DE1177824B - Process for the production of water-soluble condensates based on polyamides and epichlorohydrin - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 08 g

German class: 39 c-10

Number: 1177 824

File number: H 34226 IVd / 39 c

Filing date: September 2, 1958

Opening day: September 10, 1964

The invention relates to the production of new condensation products.

A process is known for producing polyamides by reacting diamines with dicarboxylic acids. Insoluble products are obtained in this way. Amino acid derivatives, viz Lactams, polymerized with the addition of small amounts of accelerators such as epichlorohydrin. Here too insoluble products are obtained. Another method is a three-component system, consisting from a natural or synthetic resin or a reaction product obtained therefrom, furthermore a polyfunctional amine and, thirdly, a monoepoxide processed into synthetic products. The epoxide is reacted with the amine, if appropriate with prior mixing with the resin. Insoluble, infusible synthetic resins are obtained in this way.

The invention now relates to a process for the production of water-soluble condensates based on polyamides and epichlorohydrin through the conversion of polyvalent amines with dicarboxylic acids with 3 to 10 carbon atoms in the heat, which is characterized in that one as polyvalent Amines Polyamines with at least three amino groups are used and the polyamides formed then reacted with epichlorohydrin.

The reaction can be carried out in the presence of a quaternizing agent. Preferably the polyalkylenepolyamine is in a molar ratio to the dibasic carboxylic acid of about 0.8 to 1.4: 1 used. The epichlorohydrin is preferably in a molar ratio to the secondary amino groups of the polyamide of about 0.5 to 1.8: 1 are used.

In the manufacture of these products, the dibasic method is used according to a method not claimed here Carboxylic acid first with a polyalkylenepolyamine to a water-soluble polyamide with the repeating groups

- NH (C _w H ₂ «HN) z - CORCO -

implemented, in which both η and χ the number 2 or a larger and R is the divalent hydrocarbon radical of the dibasic carboxylic acid.

According to the invention, this long-chain polyamide is then mixed with epichlorohydrin, optionally in the presence a quaternizing agent, converted to form the water-soluble condensation products.

The polyamides used as starting materials in the process according to the invention are according to method not claimed here by

Process for the preparation of water-soluble
Condensates based on polyamides
and epichlorohydrin

Applicant:

Hercules Powder Company, Wilmington, Del.

(V. St. A.)

Representative:

Dr.-Ing. A. van der Werth,

Hamburg-Harburg 1, Wilstorfer Str. 32,

and Dipl.-Chem. Dr. F. Lederer, Munich 8,

Patent attorneys

Named as inventor:

Alfred Chandler Schmalz, Wilmington, Del.,

William Donald Thompson, Middletown, DeL,

Paul Harwood Aldrich,

Robert Westbrook Butler, Wilmington, Del.,

Gerald Inman No, West Grove, Pa.,

Stearns Tyler Putnam,

Robert Wilder Davison,

John Dewitt Floyd, Wilmington, Del. (V. St. A.)

Claimed priority:

V. St. ν. America September 5, 1957
(682 089),

of March 27, 1958 (724 235),
dated July 22, 1958 (750 073) -

Settlement of a saturated aliphatic dibasic Carboxylic acid having 3 to 10 carbon atoms, such as. B. malonic acid, succinic acid, adipic acid or Azelaic acid, obtained with a polyalkylenepolyamine, preferably in aqueous solution. The saturated ones Dibasic acids with 4 to 8 carbon atoms in the molecule are preferred. Mixtures of two or more saturated dibasic carboxylic acids can also be used.

According to the invention, a large number of poly-

alkylene polyamines including polyethylene polyamines, Polypropylene polyamines and polybutylene polyamines are used, of which the polyethylene polyamines which in economic terms

409 660/444

3 4

represent preferred class. In the Polyalkylen- erfir.dungsgerräß to a cationic, heat polyamines, the alkylene groups have more than hardening resin by converting 1 carbon atom, and there are two to eight epichlorohydrin in the molecule at a temperature of about such groups. The nitrogen atoms can be converted from 45 to about ICO ⁰ C, preferably between about 45 to adjacent carbon atoms in the group 5 and 70 ⁰ C, until the viscosity of a - C "H ₂ , i - or to more distant carbon - 20 ° / _c igen solution of solid substances at 25 ⁰ C about C atoms, but not bound to the same carbon atom or a higher value on the Gardner-Holdt bond. According to the invention can not only have reached scale. This reaction is preferably carried out polyamines such as diethylenetriamine, triethylenetetramine, in aqueous solution. The setting of the tetraethylene pentamine, dipropylene triamine and N-bis-io ρκ-value is usually not necessary. Because (aminopropyl) methylamine is used alone, but the pH value decreases during the polymerization, but also mixtures thereof and their crude phase of the reaction, it can sometimes be produced. For example, it is desirable to add alkali to the mixture of poly- ethylene in order to bind at least ethylene polyamines, as would be the case by reacting some of the acid formed.
Ammonia and ethylene dichloride and purification only 15 In the polyamide-epichlorohydrin reaction according to the extent of the removal of chlorides, the process according to the invention is preferred to use water, excess ammonia and ethylene- epichiorhydrin so much that all the secondary diamine is obtained, a very much satisfactory expansion of amino groups into tertiary amino groups, transition material. Products that are made from a distillery. However, more or less ionic residue from refining the low 20 can be added to substantially moderate or increase the rate of reaction of the polyethylene polyamines being produced. Generally borrowed from polyamines higher than tetraethylene, satisfactory results when using pentamine can also be used. from about 0.5 to 1.8 mol epichiorhydrin for each

Of course, compounds containing secondary amino groups of the polyamide can also be obtained

which smaller nitrogen-bonded groups, 25 become. Preferably about 1.0 to 1.5 mol

such as - CH ₂ CH ₂ OH, and almost always differ for every secondary amino group of the polyamide.

know dimensions in commercial polyamines as turned.

Result of a side reaction in the usual According to another embodiment of the invention

Processes are available according to which polyalkylene or process more resistant poly-

polyamines can be used. You get 30 amide-epihlorohydrin resins if you have a

can also use oxyalkyl-substituted polyamines. Polyamide with epichiorhydrin in the presence of a

The implementation of the quaternizing agent not claimed here converts, the reac-

Implementation between the dibasic acid and ionic conditions and the reactants, from

the temperature applied to the polyalkylenepolyamine seen from the inclusion of the quaternizing

Doors can be from about 110 to about 250 ° C or higher 35 means that are the same as previously described,

fluctuate at atmospheric pressure. However, in a preferred embodiment for through-

The epichiorhydrin is used for most purposes temperatures between about carrying out the process

160 and 210'C have been found to be satisfactory and first contributed to an aqueous solution of the polyamide

are preferred. If reduced pressure at a temperature of about 45 to 55 ⁰ C is added. That

the temperature can be slightly lower

fittings are used. The reaction time depends from 50 to 100 ° C, preferably from 60 to 8O ⁰ C, in

on the temperatures and pressures used, depending on the desired polymerization

and is usually ^{heated at between about 1} J ₂ to 2 hours at a rate. After a suitable time

fluctuate, although shorter or longer reaction times at this temperature, that is up to about IGO minutes,

times depending on the reaction conditions and preferably when the viscosity is about 25%

to be used. In any case, solids-containing reading of the reaction

the reaction desirably to a substantial mixture at 25 ° C of about <A to <ß on the

for best results - Gardner-Holdt scale is - after what time

set. most of the epoxy groups of epichlorohydrin with

In this reaction, a reaction of the primary amino groups of the polyamide will have reacted for the complete 5 ° of the secondary amino groups of the polyamide - the quaternizing agent alkylenepolyamine is added sufficient amount of dibasic urd the reaction mixture to a Tem-acid used, which is insufficient is kept at about 60 to 80 C until the viscosity reacts with the secondary amino groups to a noticeable extent of about 25% solids. This will usually be a 55 solution at 25'C at least A and \ preferably molar ratio of polyalkylenepolyamine to two- at least B to C on the Gardner-Holdt scale. basic acidity of about 0.9: 1 up to about 1.2: 1 Eas solids to viscosity ratio may require maintaining. However, molar ratios can be about through

0.8: 1 up to about 1.4: 1 with a completely satisfactory. . _,. , ■ ■ ^,,

Results are used. Molar ratios of extra 60 '■ direct Folyrrensat.on be. a salary of

half of these areas are generally unsatisfied- ^{/ c} "

gend. For example, molar ratios below about 0.8: 1 result in 2nd foliarization at a higher content to a gelled product or one with subsequent dilution to 25% solids Tendency to celiate, while molar content cder

Ratios above 1.4: 1 to low molecular weight 65 3. Polymerization at a lower content with

Lead polyamides. subsequent concentration at less than

That after the above described, here not <0 C and under \ errirgerlem pressure on 25%

The polyamide formed in the claimed process can be solid.

The pH of the reaction mixture is then adjusted to about 4.0, but preferably to about 2.0 to 3.0 rr., By means of sulfuric, hydrochloric or formic acid. cerium initial degree of polymerization, the amount of quaternizing agent and the eventual pH are all essential for controlling the stability of the resins.

The amount of quaternizing agent should be sufficient to be from about 25 to about 75%. preferably about 50%. to convert the tertiary amino groups into quaternary groups. The amount of Epichlorohydrin used is the same as before.

The quaternisierer.de agent can be any compound that contains a tertiary nitrogen able to quaternize in an aqueous medium. Such agents are the lower alkyl esters of mineral acids, like the halides, sulfates and phosphates, substituted alkyl halides. Examples of useful Compounds are: dimethyl, diethyl and dipropyl sulfate, methyl chloride, methyl iodide, methyl bromide, Ethyl bromide, propyl brimide, the mono-, di- or tri-methyl, ethyl and propyl phosphates, 1,3-dichloropropanol-2, 1-chloroglycerin. Certain aromatic compounds also know to be used. Typical for these are eenzyl chloride and methyl p-toluenesulfonate.

According to the invention, water-soluble condensates of epichlorohydrin and a polyamide of the type described here are also produced, which, while they are useless as wet strength resins per se, can easily be converted into such by further condensation. In the preparation of these condensates, the polyamide formed as above is reacted with epichlorohydrin, the amounts of reactants and the reaction conditions being the same as described above, except that in this case the reaction is terminated when the above-described reaction 1 is terminated before a substantial one Amount of networking is taking place. In practice, this is done by terminating the reaction before the viscosity of a solution of the condensate with 35 to 40% solids content C preferably reaches a value between A and B on the Gardner-Holdt scale.

When the desired viscosity is reached, this usually involves heating for a time of about 2 to about 15 minutes within the already specified Requires temperature range, the reaction is terminated immediately. This can be more effective Way by adding enough acid to reduce the Ph to 7 and then quickly Cooling the mixture to 25 ° C can be accomplished. The mixture is then made by adding sufficient acid to reduce the pn value to at least 5 stabilized.

55

example 1

First of all, 225 g (2.18MoI) of diethylenetriamine and 100 g of water were placed in a three-necked bottle equipped with a mechanical stirrer, thermometer and condenser to produce the starting material to be used according to the invention by a method not claimed here. To this, 290 g (2.0 mol) of adipic acid were added. After the acid had dissolved in the amine, the mixture was heated to 185 to 200 ° C. and held there for 1V for ₂ hours. Vacuum from a water aspirator was then applied to the bottle for the time required to cool the contents of the bottle to 140 ° C, followed by the addition of 430 grams of water. The polyamide solution contained 52.3 percent solids and had an acid number of 2.1.

To 60 g of this polyamide solution in a round bottom flask was added 225 g of water. This solution was heated to 5O ⁰ C and according to the invention 12.5 g of epichlorohydrin was added dropwise over a period of 11 minutes. The contents of the flask were then heated to 60-70 ° C until they had a Gardner viscosity of > E. Then 150 g of water was added to the product and cooled to 25 ° C. 11 ecm of 10% HCl was then added to adjust the pH to 5.0. The product contained 9.0% solids and had a G ardner viscosity of C to D.

Example 2

In a process not claimed here, a polyamide was obtained from 319 g (2.18 mol) of triethylenetetramine and 290 g (2.0 moles) of adipic acid prepared by following the procedure of Example 1. The polyamide solution contained 49.8% solids and had a pH of 10.8 and an acid number of 3.2.

63 g of the polyamide solution were dissolved in 225 g of water. The solution was stirred mechanically and heated to 50 ° C. Then, according to the invention, 25 g of epichlorohydrin were added dropwise over 3 minutes. The solution was then ^{heated to 60 to 70 °} C. until it reached a viscosity of f (Gardner). Then it was diluted with 225 g of water, cooled to 25 ⁰ C and adjusted to pH 5.0 with 11 cc of 10% HCl.

Example 3

According to the method not claimed here and according to the information in Example 1, a polyamide was obtained from 88 g (0.855 mol) of diethylenetriamine, 29.5 g (0.22 mol) of N-bis (aminopropyl) methylamine and 145 g (0.99 mol ) Adipic acid produced. 60 g of the polyamide solution (52.8% solids) were heated ^{to 50 ° C. in 225 g of water.}

According to the invention, 14 g of epichlorohydrin were added dropwise to this solution over a period of 15 minutes with stirring. This solution was then ^{heated to 60 to 70 °} C. until its viscosity reached £ on the Gardner scale (2 hours and 5 minutes). 175 g of water were then added and the resin was cooled to 25 ° C. To this was then 13 cc of 10 °, if _NG HCl to adjust the pH to 5.0. The product had a viscosity from B to C (G ard η er) and contained 8.6% solids.

Example 4

According to a method not claimed here, a polyamide was prepared as described in Example 1 using 225 g (2.18 mol) of diethylenetriamine, 218 g (1.5 mol) of adipic acid and 94 g (0.5 mol) of azelaic acid. 57.5 g of the polyamide solution (55% solids) were dissolved in 115g water and heated to 50 ⁰ C.

According to the invention, 15 g of epichlorohydrin were added over the course of 6 minutes. This solution was then ^{heated to 60 to 70 °} C. until the viscosity of the condensate reached > E (Gardner). Then 150 g of water were added and the product

was cooled to 25 ~ C. It got through to Ph 5 Addition of 10 ecm 10% HCl stopped. The finished resin had a viscosity of ß (Gardner) and contained 9.5% solids.

Example 5

A polyamide was made from a method according to the information in Example 1, which is not claimed here the following components:

Diethylenetriamine 204.4 g (1.98 mol)

Ethylenediamine 14.0 g (0.24 mol)

Adipic acid 290.0 g (1.98 moles)

Water 100.0 g

The procedure of Example 1 was followed with the following modifications:

1. The reaction mixture was kept at 180 to 195 ^° C. for 45 minutes;

2. a suction vacuum was applied all this time;

3. The mixture was cooled to 140 ° C and diluted with 430 ecm of distilled water at 80 ° C.

The polyamide solution contained 52.4% total solids and had an acid number of 3.4. At 60.5 g 225 g of water were added to this polyamide solution.

This solution was heated to 50 ° C. and, according to the invention, 11.25 g of epichlorohydrin were added dropwise over about 11 minutes. The solution was then heated to 70 to 80 ° C. and held at this temperature until it had a viscosity of E (Gardner - Holdt). It was then diluted with 173 ecm of water and adjusted to pn 5.0 with dilute HCl. The product contained 8.9% solids and had a Gardner viscosity from B to C.

was then ^{heated to 70 °} C., and after 10 minutes at this temperature, 17.0 g of dimethyl sulfate were added dropwise over the course of 7 minutes. The solution was heated to 70 ° C. with stirring until a Gardner viscosity of <C was obtained (after 4 hours and 16 minutes). It was then cooled to 25 ⁰ C and to pn 4.0 with 3.1 cc of 10% sulfuric acid adjusted. The product contained 27.0% solids and had a Gardner viscosity of ~ R at ίο 25 ° C (Brookfield viscosity 51.2 cP at 25 ° C).

Example 7

A polyamide produced by the method not claimed here and in accordance with the information in Example 6 was converted into a usable wet strength resin as follows:

To a solution of 63.0 g (dry basis) of the polyamide in 185.0 g of water, which was heated to 50 ° C., 31.0 g of epichlorohydrin were added according to the invention within 3 minutes with stirring. The temperature of the solution was increased to 7O ⁰ C. After 10 minutes at 7O ⁰ C 17.0 g of dimethyl sulfate was added over 5 minutes. The mixture was ^{heated to 70 °} C. with stirring until its viscosity at 25 ^° C. reached <£ on the Gardner scale (after 3 hours and 38 minutes). It was then diluted with 195 g of water and held at 7O ⁰ C until its viscosity at 25 ° C on the Gardner scale (after 5 hours and 42 minutes) attained. The solution was cooled to 25 ⁰ C, to pH 4.0 with 0.8 cc of 10% sulfuric acid adjusted and concentrated by heating at 25 to 40 ⁰ C under reduced pressure. The product contained 30.9% solids and had a Gardner viscosity of <J at 25 ^° C.

Example 8 Example 6

The starting material to be used according to the invention was produced by a process not claimed here manufactured as follows:

In a 1-1 three-necked round bottom flask equipped with a mechanical stirrer, thermometer and condenser, 200 g (1.94 mol) of diethylenetriamine and 100 g of water were placed. The flask was purged with nitrogen and a nitrogen blanket was maintained therein during the reaction. To the well-stirred mixture, 290 g (2.00 moles) of adipic acid were added in six approximately equal portions. After dissolution of the acid in dem.Amin the solution was heated to 190 ± 5 ° C and maintained there for ¹ l / »hours. The reaction mixture was then cooled to 14O ⁰ C and diluted with 430.0 g of water. The polyamide solution contained 54.6% solids and had a true viscosity (2% solution in 1N ammonium chloride) of 0.116. 210 g of water were added to 116 g (63 g dry basis) of this polyamide solution in a round-bottom flask equipped with a mechanical stirrer and thermometer.

The solution was ^{heated to 50 °} C. with stirring and, according to the invention, 25.0 g of epichlorohydrin were added over a period of 2 minutes. The solution A polyamide produced according to the method described in Example 6, which is not claimed here, was converted into a resin that can be used for the production of wet-strength paper:

According to the invention, 31 g of epichlorohydrin were introduced over the course of 3 minutes with stirring to a solution of 63.0 g (dry basis) of the polyamide in 210 g of ^{water heated to 50 ° C.} The temperature of the solution was increased to 70 ⁰ C. After 23 minutes at 7O ⁰ C. 17 g of dimethyl sulfate was added over 5 minutes. The solution was heated with stirring at 7O ⁰ C until its viscosity at 25 ⁰ C> C on the Gardner scale (after 36 minutes) attained. It was cooled to 25 ⁰ C and adjusted to pH 4.0 with 7.5 cc of 10% sulfuric acid adjusted. The product contained 26.6% solids and had a Gardner viscosity of > D at 25 ^° C.

Example 9

A polyamide produced by the process described in Example 6 and not claimed here was converted into a resin suitable for the production of wet-strength paper as follows:

According to the invention, 75 g of epichlorohydrin were introduced over the course of 6 minutes with stirring to a solution of 189 g (dry basis) of the polyamide in 630 g of water which was ^{heated to 50 ° C.} The temperature of the solution was increased to 70 ° C and 51 g of dimethyl sulfate immediately within

Added 6 minutes. The solution was heated with stirring at 7O ⁰ C until its viscosity at 25 ⁰ C on the Gardner scale <C (after 4 hours and 59 minutes) reached. It was cooled to 25 ⁰ C. and adjusted to 4,0 'ger with 7.0 cc of 10% sulfuric acid to pH. The product contained 25.8% solids and had a Gardner viscosity of <C at 25 ^° C.

Example 10

A polyamide produced by a process not claimed here in accordance with the information in Example 6 was converted into a resin suitable for the production of wet-strength paper as follows:

According to the invention, 34 g of epichlorohydrin were introduced within 2 minutes with stirring to a solution of 63 g (dry basis) of the polyamide in 100 g of ^{water heated to 50 ° C.} The solution temperature was increased to 7O ⁰ C, and 17.0 g of dimethyl sulfate were added immediately within 2 minutes. The solution was heated to 70 ° C. with stirring until its viscosity at 25 ° C. reached <D on the Gardner scale after one hour and 12 minutes. It was diluted with 140 g of water, cooled to 25 ° C and at p _H 7 cc of 10% sulfuric adjusted 4.0. The product contained 20.1% solids and had a Gardner viscosity of <A at 25 ^° C.

Example 11

A polyamide produced by a process not claimed here in accordance with the information in Example 6 was converted into a resin suitable for the production of wet-strength paper as follows:

To a solution of 31 g (dry basis) of the polyamide in hog water which was heated to 5O ⁰ C, according to the invention 18.2 g of epichlorohydrin were added while stirring for 3 minutes. The temperature of the solution was raised to 70 ° C and maintained at this point until the viscosity of the solution at 25 ⁰ C <D on the Gardner scale at 35 minutes reached. 8.5 g of dimethyl sulfate were added all at once to this solution. It was then cooled to 25 ⁰ C and adjusted to pn 4.0 with 7 cc of 4% hydrochloric acid. The product contained 25.8% solids and had a Gardner viscosity of > ß at 25 ^° C.

The following examples illustrate the use of other quaternizing agents.

Examples 12-17

Various samples of a method not claimed here according to the information in the example 6 produced polyamides were further processed according to the invention as follows:

240 g of water were added to 116 g (63 g dry basis) of the polyamide solution in a round-bottom flask equipped with a mechanical stirrer and thermometer. The solution was heated to 5O ⁰ C and according to the invention 31 g of epichlorohydrin was added within 2 minutes. The solution was then ^{heated to 70 °} C. until the viscosity at 25% solids content reached approximately A on the Gardner-Holdt scale. The solution was then cooled to a temperature of about 55 to about 65 ° C, the quaternizing agent is added and the heating in this temperature range continued until the viscosity at 25% solids and about 25 ⁰ C for about> B to <C on the Gardner Holdt scale was. It was then ^{cooled to 25 °} C. and adjusted to a pH of about 2.0 to 2.5 with concentrated sulfuric acid. The solids concentrations of the products (listed in the order of the table) were 24.5, 27.0, 23.5, 25.2, 24.3 and 24.7%

The following quaternizing agents were used: methyl iodide (20.9 g), diethyl sulfate (22.6 g),

ίο ethyl bromide (16.0 g), 1-chloroglycerine (16.2 g), 1,3-dichloroglycerine (19.0 g), benzyl chloride (18.6 g).

Quaternizing agents lot
in g ° / o admitted Wet tensile strength Broad)
ge
hardens At- Art 20.9 put it (kg per centi 2.05 15 game Methyl iodide 22.6 resin
(Dry
fabric base) meter
unge
hardens 1.80 12th Diethyl sulfate 16.0 1 1.07 1.89 ao ¹³ Ethyl bromide 16.2 1 0.91 1.78 14th 1-chlorine- 1 1.09 15th glycerin 19.0 1 0.98 1.69 1,3-dichloro 16 glycerin 18.6 1 0.96 1.64 Benzyl chloride 17th 1 0.95

The basis weight of all leaves was 18.1 ± 0.2 kg per 278.7 m ² . Sheets made from the same pulp, taken from the felt, gave wet tensile strengths of 0.14 kg (uncured) and 0.21 kg (cured) per centimeter of width.

Example 18

According to the method not claimed here, 615 g of diethylenetriamine and 300 g of water were poured into a three-necked, Brought a flask equipped with a stirrer, condenser and thermometer. To this 870 g of adipic acid were given. Upon dissolving the acid in the amine, the solution became Heated 180 to 185 ° C for one hour and 15 minutes. The solution was then taken to 140 ° C Vacuum cooled by about 30 mm of mercury. The vacuum was released and 1290 g of water slowly added. The product contained 50% solids.

150 g of water were added to 260 g of this polyamide solution in a flask with a round bottom.

This solution was slowly warmed to 5O ⁰ C

and according to the invention, 50 g of epichlorohydrin were added dropwise over 10 minutes. The solution was then heated to 60 ° C for 11 minutes 6 cc of concentrated hydrochloric acid was added and the product cooled to 25 ⁰ C. Then 25 ecm of concentrated hydrochloric acid were added to adjust the pn to 5.0. The solution contained 37.7% solids and had a viscosity of B on the Gardner scale.

Example 19

According to a method not claimed here, 200 g of diethylenetriamine and 100 g of water were placed in a three-necked flask equipped with a discharge condenser, mechanical stirrer and thermometer. 290 g of adipic acid were added to this. After dissolving the acid, the solution was heated to 180 ° C. for 55 minutes. The polyamide was cooled ecm to 14O ⁰ C under a vacuum of 30 and 430 cc water added. The product was

409 660/444

then cooled to 25 ° C. Analysis of the polyamide solution resulted in the following:

Total solids content 50.5%

Acid number 3.3 g

An epichlorohydrin complex was prepared from the polyamide in the following manner: 258 grams of the above polyamide plus 150 grams of water were weighed into a 500 cubic centimeter three-necked flask. According to the invention, 50 g of epichlorohydrin were added to this at room temperature. This solution was then heated to 60 ⁰ C. It was held for 10 minutes at 6O ⁰ C and then 10 cc of concentrated hydrochloric acid. The solution was then immediately cooled to room temperature and adjusted to pH 5 with 24 ecm of concentrated hydrochloric acid. The final viscosity of the solution was B on the Gardner scale and it contained 37.4% solids.

B e i s ρ i e 1 20

According to a method not claimed here, 225 g (2.18 mol) of diethylenetriamine and 100 g of water were placed in a three-necked flask equipped with a mechanical stirrer, thermometer and condenser. To this, 290 g (2.0 mol) of adipic acid were added. After dissolution of the acid in the amine, the solution was heated to 185-200 ⁰ C then held for 1 ¹ I ₂ hours. Vacuum from a water pump was then applied to the flask for the time required to cool the contents of the flask to 41 ° C. Then 430 g of water were added. The polyamide solution contained 52.3 percent solids and had an acid number of 2.1. 225 g of water were added to 60 g of this polyamide solution in a round bottom flask.

This solution was heated to 50 ° C. and, according to the invention, 12.5 g of epichlorohydrin were added dropwise over the course of 11 minutes. The contents of the flask were then heated to 60 to 7oC until a Gardner viscosity of "-.. ■ E had reached Then 150 g of water were added to the product, and it was cooled to 25 ⁰ C 11 cc of 10% Hydrochloric acid was then added to adjust the pH to 5.0. The product contained 9.0% solids and had a Gardner viscosity of C to D.

Claims (4)

Patent claims: 1. Process for the production of water-soluble condensates based on polyamides and epichlorohydrin by conversion of polyvalent amines with dicarboxylic acids with 3 to 10 carbon atoms in the heat, characterized in that polyamines having at least three amino groups are used as polyvalent amines used and the polyamides formed then reacted with epichlorohydrin. 2. The method according to claim 1, characterized in that the reaction is carried out in the presence of a quaternizing agent. 3. The method according to claim 1, characterized in that the polyamine is a polyalkylene polyamine and this in a molar ratio to the dibasic carboxylic acid of about 0.8 to 1.4: 1 used. 4. The method according to claim I, characterized in that the epichlorohydrin in one Molar ratio to the secondary amino groups of the polyamide of about 0.5 to 1.8: 1 is used. Considered publications:
German Patent No. 758 619;
French Patent No. 868 127;
German interpretative document No. 1 066 741. When the application was announced, three priority documents were displayed. 409 660/4 «9.64 © Bundesdruckerei Berlin