DE3023947A1 - NEW POLYHYDROXYALKYLPOLYAMINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A TEXTILE SOFTENER - Google Patents

Description

4000 Düsseldorf, June 23, 1980 £. HENKELKGaA

ZR-FE / Patents Henkelstrasse 67 Dr.Ms-sch

Patent application

D 6158

"New polyhydroxyalkyl polyamines, methods of making them and their use as textile softeners "

The present invention relates to reaction products of epoxyalkanes with polyaminoalkanes, their salts with organic or inorganic acids and the addition products of alkylene oxide to the reaction products or their salts. The invention also relates to a process for the preparation of these compounds and their Use as a textile softener.

With epoxyalkanes, reactive raw materials are available for the implementation with compounds available that contain active hydrogen atoms. The present invention uses the resulting possibilities for the synthesis of new polyhydroxyalkyl polyamines, by reacting epoxyalkanes, which have terminal or internal epoxy groups, with polyaminoalkanes, which have two or more N-H groups are prepared. The new substances are polyhydroxyalkyl polyamines produced by reaction from

a) Epoxyalkanes with 6 to 20 carbon atoms and with a terminal or internal epoxy group
b) Polyaminoalkanes with two or more NH groups in the molecule

in a molar ratio a: b of 5: 1 to 2: 1 and their reaction products with 1 to 5 moles of C ^ -C ^ epoxyalkane and the salts of the polyhydroxyalkyl polyamines and the reaction products with organic or inorganic acids.

130063/0155

Patent application β 6158 - / - ^ 'HENKELKGaA

Γ ZR-FE / patents

The epoxyalkanes to be used as starting materials are available in large quantities. You u / earth in a known manner from the appropriate Obtained olefins or olefin mixtures. To the epoxyalkanes with terminal epoxy group comes from 1,2-monoolefins, for example by polymerization of ethylene with organic aluminum compounds as catalysts or by thermal cracking obtained from paraffin hydrocarbons. examples for suitable epoxyalkanes are the compounds 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane and 1,2-epoxyeicosane. Likewise Epoxy mixtures such as C, ",, .- 1,2-epoxy with approx. 70 percent by weight of C, - and approx. 30 percent by weight of C, - epoxyalkane or 0 ,,,, 0-1,2-EpOXId with approx. 40 weight percent C ,, - and approx. 60 percent by weight of C, "- epoxyalkane.

The internal epoxyalkanes are obtained, for example, by epoxidation of olefins or olefin mixtures which are produced by catalytic dehydrogenation or by chlorination / dehydrogenation of linear paraffinic hydrocarbons. Monoolefins with an internal double bond can also be produced by isomerization of λ-olefins. Suitable internal epoxyalkanes of a C ,, / ,, - olefin fraction contain approx. 22% by weight of C ,, -, approx. 30% by weight of C ,, -, approx. 26% by weight of C ,, -, approx. 22% by weight of C ,, - epoxyalkane. A likewise suitable epoxyalkane mixture of a C, ₅ "" -olefin fraction contains approx. 26 weight percent C ₁₅ -, approx. 35 weight percent C ,, -, approx. 32 weight percent C ₁₇ - and approx. 7 weight percent C, "- epoxyalkane .

130063/0155

Patent application D 6158 _ / _f. HENKELKGaA

f ZR-FE / patents

Preferred epoxyalkanes (a) v / iron on a terminal epoxy group, where particularly valuable polyhydroxyalkyl polyamines are obtained, if one starts from epoxyalkanes with 10 to 18, in particular 12 to 14 carbon atoms in the molecule. Suitable polyaminoalkanes have two or more N-H groups in the molecule. These N-H groups are separated from one another by at least two carbon atoms, each N-H group having at least one N-H bond. This N-H bond enables the polyaminoalkanes to react with the Epoxyalkanes enabled. Such polyaminoalkanes are commercially available products. The simplest compound of this type is ethylene diamine. Preferred polyaminoalkanes are, for example, propylenediamine, diethylenediamine, Dipropylenetriamine, symmetrical methyldipropylenetriamine, Triethylenetetramine, tripropylenetetramine and tetraethylenepentamine. Dipropylenetriamine is a particularly suitable one Link.

The molar ratio in the reaction of epoxyalkanes (a) with polyaminoalkane (b) depends on the number of carbon atoms of the epoxyalkane molecule; it generally lies for the ratio of (a): (b) between 5: 1 and 2: 1, with a ratio of about 5: 1 for the reaction of C 1 - epoxyalkane and for the reaction of C -, .- or longer-chain epoxyalkane a ratio (a): (b) of . about 2: 1 to obtain particularly useful polyhydroxyalkyl polyamines. For the conversion of epoxyalkane with 8 to 12 carbon atoms the ratio (a): (b) lies between these two limit values. Particularly interesting polyhydroxyalkyl polyamines are by reacting an epoxyalkane with 12 to 14 carbon atoms in the molecule and a terminal epoxy group with dipropylenetriamine in the molar Ratio of 2: 1 manufactured products.

130063/0155

Patent application _D 6158 - / - ty. HENKEL KGaA

(' ZR-FE / Patents

If these polyhydroxyalkyl polyamines are mixed with an excess organic or inorganic acid, excellent water-soluble salts of the polyhydroxyalkyl polyamines are obtained. Per nitrogen atom 1 to 5 acid equivalents, preferably about 1 to 2 acid equivalents, are used in the polyaminoalkane used. Suitable acids are, for example, formic acid, acetic acid, citric acid, tartaric acid, adipic acid, maleic acid, succinic acid, Diglycolic acid, malic acid, lactic acid, sulfamic acid, hydrochloric acid, Sulfuric acid, phosphoric acid, nitric acid, of which formic acid is particularly preferred. During the salt formation, enough acid is added that an aqueous solution containing 8 weight percent polyhydroxyalkyl polyamine contains, becomes clear; this is generally one corresponding to the number of nitrogen atoms in the polyhydroxyalkyl polyamine molecule Number of equivalents of the above acids. In some cases, to achieve clear solubility, a lower solubility is also required or larger amount of acid required. Particularly interesting compounds are those polyhydroxyalkylpolyamine salts which, by reaction of an epoxyalkane with 12 to 14 carbon atoms in the molecule and a terminal epoxy group with dipropylenetriamine in the molar ratio of 2: 1 and in which the salt formation was carried out with formic acid.

The properties of the neutralized polyhydroxyalkyl polyamines can be modified further by adding alkylene oxide, in particular ethylene oxide and / or propylene oxide. As a result, the solubility of the compounds and the absorbency of textiles treated therewith, on the one hand, and the smoothness of the treated textiles, on the other hand, can be further improved. Compounds particularly balanced with regard to these properties contain at least 1 mol of ethylene oxide and / or propylene oxide per NH group of the polyhydroxyalkyl polyamine. In this case, adduct compounds which have been prepared by reacting χ moles of C, “- C ,, - epoxyalkane with a terminal epoxy group with ü moles of dipropylenetriamine, 3 21 moles of ethylene oxide were then added to these reaction products and finally the salt formation with 1.5 - Molar formic acid was made to show particularly valuable properties.

130063/0155 ^Λ

Patent application D 6158 - jf- {Q. HENKELKGaA

ZR-FE / patents

The invention also relates to a process for the preparation of the new compounds. This process is characterized in that 2 to 5 moles of epoxyalkane with 6 to 20 carbon atoms in the molecule and with terminal or internal epoxy groups with 1 mole of polyaminoalkane with two or more NH groups in the molecule at temperatures between 80 and 250 ⁰ C 0, Reacts for 5 to 10 hours with stirring at normal pressure, then the pressure in the reaction vessel is reduced to 0.1 to 50 mbar, low-boiling parts of the batch are distilled off at a bottom temperature between 150 and 250 ° C, optionally to the polyhydroxyalkyl polyamine thus obtained as the distillation residue Autoclave 1 to 5 moles of ethylene oxide and / or propylene oxide per NH group of the polyaminoalkane is added that, if necessary, the adduct obtained in this way by adding 1.1 to 5, preferably about 1 to 2, equivalents of organic or inorganic acid per NH group in the molecule of the polyaminoalkane converted into a salt.

Particularly light-colored products are obtained if one does the implementation. of the epoxyalkane with the polyamine in an inert gas atmosphere. This procedural measure is therefore preferred. In addition, the reaction can still be carried out in the presence of reducing components, such as e.g. tin or sodium boronate, which causes a further lightening of the color of the reaction products. the The addition of alkylene oxide to the hydroxyalkyl polyamine in the autoclave is preferably carried out at from 60 to 200 ° C., a The alkylene oxide pressure in the autoclave does not exceed 10 bar. The temperature in the neutralization batch should be used for salt formation do not allow it to rise above 50 ° C. The best way to ensure this is that the acid, which may have been diluted with water, is slowly removed is added to the polyhydroxyalkyl polyamine and mixes immediately. However, it is also possible to use the amine to mix the undiluted acid, if care is taken by appropriately careful mixing that in the neutralization approach a temperature of 50 C is not exceeded. This precaution is to avoid mostly undesirable ones Color deepening required.

/ 6

130063/0155

Patent application q gn ng _ j / HENKEL KGaA

"V" ~ 4 1. ZR-FE / patents

ZR-FE / patents

With the addition of ethylene oxide and / or propylene oxide in the autoclave is generally used per N-H group to implement with the epoxyalkane used polyaminoalkane etu / a 1 mol alkylene oxide attached. If you want to achieve pronounced effects, you can do more Moles of alkylene oxide per nitrogen atom attached and / or earthed, with about 5, preferably about 3 to 4 moles of alkylene oxide per N-H group in terms of one optimal properties of the new compounds should represent the upper limit. By adding ethylene oxide can increase the solubility of the compounds in water and increase the absorbency of the Textiles treated with these compounds improve, while the addition of propylene oxide improves the softness of treated textiles can increase. For setting special. Combinations of properties can be both ethylene oxide and propylene oxide are accumulated. The compounds are expediently neutralized after the addition of alkylene oxide. As already stated, it is important that a temperature of 50 ° C. is not exceeded in the neutralization batch.

The salts of the polyhydroxyalkyl polyamines according to the invention and their alkylene oxide addition products dissolve in water in any concentration and form clear, stable solutions. The solutions may also contain water-miscible solvents, e.g. short-chain alcohols such as ethanol, isopropyl alcohol, propylene glycol or Butylene glycol. The pH of the solutions depends on the type and amount of organic or inorganic acid used to form the salt.

If you treat textiles in the washing or rinse cycle or in the tumbler the compounds according to the invention, after drying they have a pleasantly soft handle and good electrostatic properties on. The absorbency of the treated textiles is excellent. The use of the process according to the invention produced new compounds as softening and antistatic agents is therefore a further subject of the invention, where the application in concentrated or diluted form e.g. for Post-laundry treatment can be done in commercial or household washing machines or in separate liquors.

130063/0155 ^/?

Patent application ^) gj ^ g -Jl- AO HENKELKGaA

^Λ * - ' ZR-FE / patents

The new connections are used, for example, in a liquid agent for washing after-treatment in amounts of 2 to 15, preferably 2 to 10 percent by weight of the new compounds, which are dissolved in a liquid carrier medium. In addition, this agent can contain at least one other compound from the group Contain emulsifier, dye, fragrance, preservative, viscosity adjusting agent and possibly other common additives.

The nonionic surfactants ("nonionics") are particularly suitable as emulsifiers. This includes products that demonstrate their hydrophilic properties the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups and, in general, an accumulation of hydroxyl groups. Such Nonionics contain at least one hydrophobic radical of 8 to 26, preferably 10 to 20 and in particular 12 to 18 in the molecule Carbon atoms, and at least one nonionic water-solubilizing group. The preferably saturated hydrophobic residue is mostly aliphatic, possibly also alicyclic, in nature; it can work with the water-solubilizing groups directly or via intermediate links be connected. Benzene rings, carboxylic acid ester or carbonamide groups, bound ether or ester-like, are used as intermediate links Residues of polyhydric alcohols, such as those of ethylene glycol, propylene glycol, glycerine or corresponding polyether esters in question.

Of particular practical interest are those caused by the addition of Ethylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides Products, these nonionics 4 to 100, preferably 6 to 40 and in particular 8 to 20 ether residues, especially ethylene glycol ether residues may contain per molecule. In addition, in these polyether chains or at the end of which propylene or butylene glycol ether residues or polyether chains may be present.

• /8th

130063/0158

3Q239A7

Patent application D 6158 - γ- / fy . HENKEL KGaA

ZR-FE / patents

Furthermore, nonionics include products that are made of themselves water-insoluble polypropylene glycols or from water-insoluble propoxylated lower, 1 to 8, preferably 3 to 6 carbon atoms containing aliphatic alcohols or from water-insoluble propoxylated alkenediamines are obtained by ethoxylating them until they are water-soluble.

The nonionics also include fatty acid or sulfonic acid alkylolamines, e.g. from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g. the glycamines. They can be replaced by amides from higher primary or replace secondary alkylamines and polyhydroxycarboxylic acids.

The capillary-active amine oxides include, for example, those of higher tertiary, one hydrophobic alkyl radical and two shorter alkyl and / or alkylol radicals containing up to 4 carbon atoms each Amines derived products.

In addition to the mostly readily water-soluble surfactants, suitable nonionic dispersants may also be water-soluble or in Water-emulsifiable or dispersible compounds which either do not have any hydrophobic radicals in the sense of the nonionic ones described above Contain surfactants, or where the nature or number of hydrophilic groups to achieve complete water solubility not suffice. The former include, for example, solid or liquid polyethylene glycols, which are known as condensation polymers of ethylene oxide with ethylene glycol or water, ethylene oxide adducts of glycerin and other polyalcohols, etc .; belong to the latter e.g. partial fatty acid glycerides or water-insoluble or not completely water-soluble alkoxylation products, e.g. those with 2 to 5 Ethylene glycol ether residues in the molecule.

1 30063 / 015S

Patent application q 6158 - ^ - i ti HENKEL KGaA

'Λ V * ZR-FE / Patents

The new connections can also be used in a concentrated composition with 30 to 85 percent by weight of the new compounds, in combination with 5 to 25 percent by weight of one Emulsifier and at least one other compound from the group of dyes, fragrances, preservatives, viscosity regulators, liquid carrier medium. The liquid carrier medium used is primarily water, but it is also possible alcoholic or aqueous / alcoholic carrier media containing lower alcohols or glycols with 2 to 6 carbon atoms, such as ethanol, isopropanol, Contain or consist entirely of ethyl glycol monobutyl ether. These concentrated products can be broken down into either correspondingly small amounts Use amounts for washing after treatment in the last rinse bath or they are used as pus to be thinned just before use Stock liquor approaches.

Another possible use is the use in sour set laundry treatment agents containing the new substances in amounts of 2 to 10 percent by weight in combination with about 0.5 to Contains 15 percent by weight of acidic additives as excrusting constituents. Acid additives become inorganic Mineral acids and non-surface-active organic acids with 1 to 8 carbon atoms, such as amidosulfonic acid, urea compounds orthophosphoric acid, boric acid, oxalic acid, lactic acid, glycolic acid, Citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, formic acid, acetic acid and propionic acid as well as the benzene, toluene or xylenesulfonic acid, sulfoacetic acid or sulfobenzoic acids or understood acidic alkali salts of these acids. Glycolic acid and citric acid are preferred because of their ready availability and non-toxicity Acids. If, for example, the laundry is treated with such agents in the last rinsing bath, incrustation becomes reliable prevented, while at the same time giving the laundry a pleasant, soft feel and good absorbency. Already in Incrustations present in the laundry are broken down again by using such agents.

1 30063 / 015S

Patent application _{D 6158} _ \ fi_ / ^. HENKELKGaA

/ ZR-FE / patents

ZR-FE / patents

The polyhydroxyalkyl polyamines of the invention can also be used use in tumbler aids. If you add a flexible flat structure to an item of freshly washed, damp laundry in the tumbler, for example from nonwoven or foam, which contains a suitable amount of the new compounds, the Laundry communicated a pleasant grip and excellent absorbency. In addition to the new compounds as an active ingredient, the Flat structures, if necessary auxiliary substances and additives, such as other textile softening agents, emulsifiers, fragrances, preservatives, Contain solvents, dyes, pigments or other substances common in such agents.

The inventive new compounds develop a softening effect. In particular, mild detergents with a content of about 2 to 15 percent by weight these active ingredients clean and care for the laundry at the same time, making it comfortable to wear.

130063 / Ö 1 5 5

Patent application _{D 615} g _ V.., HENKELKGaA

/ Uf '- ZR-FE / Patents

Examples

Example 1 describes the preparation of a new compound according to the invention from 1,2-C, -epoxyalkane and dipropylenetriamine.

example 1

197 g (1.5 mol) of dipropylenetriamine were heated to 150.degree. To this end, 676 g (3 mol) of 1,2-C, ^ - epoxyalkane (technical distillate with 7.10% epoxy oxygen, calculated molecular weight 225) were allowed to flow within 30 minutes with stirring and under a nitrogen atmosphere. After three hours of stirring at 150 C. 64 g of lead (bottom temperature to about 240 ⁰ C) were distilled off to obtain 809 g of the main product (amine value 306) as a residue at a pressure of 0.6 mbar. That from the. Amine number (= 306) calculated molecular weight of the main product was 550 (theoretical molecular weight of a bis-hydroxyalkyl polyamine consisting of 2 moles of epoxyalkane and 1 mole of polyamine: 555). The main product solidified at room temperature to form a semi-solid mass which turned into a clear melt at 60.degree.

^{After purging three times with nitrogen at 0.5 bar at 120 °} C., 192 g (about 4.7 mol) of ethylene oxide were added to 801 g (approx. 1.5 mol) of this reaction product in the autoclave. The addition took about 2.5 hours at an ethylene oxide pressure of a maximum of 5 bar; 993 g of a pale yellow, clear liquid product with an amine number of 241 were obtained. This gives a molecular weight of 698 (theoretical molecular weight: 687). 762 g (approx. 1.1 mol) of this adduct were stirred into 238 g (5.1 mol) of formic acid so slowly that a temperature of 50 ° C. was not exceeded.

Examples 2-12

As described in Example 1, polyhydroxyalkylpalyamine salts were prepared made from the following raw materials in the specified molar ratios:

130063/0155

Patent application q £ 158

HENKELKGaA ZR-FE / Patents

Table 1

No. Epoxyalkane Polyamine Alkylene oxide acid 2 2 moles of 1,2-C ₁₄ 1 mole of DPTA 3 moles of EO AMS / ASS 3 2 moles of 1,2-C ₃₄ 1 mole of DPTA 1 mole of EO AMS 4th 2 moles of 1,2-C ₁₄ 1 mole of DPTA 2 moles of EO AMS / ASS 5 2 moles of 1,2-C ₁₄ 1 mole of DPTA 2 moles of EO AMS 6th 2 moles of 1,2-C ₁₂ 1 mole of DETA 3 moles of EO AMS 7th 2 moles of 1,2-C ₁₂ 1 mole of DETA 3 moles of EO ASS 8th 2.25 moles iC _11/14 1 mole of DPTA 3 moles of EO - 9 2 moles of 1-C _11/14 1 mole of MDPTA - AMS 10 5 moles of 1,2-C ₆ 1 mole of DPTA AMS 11 2 moles of 1,2-C ₁₄ 1 mole of DPTA 3 moles of EO
+3 moles PO AMS 12th 2 moles of 1,2-C ₁₄ 1 mole of DPTA 1 mole of PO AMS 13th 2 moles of 1,2-C
14th 1 mole of DPTA 3 moles of EO , -

/ 13 · ■ · -,

130063 / 01B6

Patent application D 6158

In this table:

HENKELKGaA

ZR-FE / patents

1,2-C-, 1,2-C, 2 »1,2-C,.: Epoxyalkane with a terminal epoxy group

and 6 or 12 or 14 carbon atoms, respectively;

DPTA: DETA: MDPTA: EO: PO: AMS: ASS: AMS / ASS:

example

Epoxyalkane with an internal epoxy group and 11 to 14 carbon atoms;

Dipropylenetriamine; Diethylenetriamine; symmetrical methyldipropylenetriamine; Ethylene oxide; Propylene oxide; Formic acid; Sulfamic acid;

mixed salt of formic and amidosulphonic acid.

With the reaction products of Examples 1 to 7, terry cloth fabric treated previously by a 96-hour treatment in a liquor containing 4 g of sodium tripolyphosphate per liter of water, was made hard; the hardened, untreated terry-20 fabric received the grade Q (= very hard). Very soft terry cloth received a grade of 6. Persons who are trained and experienced in assessing the softness of textiles have received the

/ 14

130063 / 015S

Patent application D 6158 - ψ- IQ HENKELKGaA

' ZR-FE / Patents

Softness of the new compounds according to the invention in one Concentration of 0.3 g per liter of treated textiles within the range 0 to 6 and assessed with the treatment result an excellent emollient, but the absorbency worsening active ingredient of the distearyldimethylammonium chloride type compared.

In addition to the softness, the absorbency of the treated textiles was determined by the height of rise method (DIN 53924). For this purpose, so-called "Krefeld test fabric", which had previously been washed three times with a commercial heavy-duty detergent, was treated with the new compounds in a concentration of 0.3 g per liter at a liquor ratio of 1:10 for 5 minutes in a launderometer with the addition of 10 steel balls shaken per container. Adhering liquid was then largely removed by spinning (30 seconds) in a terry towel. The Probeläppchen were conditioned for 24 hours at 23 ⁰ C and 60 to 70% relative humidity. The pieces of fabric pretreated in this way were then dipped with one edge in distilled water; It was measured after 1, 5, 10 and 30 minutes how high the water in the pieces of fabric had risen, with a high rise corresponds to good absorbency. Again, the comparison was made with samples which had been treated in the same way with a commercially available textile softener of the distearyldimethylammonium chloride type. When comparing the various test and measurement results in Table 2 below, it should be noted that the values were not all determined in a row and therefore a quantitative comparison is not possible; At the same time, the balanced combination of properties of the active ingredients according to the invention is clearly recognizable compared to the commercially available textile softener.

130063/0155

Patent application D 6158

Table 2

HENKEL KGaA ZR-FE / Patents

Active ingredient from
Example no. Softness Climb
1 he (in
5 cm) nac
10 h min.
30th 1 3.6 3.1 4.7 5.7 7.7 2 2.4 3.1 4.9 6.0 8.5 3 2.2 2.5 3.5 4.3 5.8 4th 2.1 2.6 3.5 4.0 5.0 5 2.0 2.7 3.6 4.2 5.2 6th 2.5 3.6 6.4 8.2 11.7 7th 2.5 3.4 6.3 8.0 11.5 trade
common 4.8. 0.8 ¹ ^ ² 1.4 1.6

The test results show that the new compounds according to the invention with good softening performance, the textiles treated with it have a much better absorbency than a commercial known active ingredient.

Examples 15 and 16

These examples describe the composition of concentrated fabric softeners, which are either in this form in accordance with lower dosage or after prior dilution with water to, for example, 10 times the volume for post-wash treatment are used in the rinse cycle of commercial washing machines, household washing machines or in separate fleets.

/ 16

130063/0155

Patent application D 6158 - l / - # i- ' HENKELKGaA

ZR-FE / patents

Example 15

60 wt .-? I active ingredient of Example 8,

5 Ge \ tf .-? O formic acid,
25 geu /.-? I ethanol,
10 wt .-? O 'water.

Example 16

60 Ge \! I. ~% Active ingredient of Example 13,
10 Gev /.-? O hydrochloric acid (37? Iig),
30% by weight of ethanol.

Example 17

A laundry / calibration detergent in diluted form, its active ingredient concentration roughly corresponds to that of commercially available products for household washing machines, has the following composition, for example:

7.0 Ge \ i /.-? O active ingredient of Example 13,
1.0 wt .-? O formic acid,
1.7 Ge \ i /.-? O ethanol,

Remainder small amounts of dye, fragrance, shear metal complexing agent, Water.

Example 18

If a viscose fiber is impregnated with the active ingredient from Example 1

2 fleece with low absorbency in such a way that about 40 to 45 g of active ingredient are contained per m on the fleece and if this is impregnated

2
ned fleece (approx. 350 cm) to a batch of laundry in the tumbler, the active ingredient is transferred to the laundry during the drying process and causes a noticeable improvement in the softness of the laundry items treated in this way.

130063/0155
ORIGINAL INSPECTED

Patent notification D 6158-1? < H . HENKEL KGaA

ZR-FE / patents

Example 19

A fabric softener that not only has a softening effect but also excrusting Has an effect, for example, has the following composition:

8% by weight of active ingredient from Example 1,
10 Ge \ ii .-% citric acid,
Rest water.

If you put such an agent in the last rinsing bath in a concentration from about 2.5 g / l of washing liquor to, incrustations will occur prevented. Similar effects are achieved with agents that contain other suitable acidic additives.

Example 20

A laundry detergent of the specified composition has an excellent one Washing power and at the same time gives the washed textiles a pleasant grip with very good absorbency.

9.5 wt .- & C ,. ,, _5- oxo alcohol with 7 mol of ethylene oxide, 9.5% by weight of Si C, "," - fatty alcohol with 6 mol of ethylene oxide, 4.0% by weight of active ingredient from Example 13,
4.0 wt .- & ethanol,
3.0% by weight of propylene glycol-1,2,

Remainder of water and small amounts of the usual components of liquid mild detergents.

130063/0158

Claims (23)

Patent application D 6158 - j / - HENKELKGaA ZR-FE / patents "New polyhydroxyalkyl polyamines, processes for their preparation and their use as fabric softeners" C lyPolyhydroxyalkylpolyamine claims, prepared by reacting a) Epoxyalkanes with 6 to 20 carbon atoms and with terminal or internal epoxy group with b) polyaminoalkanes with 2 or more N-H groups in the molecule in a molar ratio a: b of 5: 1 to 2: 1 and their reaction products with 1 to 5 moles of CL-C-j-epoxyalkane and the Salts of the polyhydroxyalkyl polyamines and the reaction products with organic or inorganic acids. 2. Polyhydroxyalkylpolyamines according to claim 1, characterized in that that the epoxyalkane according to a) has a terminal epoxy group. 3. Polyhydroxyalkylpolyamines according to Claims 1 and 2, characterized in that the epoxyalkane is 10 to 18, preferably Has 12 to 14 carbon atoms. 4. Polyhydroxyalkylpolyamines according to Claims 1 to 3, characterized in that the polyaminoalkane is a compound from the group propylenediamine, dipropylenetriamine, symmetrical methyldipropylenetriamane, diethylenediamine, triethylenetetramine, Is tripropylenetetramine, tetraethylenepentamine or mixtures thereof. 5. Polyhydroxyalkylpolyamines according to Claims 1 to 4, characterized in that the polyaminoalkane is dipropylenetriamine is. 130063/0155 ORIGINAL INSPECTED Patent application ρ ₆₁₅₈ _ y ^ _ j / HENKELKGaA ■ s ZR-FE / patents 6. polyhydroxyalkyl polyamine according to claims 1 to 5, produced by reacting an epoxyalkane with 12 to 14 carbon atoms in the molecule and a terminal epoxy group Dipropylenetriamine in a molar ratio of 2: 1. 7. Salts of the polyhydroxyalkyl polyamines according to claims 1 to with organic or inorganic acids from the group formic acid, Acetic acid, citric acid, tartaric acid, adipic acid, maleic acid, succinic acid, diglycolic acid, malic acid, lactic acid, Amidosulphonic acid, hydrochloric acid, ivory acid, phosphoric acid, salt-pitric acid, preferably formic acid. 8. Salts of the polyhydroxyalkyl polyamines according to claim 7 with a the number of acid equivalents corresponding to the number of nitrogen atoms in the polyhydroxyalkyl polyamines. 9. Polyhydroxyalkyl polyamine salt according to Claims 7 and 8 of a polyhydroxyalkyl polyamine according to claim 6 and formic acid. 10. Addition compounds of ethylene oxide and / or propylene oxide to the polyhydroxyalkyl polyamines according to claims 1 to 6 in a ratio of at least 1 mol of ethylene oxide and / or Propylene oxide per N-H group of the polyhydroxyalkyl polyamine and their salts with the acids according to claim 7. 11. addition compounds according to claim 10, prepared by reaction uon χ mol of epoxyalkane with 12 to 14 carbon atoms in the molecule and with a terminal epoxy group with - mol of dipropylenetriamine, subsequent addition of 3 moles of ethylene oxide to this 2 χ Reaction product and salt formation with 1.5 mol of formic acid. 130063/0155 Patent application D 6158-20 ^ - J HENKELKGaA ' ZR-FE / Patents 12. A process for the preparation of compounds according to the claims 1 to 11, characterized in that 2 to 5 moles of epoxyalkane with 6 to 20 carbon atoms in the molecule and with terminal or internal epoxy group with 1 mole of polyaminoalkane with 2 or more N-H groups in the molecule at temperatures between 80 and 250 C for 0.5 to 10 hours with stirring, then the Pressure in the reaction vessel reduced to 0.1 to 50 mbar, low-boiling parts of the batch at a bottom temperature between 150 and 250 C distilled off, optionally to the polyhydroxyalkyl polyamine obtained as a distillation residue in the Autoclave 1 to 5 moles of ethylene oxide and / or propylene oxide per N-H group of the polyaminoalkane added, if necessary adduct obtained by adding 1.1 to 5, preferably about 1 to 2, equivalents of organic or inorganic acid per N-H group converted into a salt in the molecule of the polyaminoalkane. 13. The method according to claim 12, characterized in that the Implementation of the epoxyalkane in an inert gas atmosphere. 14. The method according to claims 12 and 13, characterized in that that the addition of the alkylene oxide is carried out in the autoclave at a temperature of about 60 to about 200.degree. 15. The method according to claims 12 to 14, characterized in that that an alkylene oxide pressure of 10 bar is not exceeded in the addition of the alkylene oxide. 16. The method according to claims 12 to 15, characterized in that that the heat of neutralization is removed during salt formation in such a way that a temperature of 50 ° C. is not reached in the neutralization batch exceeds. 130063/0155 Patent application η ßl58 - 21 - Γ- HENKELKGaA '2R-FE / patents 17. Use of the compounds according to claims 1 to 16 as u / calibration and antistatic-making active ingredients for textile structures. 18. Use according to claim 17 for treating laundry in a liquid agent in amounts of 2 to 15, preferably 2 to 10 'Weight percent. 19. Use according to claims 17 and 18 in an agent with at least one further compound from the group emulsifier, Dye, fragrance, preservative, viscosity control agent, liquid carrier medium. 20. Use according to claim 17 in an agent in amounts of 30 to 85 percent by weight, in combination with 5 to 25 percent by weight of an emulsifier _: and at least one compound from the group consisting of dye, fragrance, preservative, viscosity adjusting agent, liquid carrier medium. 21. Use according to claim 17 in a composition in amounts of 2 to 10 percent by weight, in combination with 0.5 to 15 percent by weight of acids from the group comprising amidosulfonic acid, urea compounds orthophosphoric acid, boric acid, oxalic acid *, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, Gluconic acid, formic acid, acetic acid and propionic acid as well as benzene, toluene or xylene sulfonic acid, sulfoacetic acid or sulfobenzoic acids, preferably glycolic acid or citric acid or acidic alkali salts of the acids of this group, The remainder is the liquid carrier medium and the usual auxiliaries and additives for laundry aftertreatment agents. 22. Use according to claim 17 in tumbler aids, consisting of a flexible sheet-like structure as a carrier for the connections according to claims 1 to 16, wherein the textile sheet-like structures in addition to these compounds, they may optionally contain additives and auxiliaries. / 22 1-30063 / 01 55 Patent application η £ 158 - 22 ^ CT HENKEL KGaA " * ' ZR-FE / patents 23. Use according to claim 17 in laundry detergents and auxiliary washing agents in Amounts of 2 to 15 percent by weight of compounds according to the Claims 1 to 16 for the simultaneous washing and care of textiles. 130063/0155 ORIGINAL INSPECTED