DE2104097A1 - Preparations of reaction products from epoxides, fatty amines and basic poly amides, processes for their production and their use - Google Patents

Description

CIBA-GEIGY AG BASEL (SCHw ² EiZ ⁰ ) ⁴⁰⁹⁷

Case 6958 / E

Germany

Preparations of reaction products from epoxides., Fatty amines and basic polyamides, processes for their preparation and their use.

The invention relates to a process for the production of stable preparations of water-soluble or water-dispersible reaction products from epoxides,
Pettarnines and basic polyamides.

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net that one

a) a reaction product of at least

a ') an epoxy which contains at least two epoxy groups per molecule and at least

a ") a higher molecular weight pettamine,

the equivalent ratio of epoxy groups to amino groups being 1: 0.1 to 1: 0.85, with

b) a basic polyamide, which by condensation of

b *) polymeric, unsaturated fatty acids and b ") polyalkylenepolyamines are obtained,

in the presence of an organic solvent at temperatures up to 95 C, the equivalent ratio of epoxy groups of component a) to amino groups of .Komponente b) is 1: 1 to 1: 6, preferably 1: 1 to 1: 5, and by adding acid at the latest after the end of the reaction ensures that a sample of the reaction mixture has a p "value of 2 to 8 after adding water.

An equivalent is to be understood as the amount of basic polyamide in grams which is equivalent to one mole of monoamine is.

The epoxides a ') from which component a) is obtained are preferably derived from polyvalent ones Phenols or polyphenols, such as resorcinol, phenol-formaldehyde condensation products of the resol type or

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Novolak off. In particular bisphenols such as bis (4-hydroxyphenyl) -methane and especially 2,2-BiS- (V -hydroxyphenyl) -propane are preferred as starting compounds for the production of epoxides,

Epoxides of 2,2-bis- (V-hydroxyphenyl) -propane are particularly mentioned here, which have an epoxy content of

1.8 to 5.8 epoxy group equivalents / kg, but preferably at least 5 epoxy group equivalents / kg and polygamy the formula. '

where z, is an average number in the V / erte from 0 to 0.65. Such epoxides are obtained by reacting epichlorohydrin with 2,2-bis (V-hydroxyphenyl) propane.

Particularly suitable components a ") have proven to be monofatty amines with 12 to 24 carbon atoms '- ■ proved. As a rule, these are amines the formula

H-, C- (OH ₀ -) -

y * χ

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wherein χ represents an integer from 11 to 23, preferably 17 to 21. So it is with the amines e.g. lauryl, palmityl, stearyl, arachidyl or behenylamine. Mixtures of such amines, such as those available as technical products, can also be used.

The reaction of component a ¹ ) with component a ″) is expediently carried out at 80 to 120.degree. C., preferably 100.degree.

The ratio of epoxides a 'to amines a ") is in component a) according to the invention chosen so that a Excess epoxy is used, leaving on every amino group rr.eiir comes as an epoxy group. The implementation products a) contain epoxy end groups. Invention is the Set the amount of components a ') and a ") so that an equivalent ratio of 1 epoxy group to 0.1 to 0.5 Amino groups is present, i.e. the amount of epoxide that corresponds to one epoxide group equivalent is compared with the amount of Amln that corresponds to an amino group equivalent of 0.1 to 0.5, implemented. The equivalent ratio of epoxy groups to amino groups is preferably 1: 0.1 to 1: 0.5 or in particular 1: 0.25 to 1: 0.5. ■ -

The polymeric unsaturated fatty acids used as component b ^f ) for the production of the basic polyamides b) are preferably aliphatic, ethylenically unsaturated di- to trimeric fatty acids. The reaction products b) are preferably prepared from the polyalkylenepolyamines b ")

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and aliphatic unsaturated di- to trimeric fatty acids b ¹ ) which are derived from monocarboxylic acids having 16 to 22 carbon atoms. These monocarboxylic acids are fatty acids with at least one, preferably 2 to 5, ethylenically unsaturated bonds. Representatives of this class of acids are, for example, oleic acid, hiragonic acid, elaostearic acid, licanic acid, arachidonic acid, clupanodonic acid and, in particular, linoleic and linolenic acid. These fatty acids can be obtained from natural oils, in which they occur primarily as glycerides.

The di- to trimeric fatty acids b ¹ ) used according to the invention are obtained in a known manner by dimerization of monocarboxylic acids of the type indicated. The so-called dimeric fatty acids always have a content of trimeric and a small content of monomeric acids.

Dimerized to trimerized linoleic or linolenic acid are particularly suitable as component b '). The technical products of these acids generally contain up to 95 percent by weight of dine acid, K up to 25 percent by weight of trimeric acid and a trace of up to 3% monomeric acid. The molar ratio of dimeric to trimeric acid is accordingly about a ¹ : 1 to 36: 1.

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β -

2 1 0-097

Particularly suitable as component b ") are polyamines, such as diethylenetriamine, triethylenetetramine or tetra ethylene pentamine, i.e. amines of the formula

(3) H ₂ N - (CH ₂ -CH ₂ -NH) _n - CH ₃ - CFI ₂ - !! H

₂ -CH ₂ -NH) _n - CH ₃ - CFI ₂ - !! Hg

where η is Ij 2 or 3.

In the case of mixtures of arning one can also assume a non-integer average value, e.g. between 1 and 2.

A basic polyamide made from di- to trimerized linoleum is a component of particular interest. or linolenic acid and a polyamine of the formula (3) are used .

As organic solvents, in the presence of which the unisposition of component a) with b) takes place, First of all, water-soluble organic solvents come into consideration, expediently those with Water can be mixed as desired. Examples include dioxane, isopropanol, ethanol and methanol, and ethylene glycol n-butyl ether (- n-butyl glycol), diethylene glycol, monobutyl ether.

In addition, however, it is also possible to carry out the reaction in the presence of water-insoluble organic solvents to be carried out, e.g. in Benzinkohlonwanöorstoi'fon like

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Gasoline or petroleum ether, benzene, halogenated or with lower alkyl groups substituted benzenes such as toluene, xylene, chlorobenzene and allcyclic compounds such as tetralin or cyclohexane; halogenated hydrocarbons such as methylene chloride, methylene broinide, chloroform, carbon tetrachloride, Ethylene chloride, ethylene bromide, s-tetrachlorethylene and especially trichlorethylene or perchlorethylene.

The reaction products obtained in this way are soluble or at least dispersible in water.

The reaction products from a) Epoxy-Lettamine and b) know polyamide, optionally also with the use of a third component c), namely a further one mono- or bifunctional compound which is different from a) and b) can be obtained. These mono- or bifunctional Compounds exhibit as functional groups or Atoms mobile halogen atoms, vinyl, acid, ester, acid anhydride, Isocyanate or epoxy groups. Become useful of the monofunctional compound c) used about 0.25 mol per amino group equivalent of component b), but this content can also be increased to e.g. 0.5 mol per amino group equivalent. From bifunctional connections who which is preferably used from 0.05 to 0.5 mol per amino group equivalent of component b).

These components c) are preferably aralkyl or alkyl halides, nitriles or amides of acids of the acrylic acid series, aliphatic PÄ ^ 'o ^'P'ty ^ 'i ^^ ⁰ carboxylic acids, their esters

2104037

or anhydrides, as well as aliphatic or aromatic isocyanates, Epoxies or epihalohydrins.

Are advantageous as monofunctional components c) alkyl halides such as ethyl bromide or butyl chloride, aralkyl halides such as benzyl chloride; Nitriles or amides of Acrylic or methacrylic acid such as acrylonitrile or acrylic acid amide; Alkanecarboxylic acids with up to 18 carbon atoms such as Coconut fatty acid or stearic acid, or their esters with alkanols which contain at most 5 carbon atoms, e.g. Methanol, ethanol or n-butanol, or their anhydrides such as acetic anhydride; aromatic isocyanates such as phenyl isocyanate; or aliphatic or aromatic epoxides such as propylene oxide, butylene oxide, dodecene oxide or styrene oxide. The preferred bifunctional Component c) is the epichlorohydrin.

Particularly suitable components c) are alkylon oxides with a maximum of 12 carbon atoms, alkanecarboxylic acids with a maximum of 18 carbon atoms, monocyclic Aralkyl halides or acrylonitrile.

The order in which the polyamides are reacted with the monofunctional compounds and epoxy-fatty amine reaction products is of minor importance. You can see the polyamide first with an ^r moriCKCunktionellen connection and then by implementing epoxy fatty amine reaction product or vice versa. In some cases, v / erin in responsiveness

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there are no major differences, the implementation can. can also be made at the same time.

The conversion to the conversion product from the Components a) and b) are now carried out in such a way that polyadducts which are soluble or dispersible in water arise by adding the p "value, late -

at the latest after completion of the reaction, 2 to 8, preferably 2 to 7 ι but in particular to 5 to 6, is established. To set this p "value one uses, for example

• ti

inorganic or organic acids, advantageously volatile organic acids such as formic acid or acetic acid. It is advisable to add a certain amount of acid to the reaction mixture immediately or shortly after the beginning of the combination of the basic polyamide with the epoxy and to add further acid continuously or in portions during the further reaction. Further, preferably at temperatures up to 80 C, that is from to 8o C to 70 ⁰ C, in particular worked example 45th The solutions or dispersions thus obtained, adjusted with acid to the mentioned Ρττ value and expediently adjusted with an organic solvent or preferably with water to a content of 10 to 30 $ reaction product - mostly weakly opalescent to cloudy solutions are characterized by high resistance.

Receives products with beneficial properties

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one also, if one after the addition of the acid and of the water the preparation is still stored at room temperature or at an elevated temperature, e.g. for 4 hours at 70 C or for a longer time at a lower temperature.

The preparations of the type indicated at the outset are suitable for finishing textiles, in particular for the felt fastening of wool, either the wölk with a watery liquor, which one the preparation and, if desired, has added further additives v / ie wetting agents, dispersants and / or acids, impregnated, it then dries and subjected to an elevated temperature treatment. As particularly beneficial but the process for dyeing and felting wool proves to be, in which one after the other in any Sequence according to the extraction method on the one hand dyes the wool and on the other hand at temperatures of 35 up to 100 C and a ρ .. value of 7 to 3 with the preparations treated from epoxies and basic polyamides. Dyeing and felting can thus be done in a simple manner combined and carried out in the same apparatus without the wool between the two operations is removed from the apparatus. Felting can also be carried out using a padding process.

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Dyeing can be done in the usual, known manner with any suitable for wool Dyes, e.g. acidic wool dyes, 1: 1 or 1: 2 metal complex dyes, Reactive dyes. The additives commonly used in the dyeing of wool can also be used such as sulfuric acid, acetic acid, sodium sulfate, ammonium sulfate and leveling agents, with as leveling agents polyglycol compounds of higher aliphatic amines, which may also be quaternized, are particularly suitable and / or on the Ifydroxylgruppeη with polybasic Acids can be esterified.

In addition to the preparation of the polyaddition product, the liquor used to make the felt firm also contains the Base required for setting the alkaline medium, e.g. ammonia, di- or trisodium phosphate. The amount Polyaddition product (not including solvent and water), based on the weight of the wool, is expediently $ 0.5 to $ 5. As mentioned, you work at temperatures from 35 to 100 ° C. and required here for an extensive to practically complete fixation of the polyaddition product usually between 20 and 80 minutes.

The sequence of the two processes is arbitrary, in general it is more advantageous; first to color and then to make it felt-proof.

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The combined process of dyeing and felting wool is particularly suitable in the general Apparatus dyeing, where the goods to be dyed stand still and the liquor is moved.

Advantageous felt-proof effects are also achieved by adding oxidizing agents such as hydrogen peroxide to the treatment baths. If necessary, the Permanence of the felt finishing finishes can be improved if the wool is treated with a preparation which contains an urination product, with a dilute aqueous one Solution of dichloroisocyanuric acid or its alkali metal salt is pretreated.

When using treatment baths with a high content of organic, especially water-insoluble Solvents, or even anhydrous baths containing only organic solvents, are expediently used in moderation in closed equipment, e.g. those used in dry chemical cleaning.

The preparations can also be used as sizing agents for paper.

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When using the preparations in combination with an aminoplast precondensate on textiles, in particular Cotton, becomes a water-resistant "soil release" effect achieved. It is also possible with the preparations to finish textiles so that they are non-iron.

Furthermore, with the help of preparations which contain the present reaction products, Parbo-

substances, in particular reactive dyes on textiles, in particular Full, well fixed, which is expressed in an improved fastness to perspiration.

Finishing with the reaction products also improves the mechanical properties, 'e.g. Tear resistance, elongation at break, abrasion resistance, tendency to pilling of the treated textile material.

Furthermore, it is sometimes also possible to use the reaction products in an organic solvent, i.e. ' either as a solution or as a dispersion in an organic solvent. Come as a solvent the same as those described for the production are possible.

If the reaction products are insoluble in water-insoluble organic solvents, one can them in the presence of an organo-soluble surfactant Disperse agent in the water-insoluble solvent. You can use the urn; a product, the solvent and the

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Surfactants live together with stirring or but preferably the reaction product with the surface-active one Make the agent into a paste and then add it to the solvent while stirring. A stable dispersion is obtained.

These dispersions are applied in the same way as described for the aqueous preparations.

Percentages in the following manufacturing instructions and examples are percentages by weight.

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210A097 - 15 -

Manufacturing specification

A) 196 g (l epoxy group equivalent) one from 2., 2-bis (4'-hydroxyphenyl) propane and epichlorohydrin formed epoxy together with 3I g (0.1 amino group equivalent) a mixture of 1-amino-eikosan and 1-amino-dokosan was stirred at 100 ° C. for one hour. Man receives a clear, viscous product with an epoxy group equivalent weight of 255

B) 196 g (1 epoxy group equivalent) of the under A) described epoxy together with 62 g (0.2 amino group equivalent) of the fatty amine described under A) was stirred at 100 ° C. for one hour. You get a clear, viscous product, with an epoxy group equivalent weight of 313

C) 196 g (l epoxy group equivalent) of the epoxy described under A) are added together with 77.5 g (0.25 Amino group equivalent) of the fatty amine described under A) stirred at 100 ° C. for one hour. A highly viscous product with an epoxy group equivalent weight is obtained of 379

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D) 196 g (l epoxy group equivalent) of the under A) Epoxydes described together with 93 S (0.3 amino group equivalent) of the fatty amine described under A) was stirred at 100 ° C. for one hour. A highly viscous one is obtained Product with an epoxy group equivalent weight of 436,

E) 196 g (1-epoxy group equivalent) of the under A) Epoxy described together with 108.5 g (0.35 amino group equivalents) of the fatty amines described under-A) stirred at 100 ° C. for one hour. A highly viscous product with an epoxide group equivalent weight is obtained from 498.

F) 196 g (l epoxy group equivalent) of the under A) P described epoxy together with 124 g (0.4 Amino group equivalent) of the fatty amine described under A) was stirred at 100 ° C. for one hour. One receives a highly viscous product with an epoxy group equivalent weight of 507.

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G) 196 g (1 Epoxydgruppenäquivalent) described under A) · the epoxide are stirred together with 155 g (0.5 amino group) described under A) Fettarnines one hour at 100 ⁰ C. A highly viscous product with an epoxide group equivalent weight of 685 is obtained.

H) 91.2 g Butandioldiglycidyläther (0.8 Epoxydgruppenäquivalent) are stirred together with 62 g (0.2 amino group) of a mixture of 1-amino-1-eicosane and Aminodokosan one hour at 100 ⁰ C. A clear, viscous product with an epoxy group equivalent weight of 257 · is obtained.

I) 99 g of diglycidyl hexahydrophthalate (0.6 epoxy group equivalent) are added together with 46.5 g (0.15 Amino group equivalent) of a mixture of 1-amino-eikosan and 1-amino-dokosan was stirred at 100 ° C. for one hour. You get a clear, viscous product with an epoxy equivalent weight of 395

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- Io -

J) 98 g of one from 2,2-bis (V-hydroxyphenyl) propane and Epio.hlorhydrin formed epoxy (0.5 epoxy group equivalent) together with 33 * 7 g of stearylamine (0.125 Amino group equivalent) stirred at 100 ° C. for 1 hour. A clear, viscous product with one epoxy group equivalent is obtained from 400.

K) 96 g of an epoxy of the formula

(4)

* ^ - ^na! - ^ - ^ - CH CH ₂

X / ^dd \ W ^dd \ /

H ₂

^ (0.6 epoxy group equivalent) together with 46.5 g (0.15 amino group equivalent) of a mixture of 1-Aminoeikosan and 1-amino-dokosan stirred at 100 ° C. for 1 hour. A clear, viscous product with an epoxide group equivalent weight is obtained of 278.

L) * 99 6 g of triglycidyl isocyanurate (0.6 Epoxydgruppenäquivalent) are stirred together with 46.5 S (0.15 amino group equivalent) of a mixture of 1-amino-1-eicosane and Aminodokosan 1 hour at 100 ⁰ C. You get a clear one

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Product with an epoxy group equivalent weight of 208.

M) 156.8 g of one from 2,2-BiS - (^ '- hydroxyphenyl) propane and epichlorohydrin formed epoxy (0.8 epoxy group equivalent) together with 57 * 1 g of laurylamine (0.2 Amino group equivalent) stirred at 100 ° C. for 1 hour. A clear product with an epoxide group equivalent weight is obtained of 403

N) 98 g of one from 2,2-BiS- (4'-hydroxyphenyl) propane and epichlorohydrin formed epoxy (0.5 epoxy group equivalent) are heated to 85 to 90 C internal temperature. Then 124 g (0.4 amino group equivalent) are added within 15 minutes a mixture of 1-Amino-eikosan and 1-amino-dokosan too. The mixture is then stirred for a further 6 hours at 100 C internal temperature. A highly viscous product with an epoxy group equivalent weight of 2220 is obtained.

0) 196 a * hydroxyphenyl) -propane and epichlorohydrin, the epoxide (l Epoxydgruppenäquivalent) formed together with 32 g of lauryl propylenediamine (0.2 amine equivalent) for 1 hour at 100 ⁰ G stirred g of 2,2-bis (. 4 A clear product with an epoxide group equivalent weight of 380 is obtained.

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Ρ) 196 g of an epoxy formed from 2,2-bis (4'-hydroxyphenyl) propane and epichlorohydrin. (1 epoxy group equivalent) together with 20.4 g Tailöl propylenediamine (0.1 amine equivalent) for 1 hour at 100 C. touched.
A clear product with an epoxide group equivalent weight of 282 is obtained.

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210A097

example 1

49.4 g of a polyamide made from polymerized linoleic acid and diethylenetriamine (0.2 amino group equivalent) are dissolved in 50 g of butyl glycol and heated to an internal temperature of 53.degree. A solution of 18.95 g of epoxide C) (0.05 epoxide group equivalent) in 20 g of n-butyl glycol is then added dropwise over the course of 30 minutes. One hour later, a solution of 8 g of glacial acetic acid and 195 g of deionized water is added and the mixture is stirred until it cools. A thin liquid solution is obtained whose dry content is $ 20 and whose p "value is 1.0 .

Example 2

^ 9j ^ S (0.2 amino group equivalent) of the polymer from Example 1 are dissolved in 50 g of n-butyl glycol and heated to an internal temperature of 58 C. A solution of 3 ² I -. * 25 g of epoxide G) (0.05 epoxide group equivalent) and 35 g of n-butyl glycol is then added dropwise over the course of 40 minutes. One hour later, a solution of 7 g of glacial acetic acid and 226 g of deionized water is added and the mixture is stirred until it cools. A thin liquid solution is obtained with a dryness content of 20 $ and a p ,, ~ value of 7.0

saddened. : 108834/1492

Example 3

61.8 g of a polyamide made from polymerized linoleic acid and diethylenetriamine (0.25 amino group equivalent) are dissolved in 61.8 g of isopropanol and heated to an internal temperature of 53.degree. A solution of 12.85 g of epoxide H (0.05 epoxide group equivalent) in 12.85 g of isopropanol is then added dropwise over the course of 30 minutes. One hour thereafter, a solution of 15 g of glacial acetic acid in 200 g of deionized water is added and stirring is continued until it cools. A low-viscosity solution whose dry content 20 ^> and its _pH value is 6.0 is obtained.

Example 4

49 Λ g (0.2 amino group equivalent) of the polyamide according to Example 3 are dissolved in 49.4 g of ethanol and heated to an internal temperature of 53 ° C. A solution of 19.8 g of epoxide I (0.05 epoxide group equivalent) in 19.8 g of ethanol is then added dropwise over the course of 30 minutes. One hour later, 24 g of glacial acetic acid in 180 g of deionized water are added and the mixture is stirred until it cools. A clear, thin liquid solution is obtained whose dry content is $ 20 and whose p "value is 5.9.

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Example 5

49.4 g (0.2 amino group equivalent) of the polyamide according to Example 3 are dissolved in 49.4 g of butyl glycol and
heated to 54 C internal temperature. A solution of 20 g of Epoxy J (0.05 epoxy group equivalent) in 20 g of butyl glycol is then added dropwise over the course of 30 minutes. One hour
then 12 g of glacial acetic acid in 190 g of deionized water are added and the mixture is stirred until it cools. A clear, thin liquid solution is obtained whose dry content is $ 20 and whose p "value is 5.4.

Example 6

49 * 4 g (0.2 amino group equivalent) of the polyamide according to Example 3 are dissolved in 49.4 g of dioxane and dissolved
55 C internal temperature heated. Then leave a solution
from 13.9 g of Epoxy K (0.05 epoxy group equivalents) in 13.9 g of dioxane are added dropwise within 30 minutes.

One hour later, 12 g of glacial acetic acid in 172 g of deionized water are added and the mixture is stirred until it cools.
A thin liquid solution is obtained whose dry content is $ 20 and whose p "value is 5 * 4.

M.

1098347 VA 9 2

Example 7

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are dissolved in 79 g of butyl glycol and heated to an internal temperature of 55.degree. A solution of 16.6 g of epoxy L (0.08 epoxy group equivalent) and 16.6 g of butyl glycol is then added dropwise over the course of 30 minutes. ¹ JO minutes thereafter, 19.2 g of glacial acetic acid and 260 g of deionized water are added and stirring is continued until it cools.

Example 8

"a) In a reaction vessel, which is equipped with a stirrer, If a thermometer, inlet tube for nitrogen and a distillation head is provided, 187 g are polymerized Fatty acid and 68.5 g of diethylenetriamine. The polymerized Fatty acid, obtained by polymerizing oleic acid, has the following properties: 95% dimerized oleic acid; Equivalent weight: 289.

The reaction mixture is brought to 200 ° C. in the course of 11/2 hours under a nitrogen atmosphere and with stirring

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heated, with splitting off at an internal temperature of 160 ° C. of water begins. After a further 2 hours at 200 ° C., a total of 15 parts of water are collected. The mixture is then concentrated in vacuo for 3 hours (l4 mm Hg) at 200 ° to 210 ⁰ C. 210 g of a viscous, yellowish, clear product with an amine equivalent weight of 372 are obtained.

b) 7 ^ j ² J- S of the condensation product described under a) (0.2 amino group equivalent) are dissolved in 7 ^ j 4 g of butyl glycol and heated to 55 G internal temperature. A solution of 20.2 g of Epoxy M (0.05 epoxy group equivalent) and 20.2 g of butyl glycol is then added dropwise over a period of 30 minutes. 30 minutes later, 12 g of glacial acetic acid and 265 g of deionized water are added and the mixture is stirred until it cools down. A clear, thin liquid solution is obtained whose dry content is $ 20 and whose p "value is 6.0.

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Example 9

44.6 g of the condensation product described under 8a) (0.12 araino group equivalent) are in 44.6 g of butyl glycol dissolved and heated to 60 C internal temperature. Then leave within 30 minutes from 2 separate dropping funnels 7 * 2 g. Glacial acetic acid and a solution of 44.4 g epoxy N (0.02 epoxy group equivalent) and 44.4 g of butyl glycol are added dropwise. The mixture is then stirred for 6 1/2 hours at an internal temperature of 60 ° C. and a further 10 g of glacial acetic acid are then added. After a further 30 minutes, the mixture is diluted with 180 g of butyl glycol. A clear, thin liquid solution is obtained, the dry content of which is $ 20.

A sample diluted 1:20 with water has a

p "value of 5 * 8.
ri

Example 10

66.6 g of epoxy N (0.03 epoxy group equivalent) are dissolved in 66.6 g of butyl glycol and heated to an internal temperature of 60 ° C warmed up. Then, within 30 minutes, 5.6 g of glacial acetic acid and a solution are left from 2 separate dropping funnels from 35.4 g of the condensation product described under 8a)

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- CL ( -

tes (0.09 amino group equivalent) and 55 * 4 g of butyl glycol drip.

The mixture is then stirred for 6 1/2 hours at an internal temperature of 60 ° C. and then another 10 g of glacial acetic acid are added to. After a further 50 minutes, it is diluted with 285 g of butyl glycol, A clear, thin liquid solution is obtained, the dry content of which is $ 20. A sample diluted 1:20 with water has a p "value of 5 * 8.

Example 11

68.5 g Epoxy G (0.1 epoxy group equivalent) are dissolved in 57 g of isopropanol and heated to an internal temperature of 88.degree. Then leave within 50 minutes a solution of 24.7 g (0.1 amino group equivalent) des Add dropwise polyamides according to Example 5 and 15 g of isopropanol.

The mixture is then stirred for a further 5 hours at an internal temperature of about 88 ° C. (reflux) and then 1.85 g is added Epichlorohydrin (0.02 mol). After a further 10 minutes, a solution of 16 g of glacial acetic acid and 512 g of deionized acid is added Add water and stir until it cools. A thin liquid product is obtained whose dry content is $ 20 and which p "value is 4.6.

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Example 12

79 g (Ο, 32 amino group equivalents) of the polyamide according to Example 3 are dissolved in 40 g of butyl glycol and heated to an internal temperature of 80.degree. Then you leave within a solution of 30.4 g of epoxy 0 (0.08 epoxy group equivalent) and 30.4 g of butyl glycol are added dropwise over a period of 30 minutes.

15 minutes later, 20 g of glacial acetic acid and 336 g of deionized water are added and the mixture is stirred until it cools. A low-viscosity solution, the dry content 20 $ and its _pH value is 5 * 3 is obtained.

Example 13

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are dissolved in 40 g of butyl glycol and ^{heated to 80 °} C. internal temperature. A solution of 22.6 g of epoxy P and 22.6 g of butyl glycol is then added dropwise over the course of 30 minutes.

15 minutes thereafter, 20 g of glacial acetic acid and 311 g are added Add deionized water and stir until it cools down. A thin liquid solution is obtained with a dry content of $ 20 and whose p "value is 5.2.

1 09 834 / U92

Example l4

79 g (0.32 amino group equivalents) of the polyamide according to Example 3 are heated to an internal temperature of 180.degree. Within 2 hours, 16.7 S dodecene oxide (0.08 Mol) is added dropwise, holds at 180 ° C. for a further 2 hours, cools then to 50 C internal temperature and dissolves the product in 32 g of butyl glycol. It is then left at an internal temperature of 50.degree a solution of 20.4 g epoxy A (0.08 epoxy group equivalent) and 20.4 g of butyl glycol are added dropwise over the course of 30 minutes. The internal temperature is then increased to 60 ° C. and stirring is continued at this temperature for a further 1 1/4 hours. Then 20 g of glacial acetic acid and 391 g of deionized water are added and the mixture is stirred until it cools down. You get one thin liquid solution, its dry content $ 20 and its p "value Is 4.9.

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Example 15

79 g (0.52 amino group equivalents) of the polyamide according to Example 3 are stirred together with 10.1 g of benzyl chloride (0.08 mol) at an internal temperature of ^{100 ° C. for 2 hours.} The product is then cooled to an internal temperature of 60 ° C. and 32 g of butyl glycol are added. A solution of 20.4 g of epoxy A (0.08 epoxy group equivalent) and 20.4 g of butyl glycol is then added dropwise at this temperature over the course of 30 minutes. 25 minutes thereafter, 20 g of glacial acetic acid and 364 g of deionized water are added and the mixture is stirred until it cools down. A thin liquid solution is obtained whose dry content is 20 $ and whose p "value is 4.6.

Example l6

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are dissolved in 32 g of butyl glycol and dissolved 50 C internal temperature heated. 4.3 g of acrylonitrile are then added (0.08 mol) and stirred for 2 hours at 50 ° C internal temperature. Then a solution is left within 30 minutes from 20.4 g of epoxy A (0.08 epoxy group equivalent) and 20.4 g of butyl glycol are added dropwise. 1 1/2 hours afterwards, add 20 g of ice cream

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- 51 -

vinegar and 359 g of deionized water and stir until Keep cooling down. A thin liquid solution is obtained whose dry content is 20/6 and whose p "value is 5 * 0.

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Application examples

Example 17

1000

^ Liters of water 100 kg of woolen yarn dyed with reactive dyes as usual. After dyeing it is rinsed thoroughly. A fresh bath of ¹ K) ⁰ C consisting of 1000 liters of water and 1. ^ kg of ammonia (25%) is prepared. This is followed by the addition of 8 kg of the product according to Example 1. A stable emulsion is formed which is evenly absorbed onto the wool in about 30 minutes. Then added to trisodium phosphate, can be 10 minutes to proceed and set a further 2 kg of a 12.5 # solution ψ of a condensation product of 1 mole of octadecyl alcohol and 25 mols of ethylene oxide to. After a further 20 minutes, it is rinsed thoroughly with cold water, drained and dried. The yarn treated in this way is felt-resistant in accordance with the IWS specifications JB _t JG and 71.

Instead of a product according to Example 1 can be _t one of the examples to 16 used with equal success the product.

1D9834 / U92

Example l8

A fabric made of pure wool with the following preparation is made on a horizontal two-roll foulard impregnated and squeezed to a liquor pick-up of $ 100:

120 g / l product according to example 1

2 g / l of a condensation product of 1 mol of p-tert-octylphenol and 8 moles of ethylene oxide

30 ml / l hydrogen peroxide 848 x ml / l water

1000 g foulard liquor.

After padding, the goods are dried on a stenter. Then it is still during Pressed for 5 minutes at 120 ° C. with medium pressure (on a "Hoffmann press").

The goods treated in this way show the following shrinkage values when tested according to IWS specification 71:

untreated goods $ 53 shrinkage treated goods 2., $ 1 shrinkage

If the tissue is subjected to the known reductive treatment with monoethanolamine sulfite before the treatment just described the goods are also surface stable, i.e. they remain even after one

1Q8B3 4 / U92 Wash smooth and wrinkle-free.

Example 19

3.0 The preparation according to Example 1 is made into a paste with 10.0 g of a surfactant of the composition given below and this mixture is diluted to 1000 ml with perchlorethylene. Brief stirring gives a stable dispersion. At 20 ° C., 20 g of a knitted piece of wool are treated with this liquor for 50 minutes. After removal of excess liquor by centrifuging is dried for 10 minutes at 100 ⁰ C and fixed. The knitted piece treated in this way is felt-proof.

The following products serve as surfactants:

I: condensation product of 1 mole of coconut fatty acid and 2 moles of diethanolamine containing about 2% each of water and acetic acid.

II: Acid phosphoric acid ester of a condensation product of 1 mol of 2-ethylhexanol and 5 mol Ethylene oxide, neutralized with sodium hydroxide, as an 80% aqueous solution.

Ill: Aqueous solution containing:

38.5 # of an oleic acid polyglycol ester,

38.5 $ of a condensation product of 1 mole

p-tert-octylphenol and 8 moles of ethylene oxide,

Oleic acid.

10S834 / U92

Example 20

100 kg of bleached sulphite pulp are used in the The Dutch are ground in the usual way and then drained into a mixing vessel. The Addition of 20 kg of calcium carbonate as a filler. After the filler has spread well in the pulp suspension, 0.3 to 0.7 $ of the product is added Example 11, based on pulp and solids content. Passed through further stages of the paper-making process the mixture of substances to the paper machine.

A retention aid can be used to increase filler retention be added shortly before the headbox.

Papers produced with this or a similar composition of matter are mainly used as writing and It uses printing papers and has excellent ink strengths as a result of good sizing.

Aluminum sulphate, which is produced in smaller or larger quantities through the use of scrap paper in If this system is introduced, the gluing is not affected in any way.

In this system, the calcium carbonate can also be replaced by commercially available kaolin. The sizing effect is the same as when using calcium carbonate,

109834 / U92

Claims (21)

Claims ι Iy process for the production of stable preparations of reaction products of epoxides, fatty amines and basic polyamides which are soluble or dispersible in water, characterized in that one a) a reaction product of at least ' a ') an epoxy which contains at least two epoxy groups per molecule and at least ä ") a higher molecular fatty amine, the equivalent ratio of epoxy groups to amino groups being 1: 0.1 to 1: 0.85, with b) a basic polyamide, which by condensation of b ') polymeric unsaturated fatty acids and b ") polyalkylene polyamines be obtained in the presence of an organic solvent at temperatures of up to 95 C, the equivalent ratio from epoxy groups of component a) to amino groups of component b) is 1: 1 to 1: 6 and by adding acid at the latest after the end of the reaction ensures that a sample of the reaction mixture after adding water has a p ^ value of 2 to 8,
ri 109834/1492 2. The method according to claim 1, characterized in that the equivalent ratio of epoxy groups
of component a ¹ ) to amino groups of component a ") 1: 0.1 to 1: 0.5 is the equivalent ratio of epoxy groups of component a) to amino groups of component b) is 1: 1 to 1: 5 and the reaction of components a) and b) at temperatures up to 80 ° C takes place. 3. The method according to claim 2, characterized in that as component a ^! ) uses an epoxy derived from a bisphenol. 4. .Verfahren according to claim ~ 5, characterized in that there is a polyglycidyl ether as component a ')
of 2,2-bis (4'-hydroxyphenyl) propane is used. 5. The method according to claim 4, characterized in that component a ^T ) has an epoxy content of at least 5 epoxy group equivalents per kg. 6. The method according to claim 4, characterized in that a reaction product of epichlorohydrin with 2,2-bis (4'-hydroxyphenyl) propane is used ^{as component a f).} 7. The method according to claim 2, characterized in that component a ") is a monofatty amine with 12
up to 24 carbon atoms used. 1Q983WU92 8. The method according to claim 7, characterized in that as component a ") pettamines of the formula H ₃ C - (CH ₂ ) _x - NH ₂ is used in which χ is an integer ranging from 11 to 23. 9. The method according to claim 8, characterized in that in the formula of component a ") χ a whole Means a number ranging from 17 to 21. 10. The method according to claim 2, characterized in that that one uses as component b ') aliphatic, ethylenically unsaturated di- to trimeric fatty acids. 11. The method according to claim 10, characterized in that one ^{uses as component b f} ) fatty acids which are derived from aliphatic unsaturated monocarboxylic acids having 16 to 22 carbon atoms. 12. The method according to claim 11, characterized in that as component b ') di- to trimerized linoleic or linolenic acid is used. 13 · The method according to claim 12, characterized in that that as component b ") an aliphatic polyamine the formula H ₂ N - (CH ₂ -CH ₂ -NH) _n - CIIg - CH ₂ - 109834/1492 where η is 1, 2 or 3 is used. 14. The method according to claim 12 and 13 *, characterized in that that as component b) a basic polyamide from di- to trimerized linoleic or linolenic acid and a polyamine of the formula H ₂ N - (CH ₂ -CH ₂ -NH) _n - CH ₃ - CH ₂ - NH ₂ where η is 1, 2 or 3 is used. 15. The method according to any one of claims 13 and 14, characterized characterized in that diethylenetriamine, triethylenetetramine or tetraethylene pentamine are used as component b "). 16. The method according to any one of claims 2 to I5, characterized characterized in that the organic solvent used is a solvent which is freely miscible with water used. 17 · The method according to any one of claims 2 to 16, characterized in that the implementation be.i 25 to 80 ° C. l8. The method according to any one of claims 1 to 17, characterized in that the reaction products from the Components a) and b) with use c) a mono- or bifunctional compound, 109834/1492 which is different from a) and b) is obtained. 19- method according to claim l8, characterized in that that component c) is an epihalohydrin. 20. The preparations obtainable according to one of claims 1 to 19. 21. Use of the preparations obtainable according to one of claims 1 to 19 for finishing textiles, especially for the mushroom-proofing of wool. 109834/1 £ 92