaeetat of the formula

fa fs _Θ ο ο ■

HO-CH-CHg-ILH Ö-S-CHg-C-OH,

N-methyl-silylmorpholino-cyano-acetate of the formula

_{HN 0} -Q-CH 0 -CN

1 it ^

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ITjH-dimethylpiperazine bis-nitroacetate

θ 2

CH ₃

Typical suitable oc-substituted carboxylic acids are, for. B. Gyanoacetic acid, nitroacetic acid, acetone dicarboxylic acid, suIfo— nyldiacetic acid, thionyldiacetic acid, acetoacetic acid and Benzoylacetic acid.

According to the invention can be used the salts of the specified acids with amines which contain one or more tertiary nitrogen atoms, typical suitable such amines such. B. are tetramethylbutanediamine (TMBDA) ₁ trimethylaminoethylpiperazine (TAP), tetramethylguanidine, azabicycloheptanes, azabicyclooctanes, F-allylpiperidines, 2,2'-oxybis- (morpholinoethylether), amorpholines, N-alkylimidazoles and.

The amine salts which can be used according to the invention are generally prepared by mixing 1 mol of amine and 1 mol monobasic acid or 1 to 2 moles of dibasic acid. Bistertiary amine salts are made by mixing 1 mole of bis-tertiary amine and 1 to 2 moles of either monobasic or dibasic acid. Though a direct mixing of the amine and acid proves possible, the use of a solvent is preferred. Typical suitable Solvents are e.g. B. water, alcohols, ether and acetone. The use of acetone has proven to be particularly advantageous proven. The temperature range of the reaction is between

609822/1057

30 and 50 ^° C. After the reaction has ended, the product salt is separated off from the solvent, e.g. B. by filtration, centrifugation or with the help of other suitable separation methods, if the salt formed is a pesticide. If the product salt is a liquid, the solvent can be removed by evaporation under reduced pressure. The amine salts used according to the invention can of course be either the hydrates or anhydrous salts. So z. B. the product salt obtained in an aqueous solvent be in the hydrated form, or the anhydrous salt can be hydrated with or before use as an activator-catalyst.

Because of the careful selection of oc Oarbonsäurekomponente -substituted amine salt of the amine salts of the invention undergo an irreversible thermal decomposition at the activation temperature of the reaction below 2 and not only a reversibly extending dissociation according to the indicated reaction. 1

0 ^ ^ _n 0

Il θ® Η

Reaction 1i CH-C-O HAΟΉ -.- 0-CH + A

it Ow

Reaction 2: X-CHp-GO HA -> XCH -. + A + C0 ₂ f

In these reaction equations, A denotes an amine with at least one tertiary nitrogen atom and X has the indicated value Meaning.

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The rapid, irreversible thermal decomposition of the acid component of the salt at the activation temperature sets this tertiary amine free for effective catalysis of aromatic or aliphatic polyisocyanate and polyol precursor compounds or the epoxy precursor compounds at the activation temperature. The compound containing the precursor compounds for the production of polyurethane or epoxy resin can therefore contain the catalytic components containing the salt of the tertiary amines at room temperature and is nevertheless, whether in a mixed or unmixed form, stable over long periods of time, regardless of sensitivity against decomposition to develop activation at elevated temperature.

The catalyst compositions according to the invention can be used solely from the specified salt as an activator for the polyurethane or Epoxy resin formation exist or as Oo catalysts together present with other catalysts, be it with another amine catalyst or an organometallic catalyst, e.g. B, a catalyst derived from tin, silicon, antimony, lead, copper or iron

The catalyst compositions of the invention are also more advantageous Way in polyurethane or epoxy resin precursors Usable are the usual known additives, for example blowing agents, pigments, fillers or surface-active agents contain.

The following examples are intended to explain the invention in more detail.

example 1

A solution of 100 ml of acetone containing 0.2 mol Gyanoacetic acid was mixed with 100 ml of acetone ^ the 0.1 mol of Sri-

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Ethylenediamine contained ₉ mixed «The mixture of the two solutions led to the formation of a precipitate _? that of triethylenediamine bis-cyanoacetate of the formula

12 ^H 18 ^N 4 ° 4

Stocks This precipitate was dried in a vacuum oven at 60 ⁰ O. It was found that its melting point was 124 ° C. The analytical values given below confirmed that the composition corresponded to that of the expected bis-triethylenediamine-dicyanoacetate.

Calculated G 51.06 H 6 _? 38 HM9> 86 Found it? C 5O ₉ 72 · H 6.32 H 19 * 49 '

In further experiments, was in a similar 'orphan Triäthylendlamin-monoeyanoacetat made zersetzi ₀ This © Connection; ®, to 140 ⁰ G ₀ The .Analysenwerte for this connection the empirical formula GqIL J ^ Qp reindeer in Sublimierapparat at 135 as folgtg

Calculated C 54.82 H 7.61 I. 21 ν 32 Found G 54 «50 H 8p 50 if 20th p35

To determine the ka-fealytiseiisn activities wu ^ d® eia Vinylübsraüg © certain j, Polyisosyaaato ^ ladginappea saades Polyesteruretiiaa (Hugkson ^ s ΒΣ = Αβ2 = 12) Tsrwsndsto Is wards a © Reitis τοη Sasts performed at 100 'G raiter ¥ 33? =

/ 10S1

0.2 g of ethylenediamine bis-cyanoacetate in 10 g of des Prepolymer mixture with a curing time of 60 minutes,

0.3 g per 10 g with a curing time of 45 minutes, 0 »4 g per 10 g with a curing time of 30 minutes and 0 »5 g per 10 g with a hardening time of 26 minutes.

These conditions are summarized again in Table I below.

a b e 1 1 ... e I

Cure time at 100 ⁰ G using

g catalyst min «hardening

0 ^ 2 60

0.3 45

0.4 30

0.5 26

The same sri-ethylenediamine bis-cyanoacetate was used as the hardening agent for the coating prepolymer kept at room temperature. Ethylenediamine · Mscyanoaoetats are listed in the following case II

5 0 9 Β 2 2/1 0 p

Table II

Cure time at room temperature using

g ■ h

O ₉ 20 24

0.30 · 24

0.40 24

0.50 24

0.60 24

As a comparison sample, a solution which practically contained 35 # triethylenediamine in polypropylene glycol was used as a comparative catalyst, the same polyester urethane precursor compound being used in 10 g batches. However, there were considerable variations in the curing time as a function of the concentration of the catalyst both at room temperature and at 100 G _5, as shown in Tables III and IV below »

T a b e 1 1 e III

Curing time at room temperature using a 33% solution of N (G ₂ H ₄ KN

g 'h

3.55

3 * 62 2 ₀ 92 · ^2s38 109822/1 057 1 * 50

0 ρ 22 0 »33 0 , 44 O p55 0 .66

Table IV

Cure time at 100 ⁰ O using a 33 follow solution of

g min.

0.33 113

0.44 90

0.55 65

0.66 53

The fact that the triethylenediamine bis-cyanoacetate salt exhibited a delayed effect, resulted from the finding that it was much slower at room temperature than the solution of triethylenediamine, whereas at 100 O it worked much faster. The results show that the triethylenediamine-bis-cyanoacetate at elevated Tempe temperature an equally useful catalyst for the tested Prepolymer is, like the solution of triethylenediamine, that depending on the triethylenediamine biscyanoacetate at room temperature an advantageous stability and durability for much longer having in the mixture.

Example 2

The decomposition temperature and properties of triethylenediamine bis-cyanoacetate were examined by heating a 3 »4 g sample of the salt in a sublimer a temperature range from 130 to 150 0; d. H. i.e. above the melting point temperature of 124 ° G. That developed

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Gas from the sublimer was passed through a gas cuvette · and passed into a gas measuring device »The evolved gas was identified as carbon dioxide by passing it through a solution of barium hydroxide, forming a white precipitate formed from barium carbonate. After the salt had decomposed, the remainder was weighed, whereby showed that its weight was 1.30 g, and it was identified as triethylenediamine. The theoretical value for that Gas volume was 5 »4 dnr (0.019 cu.ft.), which corresponds to the measured · The value for the gas volume of 5.1 dm (0.018 cu.ft,) is very close came. Also the measured weight of 1.30 g for the triethylenediamine largely corresponded to the theoretical amount of 1.34 g.

It must be emphasized that the terms "decomposition temperature ¹¹ " and "thermal activation temperature" are not synonymous since the onset of decomposition of such salts usually occurs at a lower temperature than the "decomposition temperature ¹¹ " and progresses over an increasing temperature range. When used as a catalyst, these salts decompose at elevated temperatures and start an exothermic reaction in the polymer! _On? which in turn promotes the further decomposition of the catalytic salt.

Example 3

In a combined GasChromatograph (G, C.) Mass spectrometer instrument, the G ₉ O. of which was equipped with a 4 »5 m chromatography column, which was packed with 15 ^ Apiezon L on Gas-Ghromatograph-Q substrate, various aqueous or - Entered methanolic solutions in the GG at 150 ⁰ C and the temperature of the column was programmed ^{from 100 to 200 0 G.}

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The decomposition products of the salts tested were separated on the column and then fed to the mass spectrometer., with the aid of which they were identified, the results obtained are shown in Table V below.

Tabel V theoretical
Amount wt .- ^ salt Decomposition
Products approximate amount
in ^, gaschroma
tographically be
Right 31.2
29.1
39.7 TEDA-to-
cyanoaoetat CO
Acetonitrile
TEDA 34.90
29.62
35.43 27.2
17.9
54.9 Bis-DMEA-
acetone-di-
carboxylate GO
acetone
DMEA 20.0
33.6
46.2 26.7
24.8
48.5 2.2 ^f -0xybis-
(dimethyl -
ethylamine) -
bis-cyanoace-
did GO ₂
Acetonitrile
2,2'-oxybis-
(dimethylethyl
amine) 30.1
• 23.9
46.0 23.8
15.7
60.5 TEDA acetone
dicarboxylate GO ₂
Acetone
TEDA 24.2
27.7
48.1 31.7
28.0
40.3 TEDA thionyl
diacetate GO ₂
DMSO
TEDA 42.4
3.0
53.4

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2357853

Example 4

A polyurethane precursor composition containing 100 g of polypropylene glycol having a molecular weight of about 3000 (commercially available under the designation ¹ CP-BOOO "), which served as the polyol, was used for the following tests. The composition containing the precursor compound also contained 10 g of technically pure tolylene diisocyanate, the ratio of 2,4- to 2,6-isomer about 80:20. At room temperature, the use of triethylenediamine-bis-cyanoacetate showed in a series of tests in which increasing amounts of the catalyst were used , the same degree of cure for a time period of 48 hours, from which it was found that the curing was carried out spontaneously and not due to the catalyst concentration. at 100 ⁰ O curing time compared to an uncatalyzed sample was greatly shortened, whereby the effect of catalyst concentration on the Cure time was practically the same, regardless of whether the solution of the triethylenediamine or the triet hylenediamine-bis-cyanoacetate salt were used. At a concentration of 0.1 g of catalyst per 10 g of precursor compound, the curing time was 14 minutes for both the decomposable salt and the triethylenediamine solution. When using 0.2 g of catalyst per 10 g of precursor compound, the curing time was 12 minutes, for the decomposable salt and 8 minutes for the triethylenediamine solution. When using 0.4 g of catalyst per 10 g of precursor compound, the curing time was 8 minutes for the salt of triethylenediamine-bis-cyanoacetate and 6 minutes for the solution of triethylenediamine. When the triethylenediamine solution was used, the curing times at room temperature were 100, 60, 30 and 20 minutes for the amounts of 0.12, 0.24 »O» 36 and 0.48 g of catalyst used per 10 g of the polyurethane precursor compound, respectively.

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The results obtained showed that iriethylenediamine — to— cyanoacetate is an effective delayed action catalyst that can be activated by heat and the same reliable practical behavior like a free triethylenediamine catalyst shows.

example 5

It has produced a number of compounds with the desired ease of decomposition from various acids and tertiary Amines produced. It was made in a round bottom flask fitted with a reflux condenser and a mechanical Stirrer was equipped by adding the equivalent amount of the amine to the acetone solution in the flask the acid. The reaction temperature was kept below 50 ° 0 by external cooling. When the addition was complete the reaction mixture is cooled and the product formed is isolated by filtration. The yields were quantitative.

After drying in a vacuum oven, the purity and the composition of the salt is determined by chemical analysis. There were those listed in the following Table VI Catalysts according to the invention prepared.

Table VI

Analysis of amine salt Empirical formula P ( ⁰ O) calc.

Triethylenediamine 0 _in H 0O ₁ -S ₁ Ii ₉ 103 C 43.52 G 43.17

thionyl diacetate iu jo D ι ^ H 6.70 H 6.47

Έ 10.12 W 10.07

4- (2-dimethylamino- O ₁₁ H ₉ JT ₁ O.74 0 51.22 0 51.25

ethyl) morpholine- ^bis-14 ** * ° H 7.32 H 7.43

cyanoaoetat. Ii 17.07 Ή 16.96

S09822 / 10B7

Example 6

About 100 parts of a polyol blend consisting of about equal parts of polypropylene glycol having a molecular weight of about 2,000 and a polyethylene glycol having a molecular weight of about 4,000 were used for the following tests. The precursor composition contained about 12 g of tolylene diisocyanate per 100 g of polyol and 4 g of triethylenediamine bis-cyanoacetate. The precursor compound was used in a coating machine in which a textile web passed through a coating zone was provided with a uniformly thin coating of precursor compound. The coated web was passed into zones where the precursor compounds were creamed, foamed, swollen and cured to bond the polyurethane foam cover to the advancing textile web. The hardening ^{zone was kept at 100 °} C. and the hardened, polyurethane foam-coated web was drawn off from this zone. The mass containing the precursor compounds was kept practically at room temperature, and it was found to be important that it was stable for a long time so that no disadvantageous increase in viscosity occurred during normal operations.

For the preparation of the tertiary amine salts used ^ was the triethylenediamine and sulfonyldiacetic acid are mixed in acetone and the salt formed is filtered off from the acetone. at Using this salt as a catalyst, the delayed action of the catalyst proved to be very satisfactory and a good product was obtained because of the decomposition of the salt, whereas in a comparative sample, in the triethylenediamine diacetate salt was used, only dissociation of the salt occurred.

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Example 7

A mixture of 0.40 parts of catalyst per 10 parts of polyol composed of 100 parts of ethylene glycol terephthalate with a molecular weight of 3000 and 20 parts of diisocyanatochlorophenyl methane was used as the catalyst to produce a textile product with a polyirethane foam coating. The amine salt catalyst used was triethylenediamine acetone dicarboxylate, in which the two acetyl groups are linked to one another by a carbonyl group. The use of this delayed action catalyst gave results that were better than the use of a dibenzoate salt of triethylenediamine as the thermally activated catalyst. The superior results are apparently at least partially explainable by the ease of thermal decomposition of the acetone dicarboxylate anion and the reduced tendency to reversibly dissociate.

Example 8

The salt of bis-dimethyl-aminoethyl ether and thionyl diacetic acid was used as a catalyst with a delayed action. In addition, a small amount of dibutyltin diacetate catalyst, which was about 1/5 the amount of the amine salt catalyst used in the precursor composition which was 100% Parts of ethylene glycol terephthalate with a molecular weight of 3000, 20 parts of di (isocyanate-chloro-phenyl) meth.an, 2.5 Parts of the amine salt and 0.5 part of dibutyltin diacetate. The manufacture of the coated with polyurethane foam The textile fabric performed satisfactorily because of the advantageous delayed action and long stability the mixture of catalyst and precursor compounds.

50 98 22/10 57

235785S

- Example 9

To harden an epoxy resin, a mixture of 10 parts of glyeidyl polyether (Epon 828) and 1 part of amine hardening medium stirred for 2 minutes and then "at different Allowed to harden temperatures. In the following table "VI the different curing times for triethylenediamine and triethylenediamine- ^ bis-cyanoäeetatsalz are compared juxtaposed.

Table VII

Hardening Curing time in minutes TEDA-Ms- temperature cyanoacetate TEDA > Week Room temperature 420 - 50 48 - 80 11 55 100 8th 12th 135 3 8th 150 1

The results clearly show that it is desirable for applications in which stability over prolonged periods of time is, the catalysts of the invention offer great advantages, since they practice with thermal activation develop corresponding full activity

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Example 10

A polyurethane precursor composition composed of 100 parts of polyol (OP 3000) and 10 parts of tolylene diisocyanate (isomer ratio 2.4 / 2.6 = 80/20) was ^{cured at room temperature and at 100 0} using reversible amine salts The amine salt per 10 g of polymer and the curing times are listed in Table VIII below.

Table VIII

Reversible amine salt conc.

TEDA-difor- 0 , 08 miat 0 , 18 0 , 23 0 , 30

Curing time in minutes

at room temp.

85 65 45 30

at 100 ^υ 0

13th

9 6

The results show that TEDA diformiat at room temperature In contrast to the salts according to the invention, only a brief stability reveals their advantageous behavior z. B. shown in Example 1, Table II

Example 11

A prepolymer mixture of 100 parts polyol (QP 3000) and 10 parts of tolylene diisooyanat (isomer ratio 80/20) was bis-acetate triethylenediamine with various amounts of (a reversible salt) cured at both room temperature and at 100 ⁰ O. The concentrations used (in parts per 100 parts, expressed as / pph) and the cure times found are listed in Table IX below.

50982271057

Table IX

Conc.
pph. Curing time in minutes Amines al ζ 0.08
0.17
0.33 at room temp. at. 100 ⁰ O TEDA-bis-acetate 106
51
36 10
6th
4th

The results show that triethylenediamine-bis-aoetat in In contrast to the salts which can be used according to the invention, their advantageous stability is only achieved for a short time at room temperature Properties sioh z. B, from Example 1, Table II.

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Claims (8)

Request a patent 1. Catalyst composition containing an acid salt of a "tertiary amine, which when used in a polyurethane precursors rmas se has a significantly increased activity in polyurethane formation catalysis at a temperature substantially above room temperature, characterized in that the salt of an amine with at least one tertiary nitrogen atom and a carboxylic acid with a seated in α-position, the. Thermal decomposition promoting remainder is built up, which promotes _{the irreversible release of tertiary amine and GO 2} by the thermal decomposition of the salt at a temperature in the range from 70 to 200. 2. Catalyst composition according to claim 1, characterized in that the OC-substituted carboxylic acid from cyano acetic acid, Nitroacetic acid, acetone dicarboxylic acid, sulfonyl diacetic acid, Thionylacetic acid, acetoacetic acid or benzoylacetic acid consists. 3. catalyst composition according to claim 1, characterized in that that the amine from tetramethylbutanediamine, trimethylaminoethylpiperazine, Tetramethylguanidine, azabicycloheptanes, • Azabicyclooctane ^ N-Ällylpiperidinen, 2,2'-0xybis- (morpholinoäthyläther), Amidines, N-alkylimidazoles or silylmorpholines consists. 4. catalyst composition according to claim 2, characterized in that that the oc-substituted carboxylic acid from oyanoacetic acid consists· 509822/1057 5. catalyst composition according to claim 3 »characterized in that ■ That the amine consists of triethylenediamine. 6. Catalyst composition according to claim 1, characterized in that the salt from the reaction product von'Triäthylendiamin and oyanoacetic acid. 7. catalyst composition according to claim 1, characterized in that that they are polymerizable to catalyze the polymerization carried out at a temperature in the range from 70 to 200 0 Components used in a reaction mixture. which is an organic compound having a plurality of isocyanate groups per molecule, and an organic compound containing a large number of hydroxyl groups per molecule, which enables the manufacture of a polyurethane product enable. 8. catalyst composition according to claim 1, characterized in that that it is used to catalyze the hardening of a hardenable epoxy resin into a hardened epoxy resin carried out at a temperature in the range from 70 to 200 ^{0 O.} Salt of a tertiary amine and an -substituted carboxylic acid for building up the catalyst composition according to claim. 1, characterized in that the salt is ^{thermally decomposable at a temperature of below 200 0} G with liberation of the tertiary amine, based on the general formula / "AH 7 _m Γ OGG 7 X <- - ' m * - ι -' η R ¹ 509822/1057 where "mean: A is an amine with at least one tertiary nitrogen atom, m = 1 or 2, R and R ^f independently of one another are hydrogen atoms or methyl, ethyl or aryl radicals, η s = 1 or 2 and X is a remainder of the formulas GH, NO ₂ , CO ^, GOGH-, sitting in the ot position and promoting thermal decomposition. at η β 1, or the formulas SO, SOg or 00 with η = 2. 509822/1057