DE2721626A1 - COMPOUNDS OF THE N, N'-POLYOXIALKYLENE-BIS (PYRROLIDINONE-3-CARBONIC ACIDS) TYPE, METHOD FOR THEIR PRODUCTION AND THEIR USE - Google Patents

Description

afterwards fieänoort

DR. GERHARD SCHUPFNER

PATENT ASSESSOR IM MAU · «OEUTSCHE TEXACO Αβ

UbarMarlng * O aOOO Hamburg OO

T.i.fon io * o) ea TS 2T as Pamaehrat Mr. Oa 17000

Hamburg, 23.03.77 547-He

T 77 006 (D 75.010)

TEXACO DEVELOPMENT CORPORATION

135 East 42nd Street

New York, N.Y. 10017

UNITED STATES.

<-> rd, procedure to their Manufacture and its use

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The invention is directed to new compounds which are suitable as hardeners or hardening accelerators for synthetic resins.

It is known that epoxy resins by means of aromatic amines, such as. B. methylenedianiline, condensation products of aniline and formaldehyde, etc., can be cured. When hardening at temperatures of 80 ° C. and above, products are obtained which are resistant to chemicals, solvents and the like. Upon curing of epoxy resins at room temperature coatings is, however, obtained which is not fully cured, are brittle and without resistance and be attacked by many chemicals and solvents.

The invention is based on the object of creating new compounds which are more suitable than the known ones, in particular for curing epoxy resins and polyurethane foams. The products hardened with these compounds are said to have better properties than those obtained with the known hardeners or hardening accelerators.

The object is achieved by a compound of the general formula I.

[■

COOM

in the mean

a R ¹ · ·

M H

H.

a number from 0-2, a number of at least 2, a polyoxyalkylene chain of molecular weight from 200 to 2000, to the terminal carbon atoms of which N radicals are bonded, Hydrogen or an alkali metal ion and hydrogen or a monovalent substituent.

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According to the invention, the connection is produced by a process that is characterized in that a moles of an unsaturated carboxylic acid of the general formula II

HOOC C = CH-

^(H 2 ^C) x

I.
H ₂ C COOH

in the H hydrogen

or a monovalent substituent with 1 mol of a polyoxialkylenepolyarain of the formula III

■ i

R ¹ 'H (-

in which R ' ¹ ' is a polyoxyalkylene chain of molecular weight

from about 200 - 2000 and a is a number of at least 2 ,

reacted under ring formation conditions and the product obtained is isolated.

The compound of the following general ones is particularly preferred Formula I

H H

HOOC — C — CH “, C — CH COOH

(HC) N \ -K "\ N (HC)

HC-CC CH ₅

Il It * -

0 0

in which mean: χ a number from 0-2 and - R "- a polyoxyalkylene chain with a molecular weight of about 200-2000 with terminal carbon atoms that are bonded to nitrogen atoms. The compound is produced by reacting 2 moles of an unsaturated one Carboxylic acid of the general formula II given above with about 1 mol of a polyoxyalkylenediamine of the formula IV

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under ring closure conditions and isolating the product obtained.

The invention will now be described in more detail.

The unsaturated carboxylic acids that are used to prepare the inventive Compounds that can be used fall under the following general formula II

HOOC C = CH _a

(H C)

I.
H ₂ C COOK

in which χ means an integer from 0-2. For direct to C bonded Η atoms can also have monovalent inert substituents that do not interfere with the implementation.

When χ is 2, the acid can be <* - methylene-adipic acid; if χ 1 is oc-methylene-glutaric acid, and when χ is 0, itaconic acid. The preferred acid is an acid of the general formula II in which χ is 0.

The Polyoxialkylenpolyamines, which in the process according to the invention are used to prepare the new compounds can be represented by the following general formula III :

in which: a is a number of preferably 2-3 and R ¹ · 'is a polyoxyalkylene chain with a molecular weight of 200-2000 and a is terminal C atoms which are bonded to N atoms. An example of a polyoxypolyalkyleneamine of the formula III, in which a is 3, can e.g. B. be the following connection:

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CH ^ - I OCH ^ CH (CH ^) - H NH-

CH ₃ CH ₂ - C-CH ₂ - I OCH ₂ CH (CH ₃ ) 4 _{- NH 2}

- M

) I-

CH) + - NH-

where f plus g plus h is 5.3 and which has a molecular weight of about AOO. (This compound is commercially available under the name Jeffamine T-403.)

Polyoxialkylenediamines of the general formula IV are preferred

R "

in which R "is a polyoxyalkylene chain with a molecular weight of about 200-2000, the terminal carbon atoms of which are bonded to nitrogen atoms . R" is derived from an oxyalkylene group, e.g. B, oxyethylene-CH ₂ CH ₂ O-, oxypropylene-OCH ₂ CH (CH ₃ ) - etc. R " can also be a polyoxyethylene which bears a polyoxypropylene radical. The following is the formula of such diamines (which are commercially available under the name Jeffamine ED are available):

CH_ CH. CH- CH-

, 3, 3 I 3, 3

CHCH ₂ (OCH ₂ CH) _n (OCH ₂ CH ₂ ) _m (OCH ₂ CH) _k

Some polyalkylenediamines which can be used in the process according to the invention are listed below by way of example. Needless to say, these are amino-terminated diamines.

Polyoxypropylenediamine, molecular weight 427

Polyoxypropylenediamine, molecular weight 235

Polyoxypropylenediamine, molecular weight 2000

Polyoxyethylene diamine, molecular weight 600

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Many of the suitable polyoxyalkylene polyamines are commercially available as Mixtures available (Jeffamine D, T, ED, etc.).

In the process according to the invention, an equivalent amount is used Unsaturated acid is added to a reaction mixture together with 1 mole of polyoxialkylenepolyamine. The reaction can, as desired, be carried out in the presence or absence of a diluent. Suitable diluents are water, Toluene etc. Water is preferably used in an amount of 50-200% by weight, preferably about 100% by weight, based on the amine, used. During the reaction, the temperature is increased to 80-200 ° C, e.g. E.g. 100 ° C, 4 - 12 h, e.g. B. 8 During this time, the following reaction takes place:

200 ° C, e.g. E.g. 100 ° C, 4 - 12 h, e.g. B. 8 h held. While

HOOC - C = t

(H ₁ C) r ^x

H £ - C

- OH

C-C- COOH \

C-CM _x

If

/ a

If the preferred diamines are used, the following reaction takes place:

HOOC - C = C ^ K, C. - COH X Γ " H ₀ / R »J_ NH ₂ ι
_f J Il ^ N-J-H-- C ² - - Ν (H
ι \ H ₁ C 0 \ -
If 0 - CH _? H H C - COOH HOOC - C ι ι - C
Il 2 ^ x (H ₂ C 0 CH ₂ H ₂ C

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If itaconic acid is used with a polyoxyethylene di-primary arain the reaction shown below takes place:

HOOC - ^ - CH ₂ + H 2 N - I— CH - A W ΓΊ - 2 - 1 CH ₂ CH ₂ - NH ₂ - H 2 ^C - COH
ft 5 0 H
C. - COOH HOOC P. ■ CH 2 " N / I. \ - CH ₂ CH 2 0 · 15th ₂ CH \ H 2 ^C " C-N
It - ' C -
It 2 0 0 CH

Another preferred embodiment can be represented by the following equation:

HOOC - C

H ₂ C

HOOC - C

H ₂ C

= CH ₂

- COH tt

It

+ H "N · CH CH" O

-CH.

N + CH CH 0 ■ · -CH ^

■ CH "- CH - NH.

15th

CH.

Mr.

C-C-COOH

- CH - N t

CH "

C - CH.

It '

If the reaction is further continued, the water produced in the reaction (in an amount of 1 mole per mole used acid) distilled off. If desired, the water can be refluxed by azeotropic distillation with e.g. B. Toluene can be removed. At the end of the reaction period, the reaction mixture is isolated and filtered, preferably in the presence a filter aid (Supercell).

The product thus obtained is preferably by stripping in a rotary evaporator at 80-200 ° C, z. B. 95 ° C,

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worked up. The stripping can be carried out under a vacuum of 0.13-66.5 mbar, e.g. B. 0.66 rabar. The yield is about stoichiometric.

As a rule, the product is obtained as a compound (dependent on the components from which it is made, and depending on its molecular weight), considered to be a clear, viscous one Liquid, a pale brown, viscous liquid, a sticky resin, etc. can be identified.

These products are generally recognized by their solubility in Alcohols (e.g. benzyl alcohol, ethanol, hexanols, etc.). They are particularly characterized by their Solubility in polymer systems in which they are used.

These products can after their isolation or in the form of their solutions in z. B. Benzyl alcohol can be used. they draw are particularly characterized by their ability to accelerate the hardening of epoxy resins. They are also suitable, in particular when in the form of their salts, e.g. B. alkali metal salts (preferably potassium, but also sodium salt, etc.), are present as Hardener for polyurethane foams. Although they are considered monoalkali metal salts can be used, they are preferably used as di-alkali metal salts.

The dialkali metal salt can be added by adding an equimolar amount from Z. Potassium hydroxide in 5-30, e.g. B. 20% aqueous solution at 20 - 80 ° C, z. B. 50 ° C, to be prepared for the isolated reaction mixture. After 10-20 min, e.g. B. 15 min, prolonged stirring, the reaction mixture can be filtered through a filter aid bed and the resulting solution can be used as a filter aid such, e.g. B. as a 10-80%, e.g. B. 50% solution can be used. If desired, the salt can be evaporated to be isolated. Both the mono- and the dialkali metal salts can be used be won.

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The invention also includes the use of the compounds for curing epoxy resins. If hardening is carried out at 20 - 50 C, e.g. B. 30 C, made, products are obtained with excellent properties, especially with regard to strength and retention of strength after immersion in solvents. Hardeners not covered by the invention, e.g. B. those which have been obtained by reacting itaconic acid with p-phenylenediamine (see Paytash et al Journ. Amer. Chem. Soc. 72, pp. 1A15-1A16, 1950) are not satisfactory curing accelerators for epoxy resins because they are im are generally high melting point solid compounds that are difficult to mix into the viscous epoxy resin composition. The products according to the invention are particularly characterized by their good compatibility with the epoxy resin components. The fact that they are all liquid is a great advantage for the processor.

An epoxy resin that can be cured using the compounds of the present invention can e.g. B. by reacting bisphenol-A with epichlorohydrin in the presence of a base, preferably sodium hydroxide solution . After the condensation is complete , the crude resin is stripped of residual epichlorohydrin, washed to remove salt and soluble by-products , and isolated.

For hardening 100 TIn. such a resin are 20 - AO TIe., z. B. 30 TIe., An aromatic polyamine as hardener and 1-15 TIe. the compound of the invention as an accelerator in z. B. 10 - 30 TIn., E.g. B. 20 TIn., A 10-50% solution of this compound is required. A suitable aromatic polyamine hardener that can be used is the condensation product of formaldehyde with aniline (commercially available under the name Jeffamine AP-22). Further suitable hardeners are: methylenedianiline, diamino-diphenyl ether, m-phenylenediamine, tolylenediamine.

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272Ί626

The accelerator of the invention is preferably in the form the free acid mixed with the liquid epoxy resin and the hardener, the mixture degassed, poured into aluminum molds and Z. B. cured for 7 days at room temperature.

The hardened product is special due to its increased mechanical Characterized for strength and resistance to a wide variety of liquids.

The new compounds of the invention are also useful as hardeners suitable for polyurethane foams. You have opposite the familiar Hardeners have the advantage of a longer cream time, which increases the time it takes to prepare the mixture to be foamed Way extended.

A polyurethane foam which can be cured using the compounds of the present invention can be produced by reaction a polyfunctional isocyanate, e.g. B. a phosgenated condensation product of aniline and formaldehyde of an isocyanate equivalent weight of 134 and a functionality of 2.7, with a polyol with at least two reactive hydrogen atoms (determined by the Zerewitinoff method). Suitable polyols are e.g. B. Polyoxialkylene polyols with two or more reactive Η atoms, those with organic polyfunctional Isocyanates react to form polyurethanes. These polyoxyalkylene polyols typically have a hydroxyl number from 100-800, preferably 200-300, e.g. B. 200; polyester, polyether, polyisocyanate-modified polyester, Polyisocyanate-modified polyester amides, alkylene glycols, polyamines, polyisocyanate-modified alkylene glycols, etc. These polyols can of course be primary or active have secondary hydroxyl groups. The polyol can be a hydroxyl group-containing polyether or polyester, fatty acid glycerides included, be. The polyesters, which are a preferred type of polyol, can be prepared by reacting e.g. B. an aliphatic dibasic carboxylic acid with a glycol, a triol or

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a mixture thereof in such proportions that the resulting polyesters predominantly have terminal hydroxyl groups have to be received. Suitable dibasic carboxylic acids for the production of such polyester polyols are, for. B. aliphatic and aromatic acids such as adipic acid, fumaric acid, sebacic acid, phthalic acid; include suitable alcohols Ethylene glycol, diethylene glycol, trimethylol propane, etc. The fatty acid glycerides include those having a hydroxyl number of at least about 50 such as castor oil, hydrogenated castor oil, blown natural oils.

Polyethers, another preferred type of polyol, include polyalkylene glycols, e.g. B. polyethylene glycols and polypropylene glycols, which preferably have a molecular weight of at least 60, a. For the sake of simplicity, the term “polyol” or “polyoxyalkylene polyol” is used herein for substances which have two or more active Η atoms, determined by the Zerewitinoff method.

Polyurethane foams are made by reacting an organic compound with at least two active Η atoms, d. H. a polyol, an organic polyfunctional isocyanate, a foam modifier (eg. as a Dimethylpoly3iloxan with trimethyl-end blocks (Dow Corning DC-193)), a blowing agent, such. B. trifluoro-chloro-methane, and a dialkali metal halide of the compound according to the invention.

It sets the isocyanate and the polyol in such quantities that an isocyanate index in the reaction medium 1 - 10, preferably 3-6, z. B. 5, is. The blowing agent is used in an amount of 5-20 TIn., Preferably 10-14 TIn., E.g. B. 12 TIn., And the foam modifier in an amount of 0.1-15 TIn., Preferably 0.3-0.8 TIn., E.g. B. 0.5 TIn., Used. The catalyst, ie the compound according to the invention, is used in an amount of 0.5-10 tin., Preferably 1-4 tin., E.g. B. 2 TIn., Mixed in (all parts are parts by weight per 100 parts by weight of total composition).

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The polyurethane foams have the desired long cream time of over about 10 seconds, e.g. B. 15 s, improved heat resistance and improved dimensional stability at low temperatures, e.g. B. in dry air from -30 ⁰ C.

The invention will now be described in terms of preferred embodiments illustrated in more detail. All parts are parts by weight if not stated otherwise.

EXAMPLE I

393 g (3 moles) of itaconic acid, 600 g of water and 640.5 g of polyoxypropylenediamine (Molecular weight about 427, 4.69 m-equivalent primary amine per g) are heated under reflux for 8.5 hours. then Supercell filter aid is added, the reaction mixture is hot filtered and stripped at 0.66 mbar in a rotary dryer at a bath temperature of 95 C.

After cooling, a clear, viscous liquid is obtained which has an acidity of 3.26 meq / g and the following Formula has:

H HH

HOOC - C - CH ₂ C - C - COOH

N-

R "N

H ₀ C - C C- CH-

* - ti ti ^

0 0

in which R ^{n is} a polyoxypropylene radical having a molecular weight of about 400.

EXAMPLE II

526 g (4.03 mol) of itaconic acid, 600 g of water and 470 g (2 mol) of polyoxypropylenediamine having a molecular weight of about 235 and 8.53 m-equivalent prim. Amine per g are refluxed for 8 h

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heated. Then Supercell filter aid is added, the The reaction mixture is filtered hot and stripped at 0.66 mbar in a rotary dryer with a bath temperature of 95.degree.

After cooling, a light-colored, viscous, viscous resin with an acidity of 4.74 m-equivalent / g and an N content of 6.35% is obtained, which has the following formula:

HH _? H

HOOC - C - CH ₂ C - C - COOH

N R "N

HC - C C - CH ₉

if ti

ο ο

R ^w means a polyoxypropylene radical having a molecular weight of about 200.

EXAMPLE III

131 g (1 mole) of itaconic acid, 100 g of water and 1030 g (0.5 mol) Polyoxipropylendiamin a molecular weight of about 2060 and 0.97 g m-fiquivalent per primary amine under reflux for 19 h to a temperature of 98-100 ⁰ C heated. The water is removed by azeotropic distillation with 500 ml of toluene added during the reaction. Then Supercell filter aid is added and the reaction mixture is filtered hot and stripped at 0.66 mbar in a rotary dryer with a bath temperature of 138 ° C.

After cooling, a light brown, viscous liquid is obtained with an acidity of 0.82 m-Xequivalent / g according to the following formula:

HH ₉ H

HOOC-C-CH ₂ ^ C-C- COOH

N R "N

H ₅ CC C-CH

^ n it

0 0

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in which R "is a polyoxypropylene radical having a molecular weight of about 2030.

Results comparable to those in Examples I-III are obtained when the amines listed below are used will:

Example amine

IV polyoxypropylene tri-primary amine (with terminal Amino groups) with a molecular weight of AOO (Jeffamine T-403)

V Polyoxyethylene-polyoxypropylene-di-primary-amine (with terminal amino groups) of molecular weight 600 (Jeffamine ED-600)

etc.

The same results as in Examples I - III are obtained when the acids listed below are used:

Example acid

VI oC-Methylenglutaric Acid

VII oc-methyleneadipic acid

In certain examples that follow, the following properties are used certainly:

Cream Time - This is the time interval in seconds that begins with the mixing of the isocyanate and component B (a standard mixture that contains the polyol, the catalyst, the blowing agent, the wetting agent and the flame retardant) and ends when the composition changes its color changed from dark brown to cream.

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Rise time - is the time interval in seconds that begins with the mixing of the isocyanate and component B and ends when the foam stops rising.

Tack-free time - is the time interval in seconds that begins with the mixing of the isocyanate and component B and ends when the surface of the foam no longer becomes tacky to the touch.

Density (g / cm) - is the weight of a given volume of the product.

K factor (Watfrcm / ° C) - determined according to ASTM C 177-63 using the hot plate, which is modified according to Dupont .

Elongation at break (%) - determined according to ASTM D-638. Tear strength (bar) - determined according to ASTM D-638. Tensile modulus (bar) - determined according to ASTM D-638. Flexural Strength (bar) - determined according to ASTM D-790. Flexural modulus (bar) - determined according to ASTM D-790. Shore hardness D, 0-10 s - determined according to ASTM D-2240.

Heat resistance ( ⁰ C, 18.48 bar / 4.62 bar) - determined according to ASTM D-648.

Notched Izod impact strength (cm kg / cm) - determined according to ASTM D-256.

Compressive strength (bar) - determined according to ASTM D-1625-73.

Heat resistance (C) - determined by the temperature at which a standard specimen is pressed down by 0.254 cm under a load corresponding to 10% of its compressive strength in the direction of expansion.

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Closed cells (%) - determined according to ASTM D-2856-70.

Dimensional stability (%) - determined according to ASTM D-2126-75, modified to the effect that the sample has a size of 5.08 5.08 5.08 cm instead of 10.16 χ 10.16 χ 10.16 cm.

Flammability - determined according to the Butler Chimney Test -ASTM D-3019-73. It should be noted that the numbers or other information in this test are not a measure of the hazard this or any other material poses under the influence of fire, but a measure of the behavior of the material tested under certain controlled conditions.

EXAMPLE VIII

In this example, a hardened polyurethane foam is produced.

First, a B component is made from the following components:

159 g of polyol, namely a polyoxyethylene adduct of a novolak resin having a hydroxyl number of 187 and an average functionality of 2.5;

3 grams of a silicone surfactant, namely a trimethyl endblocked dimethylpolysiloxane; 72 g freon, that is trifluorochloromethane; 12 g of a 50% solution of the di-potassium salt of the product from Example I in polyethylene glycol with a molecular weight of 300, prepared by adding an equivalent amount of KOH (2 mol KOH / mol product) and polyethylene glycol to the product of Example I.

This B component becomes 354 g of a phosgenated aniline-formaldehyde condensation product with a functionality of 2.7 and an NCO equivalent weight of 134 is given. The mixture is stirred vigorously and then poured into a loaf pan and lathered up.

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Property time (s)

Cream time 15

Foaming time 140

Tack Free 150

The properties of the foam are shown in the table following the example below.

EXAMPLE IX (comparative example)

In this comparative example, the procedure was as in Example VIII, except that the following were used:

a) 160.8 grams of polyol;

b) 6 g of a 50% strength solution of potassium octoate in polyoxyethylene triol with an average molecular weight of 700 (a hardener according to the prior art) instead of the 12 g of the dipotassium salt solution of Example VIII;

c) 358.2 g of isocyanate instead of 354 g in Example VIII.

Property time (s)

Cream time 5-6

Foaming time 65

Tack Free 100

This control foam is less satisfactory than the foam of the invention. The cream time and the foaming time are far too short for practice. In the industry is a cream time for a foam composition that is intended for the plate-making of about 12 s is required; A cream time of 15-20 seconds is desirable , as is the case with Example VIII.

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properties (bar) example VIII example IX 0.035 in Density (g / cm ³ ) (Comparison example) 0.115 straighter ' K factor 0.03A Direction r Compressive strength O, 128 2.52 in foaming direction (bar) 0.80 transverse to the foaming direction 2.55 170 +5.0 Resistant to heat deformation ( ⁰ C) 0.94 92.72 + 3.9 Closed cells (V *) Vol. 202 -6.8 90.61 O + 9.1 co +5.9 in Weight 00 -4.5 straighter cn
he" Dimensional stability (%) Weight direction ■> * », ' at 70 ° C and 100% rel. Vol. -4.5 O' humidity -2, A at at 82 ⁰ C and dry -2.8 +5.6 -5.9 O at -29 ⁰ C and dry -1.6 + 3.9 +6.7 "Butler Chimney Test": -2.8 +5.3 90.7 Residue (%) -11, A 10.7 Time to extinction (s) 85.6 20.73 Flame height (cm) 1A 27.9A ₊

Friability

% Weight loss

8.5

5, A

The table shows the clear superiority of the foam according to Example VIII over that of Comparative Example IX. Additionally In addition to what has already been said, special attention should also be paid to the generally better properties, including heat resistance and low temperature dimensional stability, weight stability and the like can be addressed.

EXAMPLE X

In this example, a cured epoxy resin is made.

The uncured epoxy resin (100 g) that is used is a liquid diglycidyl ether of bisphenol A of an epoxy equivalent weight of 190. The hardening is achieved by adding 30 TIn. of a condensation product of formaldehyde and aniline Equivalent weight of 50, a polyaromatic polyamine (Jeffamine AP-22) and 20 TIn. a 20% strength by weight solution of Compound according to Example I effected in benzyl alcohol as an accelerator.

This mixture is carefully mixed, degassed, in aluminum molds poured and hardened for 7 days at about 25 C.

The properties of the composition were determined on samples cut from the cured parts.

Cured Resin Properties (3.129mm)

Notched Izod impact strength (cm kg / cm) 3.32

Tensile strength (bar) 611

Tensile modulus (bar) 28.280

Elongation at break (%) 5.1

Flexural strength (bar) 1,050

Flexural modulus (bar) 29,680

Shore hardness D (0-10 s) 86-84

Heat resistance ( ⁰ C, 18.48 bar / 4.62 bar) 44/48

Flexural strength specimens were cut and 28 days immersed in various chemicals for a long time. All tests were carried out at 25 ° C, only the test with distilled water

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was carried out at 40 C. After removing the chemicals the flexural strength of the immersed test specimen was determined. The remaining flexural strength was calculated. The results are as follows:

Retained samples immersed in flexural strength (%)

Isopropanol 104

Xylene 104

25% acetic acid 89

50% sodium hydroxide solution. 115

30% sulfuric acid 102

Distilled Water 88

It can be readily seen that the cured epoxy resins are superior in strength and strength retention after immersion are excellent in various chemicals.

EXAMPLE XI (comparative example)

In this comparative example, the procedure was as in Example X, except that curing was carried out without the accelerator. After 7 days of curing at room temperature, the resins were so brittle and uncured that it was not possible to test specimens to cut out of them. The resin was completely unsatisfactory and of poor strength.

EXAMPLES XII and XIII (comparative examples)

A liquid accelerator mixture for use in conjunction with aromatic amine hardeners is made by dissolving 20 g of polyoxypropylene <x, Äj-bis- (pyrrolidinone-3-carboxylic acid) made in 80 g of benzyl alcohol. This accelerator mixture is incorporated into an epoxy resin system with the following composition:

Approach:

Liquid Bisphenol A Diglycidyl Ether

Epoxy resin (epoxy equivalent weight 190) 100 TIe.

Aromatic polyamine (condensation product

of formaldehyde and aniline) 30 TIe.

Accelerator mixture as described above 20 TIe.

The batch is carefully mixed, degassed, in aluminum molds poured and cured for 7 days at room temperature. Test specimens are cut from the hardened resins and these tested, obtaining the following results:

Properties of the hardened resins (3.175 mm)

Notched Izod impact strength (cm kg / cm) 3.32

Tensile strength (bar) 651

Tensile modulus (bar) 28.280

Young's modulus (%) 5.1

Flexural strength (bar) 1,050

Flexural modulus (bar) 29,680

Shore hardness D (0-10 s) 86.84

Heat resistance (C, 18.48 bar / 4.62 bar) 44/48

Bending test specimens were cut and different for 28 days Chemicals dipped. After removing the chemicals, the flexural strength of the test specimens was determined. Below are the Retained flexural strength in%:

Retained specimens immersed in flexural strength (%)

Isopropanol

Xylene

25% acetic acid 50% sodium hydroxide solution 30% sulfuric acid Distilled water

Specimens of resins that cured without the accelerator mixture (Example XIII) were brittle and not fully cured after 7 days at room temperature. It could no specimens are cut out. The resins cured with the accelerator mixture were in contrast not brittle and easy to cut.

Room temperature 104 η 104 η 89 η 115 η 102 40 ° C 88

Claims (1)

Patent claims e vj compound of general formula I. H ₂
C. H C- COOM (CHJ in which: χ a number from 0-2, a is a number of at least 2, R ¹ 'a polyoxyalkylene chain with a molecular weight of 200 to 2000, to the terminal carbon atoms of which N radicals are bonded,
M is hydrogen or an alkali metal ion and H is hydrogen or a monovalent substituent. 2. N.N'-polyoxyalkylene-bis-tpyrrolidinone-J-carboxylic acid) 3. Compound of the general formula I brought into claim 1, in which a is 2 and M is hydrogen. Process for producing the connection according to one of Claims 1-3, characterized in that that a moles of an unsaturated carboxylic acid of the general formula II HOOC - C = CH, HC COOH 709850/0750 INSPECTED in the H hydrogen or mean a monovalent substituent with 1 mol of a Polyoxialky'lenpolyamins of the formula III R · · '4- in which R '''is a polyoxyalkylene chain with a molecular weight of about 200-2000 and a is a number of at least 2, are reacted under ring-forming conditions and the product obtained is isolated. 5. The method according to claim 4 for the preparation of the compound according to claim 2, characterized in that 2 moles of the unsaturated acid with about 1 mole of a polyalkylenediamine of the general formula IV - NH ₂ in which R ' ^{1 is} a polyalkylene radical with a molecular weight of about 200-2000, are reacted under ring formation conditions. 6. The method according to claim 5, characterized in that the polyalkylene diamine is a polyethylene or a polypropylene diamine is used. 7. The method according to any one of claims 4-6, characterized in that the unsaturated carboxylic acid Itaconic acid is used. 8. The method according to any one of claims 4-6, characterized in that the Ring formation is carried out at 80 - 200 ° C. 9. Use of the compound according to claims 1-3 al3 hardener or hardening accelerator of synthetic resins. 7 0 9 η 5 0/0 7 S 0 10. Use according to claim 9> characterized in that the compound in the hardening of Epoxy resins is used as an accelerator. 11. Use according to claim 10, characterized in that 1-15 Gew.Tie. the connection 100 parts by weight. Epoxy resin and 20 - 40 parts by weight. of a well-known aromatic hardener can be used. 12. Use according to claim 9> characterized in that the compound for curing polyurethane foams is used. 13. Use according to claim 12, characterized that 0.5-10 parts by weight. the connection to 100 parts by weight. a mixture of a polyisocyanate and a polyol with at least two active Η atoms and a blowing agent can be used. 14. Use according to claim 12 or 13, characterized characterized in that the compound in the form of its dialkali metal salt, preferably the dipotassium salt, is used. 70985070750