DD251689A3 - MIXTURES OF NONIONOGENIC TENSIDES WITH IMPROVED NETWORK PROPERTIES - Google Patents

Abstract

Mention is made of mixtures of nonionic surfactants having improved wetting properties and improved detergency obtained by mixing oxyalkylation products based on ethylene oxide and / or propylene oxide without further additives. The mixtures are composed of A) from 30 to 90% by weight of an alkoxylation product of a hydrophobic compound and alkylene oxides and B) from 1 to 70% by weight of a mixture of polypropylene glycol ethers and ethoxylated polypropylene glycol ethers or oxopropylated polyethyleneglycol ethers. The new mixtures make it possible to use hitherto unsuitable alkoxylation products of type A and B, for example, as wetting agents and detergents.

Description

Field of application of the invention

The invention relates to mixtures of nonionic surfactants with improved wetting properties and improved wash activity by mixing oxyalkylation products which are useful in many industrial and household sectors, including: a. as washing and wetting agents find application.

DT-AS 1093507 discloses a liquid dishwashing detergent based on mixtures of sparingly soluble mixed ethylene oxide-propylene oxide addition products at rinse temperatures with higher molecular weight compounds containing lipophilic radicals and with solution-promoting ethylene oxide addition products.

The further development DT-AS 1106907 is characterized in that poorly soluble mixed high molecular weight ethylene oxide-propylene oxide Rolymerisationsprodukte be used instead of the mixed ethylene oxide-propylene oxide addition products at rinsing temperatures.

By DT-AS 1 692016 and 1 692017 are detergents from low-foaming wash raw materials from the class of Polyäthylenglykolätherderivate of fatty alcohols, fatty acids and alkylphenols whose Glykoläthergruppen 8 to 20 carbon atoms, and a water-soluble Polyäthylenoxydaddukt of polypropylene glycol, Äthylendiaminopolypropylenglykol and alkylpolypropylene glycol known.

Also known are detergents with low foaming tendency and good cleaning power of water-soluble, surface-active Äthylenoxidaddukaten a polypropylene glycol having a molecular weight of at least 1000, a primary or secondary straight-chain or branched aliphatic alcohol having 8 to 24 carbon atoms or a substituted alkylphenol in combination with a water-insoluble but water-dispersible dialkylphenol-ethylene oxide adduct (DT-AS 1 467637).

The combination of the two components surprisingly leads to the effect that the dialkylphenol-ethylene oxide adduct surface-active, which is dispersible only in water, forms extremely little foam and has a low cleaning power, while maintaining the low foaming property becomes water-soluble, at the same time The cleaning power of the resulting mixture is generally better than the cleaning power of each of the individual components.

Described are also detergents with braked foam, which are characterized by a content of ethylene oxide, propylene oxide and / or ethylene oxide-propylene oxide adducts of higher fatty alcohols (DT-AS 1 617 065).

The known mixtures of nonionic surfactants assume that the good properties of individual surface-active adducts are combined with one another, ie. in itself suitable as washing raw materials adducts by specific combinations, z.T. in the presence of builders or other additives, to further improve certain properties (e.g., DT-OS 1467638).

This applies to the mixtures of nonionic with anionic surfactants as well as the mixtures of nonionic surfactants with each other.

For nonionic surfactants that have poor surface activity, e.g. B. insufficient washing and wetting power, possess, cause the known mixtures of nonionic surfactants no synergistic changes in these properties.

Object of the invention

The object of the invention is to make hitherto unsuitable as wetting agents and detergents alkoxylation products by suitable combination with nonionic surfactants already used in detergents applicable for these applications.

Explanation of the essence of the invention The technical problem which is solved by the invention

The object of the invention is to improve the net and wash properties of combinations of alkoxylation products, preferably of ethylene oxide and / or propylene oxide adducts, without the use of builders or other additives.

Features of the invention

The object is achieved in that

A) from 30 to 99% by weight, preferably from 50 to 80% by weight, of an alkoxylation product of a hydrophobic compound having active hydrogen atoms and alkylene oxides having a total ethylene oxide content of at least 50% by weight

B) 1 to 70 wt%, preferably 20 to 50 wt%, of a mixture of 10 to 90 wt%, preferably 20 to 50 wt%, polypropylene glycol ether and 90 to 10 wt%, preferably 80 to 50 wt. %, ethoxylated Polypropyleneglycoläthem or oxpropylierten Polyäthylenglykoläthem with a Äthylenoxid- or Propylenoxidgehalt to 50Gew .-%, preferably up to 30 wt .-%, combined.

The mixing of components A and B according to the invention surprisingly and unexpectedly synergistically improves the wetting properties and the washing activity of the starting components.

The mixtures according to the invention make it possible, hitherto unsuitable alkoxylation of type A and B for z. B.

Use wetting agents and detergents. It is also possible to further improve suitable properties of type A and B alkoxylation products.

The improvement of the wetting properties and the washing activity is achieved exclusively by mixing the alkoxylation products according to the invention, so that it is possible to dispense with further additives.

For the mixture according to the invention as component A Oxäthylierungsprodukte of C ₈ -C ₂ 4 fatty alcohols, alkylene phenols, C ₈ -C 3 ₂ fatty acids, C ₈ -C ₂ o-fatty amines, Ce-Q ^ -Fettsäureamiden, C ₈ -C ₂ O-fatty acid esters of polyhydric alcohols and Polyalkylenglykolätherderivaten of fatty alcohols, Alkyiphenolen, fatty acids, fatty amines, fatty acid amides, fatty acid esters of polyhydric alcohols used.

Thus, it is well known that alkoxylation products of longer chain fatty alcohols, fatty acids, alkylphenols, fatty acid esters, such as

z. As stearyl alcohol, stearic acid, have little or no net effect. Furthermore, it is known that the alkoxylation of C ₁₂ - to C ₆ fatty alcohols have the greatest detergency, while the Ci ₈ fatty alcohols drops sharply. The same applies to the detergency of the other compounds mentioned above. The same tendency shows the surface tension of oxyethylation products, which increases at the same HLB value as the number of carbon atoms in the hydrophobic group increases.

As component B polypropylene glycol ether are used in admixture with oxyethylated Polypropylenglykoläthem or oxpropylierten Polyäthylenglykoläthem.

In the preparation of component B z. B. in the first stage of compounds such as water, diols, lower Propylenpolyglykoläther, triols, polyols or technical mixtures of such compounds added propylene oxide until a certain molecular weight is reached. In this way, polypropylene glycol ethers which constitute one component of component B are formed.

In a second stage, propylene glycol ether is added to ethylene oxide or to polyethylene glycol ether, propylene oxide, up to a certain percentage, based on the total molecule formed. The ethoxylated polypropylene glycol ether or oxpropylated polyethylene glycol ether is the second constituent of component B.

Technical mixtures, which are well suited as starting components for the preparation of such propylene oxide-ethylene oxide adducts, have the following composition:

Octanediol technical:

45% 2-ethylhexanediol (1.5)

15% hexanediol (1,5)

5% 2-ethylhexanediol (1.3) 20% 1,3-butylene glycol 15% hexanetriol hexanetriol technical: 35% hexanetriol (1,3,5) 15% 2,4-dioxy-3-methylolpentane 20% octanediols 1 -2% butanediol (1,3)

4% cyclic acetals 24-25% octane triols

As a measure of the wetting power of the pure components and their mixtures, the wetting time of a textile fabric in the aqueous solution was determined by the immersion wetting method according to TGL 13663 at a concentration of 3 g / l and a temperature of 25 ° C.

The detergency of the pure components A and B and that of their mixtures was determined by the washing test described below.

Method of checking the washing activity

To test the washing activity, circular sections of a wool filter fabric are provided with a synthetic soil consisting of a mixture of brown coal tar and mineral oil.

D3e soiled fabric sections are washed in a ram washing machine (moving liquor - moving material) for 30 min. At 50-55 ⁰ C and visually determines the degree of washout of the pigment (lignite coal tar) and mineral oil.

Ahschmutzung

A special brown coal tar is dissolved in a ratio of 1:20 in hot benzene. After filtration of the solution, the benzene is distilled off and the residue obtained with 10 times the amount of a machine oil (viscosity of 43.2 ⁰ E at 20 ° C, 6.38 ⁰ E at 5O ⁰ C, flash point 207 ° C, pour point -27 ° C, SZ 1,20mg / KOH / g, VZ 1,54mg KOH / g) at 100 ⁰ C.

The soiling mixture is applied dropwise from a dedicated apparatus on the circular fabric sections (045mm) made of wool filter fabric. (3 drops) Finally, the soiling 3h. fixed at 120-140 ⁰ C in a drying cabinet.

Washing the stain

The laundry is done in a ram washing machine, consisting of 6 washing baskets of 60 mm diameter, in which the soiled fabric is introduced. The washing baskets are moved up and down in the test liquid at a stroke of 55 mm and a frequency of 90 strokes per minute. Washed at a concentration of 3g / l 30 min. At 50-55 ⁰ C.

It is then rinsed cold, dried and visually determined the degree of washout. As a result,% of washed-out pigment,% of washed-out mineral oil based on soiling is indicated.

Executive examples, example 1

Mixtures of an ethoxylated Cn-Cia alkyl dipropylene glycol ether with 15 ethylene oxide units as component A and a component B comprised of 30 weight percent polypropylene glycol of molecular weight 1000 and 70 weight percent of an ethoxylated polypropylene glycol ether of octahediol whose hydrophobic moiety had a molecular weight of 2,000 and its ethylene oxide content was 20% by weight.

The aqueous solutions of the mixtures give lower wetting times than the solutions of the pure mixture components or at least wetting times, which are in the range of the solution of the best wetting mixture constituent.

Table for example 1

Network time of component A = 142S

mixing component Weight share in the network time designation mixture Wt .-% 30 S Component B 50 51 70 43 100 30 30 46 Bölypropylenglykoläther 50 90 70 94 100 over 300 s 30 - äihoxylierter 50 44 Bölypropylenglykoläther 70 45 100 47 41

Example 2

It, mixtures were prepared and tested analogously as in Example 1, but used as a mixture component A an ethoxylated G "-Ci6 alcohol with 16 ethylene oxide units, the aqueous solution gave without addition even good wetting times. By adding component B, mixtures were obtained whose aqueous solutions had shorter wetting times than the solutions of the pure mixture components.

Table for example 2

Network time of component A = 47s

Wetting time of polypropylene glycol = greater than 900 s Wetting time of ethoxylated polypropylene glycol = 42s

Weight proportion of the mixture component B mesh time

Wt .-% s.

30 35

50 34

70 40

Example 3

Mixtures were prepared and tested analogously to Example 1, but ethoxylated lard was used as the mixture component A, whose aqueous solution showed very poor wetting times, greater than 900 s. By adding component B, the mixtures were more improved in their wetting power than by mixing the individual components of component B.

Table for example 3

mixing component Weight fraction% by weight network time designation 100 30 30 30 S Component A Component B Polypropylene glycol ethoxylated polypropylene glycol 900 142 192 160

Example 4

Mixtures were prepared analogously as in Example 1, but using as the component A mixed atgoxylated tallow alcohol (C ₁ BC ₁₈ alcohol) with 15 ethylene oxide units, which had poor washing properties. The aqueous solutions of the component A mixtures with component B exhibited greatly improved detergency, both pigment and oil scavenging, over the mixtures of component A and the individual components of component B.

Table for Example 4

mixing component weight proportion washing activity 60 oil 80 designation Wt .-% pigment 90 % 90 100 % 80 80 Component A 30 Component B 30 80 80 Polypropylene glycol (PPG) <20 <20 athoxylated polypropylene 30 lenglykoläther 100 20 80 PPG Ethoxylated PPG with 100 30wt .-% ethylene oxide

Example S

Mixtures were prepared and tested analogously to Example 4, but using as the component A mixture of athoxylated Cn-Cis-alkyldipropylene glycol ethers containing 15 units of ethylene oxide, the solutions of which exhibited good scavenging power, but whose pigment washing and wetting properties were inadequate.

By the addition of component B, mixtures with improved properties were obtained in comparison to the pure component A as well as to mixtures which were prepared by adding the individual constituents of component B to component A.

Table for example 5

mixing component Gewichtsant. washing activity oil network time designation Wt .-% pigment % 100 % 100 S Component A 30 80 100 188 Component B 30 100 90 47 polypropylene glycol 90 484 ethoxylated poly- 30 90 propylene glycol ether 100 80 20 68 PPG 20 äthoxyliertesPPG 100 80 mit30Gew .-% ethylene oxide 20

Example 6

Mixtures were prepared and tested analogously to Example 4, but the mixing component B and the mixing ratio of component B to component A changed.

The blend component B consisted of 30 wt% of polypropylene glycol of molecular weight 1,500 and 70 wt% of an ethoxylated polypropylene glycol ether of octanediol whose hydrophobic residue had the molecular weight of 2000 and its ethylene oxide content was 30 wt%.

The poor washing activity and the extremely poor wetting power of component A is improved to a much greater extent by mixing with component B than by mixing with the individual constituents of component B.

Table for Example 6

mixing component Gewichtsant. Wt .-% washing activity oil network time designation 100 50 50 50 pigment oo oo co oo ο ο ο ο S Component A Component B Polypropylene glycol ethoxylated polypropyleneglycol ether 60 90 80 70 1790 125 500 140

Example 7

Mixtures were prepared and tested analogously to Example 6, but using as compounding component A an ethoxylated lard polypropylene glycol ether composed of 12.3% by weight of lard, 34.6% by weight of propylene oxide and 53.1% by weight of ethylene oxide.

The extremely poor washing activity and the wetting power of component A is improved to a greater extent by mixing with component B than by mixing with the individual constituents of component B.

Table for example 7

mixing component Gewichtsant. Wt .-% washing activity Oil% network time designation 100 50 50 50 Pigment% 60 80 70 80 S Component A Component B Polypropylene glycol ethoxylated polypropylene glycol ether 30 90 70 30 220 52.1 107.8 72.0

Claims (1)

Mixtures of nonionic surfactants with improved wetting properties and improved washing activity by mixing alkoxylation products, characterized in that A) from 30 to 99% by weight, preferably from 50 to 80% by weight, of an alkoxylation product of a hydrophobic compound having active hydrogen atoms and alkylene oxides having a total ethylene oxide content of at least 50% by weight B) 1 to 70% by weight, preferably 20 to 50% by weight, of a mixture of 10 to 90% by weight, preferably 20 to 50% by weight, polypropylene glycol ether and 90 to 10% by weight, preferably 80 to 50% by weight. %, ethoxylated Polyprqpylenglykoläthern or oxpropylierten Polyäthylenglykoläthern with an ethylene oxide or propylene oxide content up to 50 wt .-%, preferably up to 30 wt .-% be combined.