DE2161554A1 - DETERGENT AND CLEANING AGENTS, CONTAINS A PHOSPHORUS-FREE SCALE SUBSTANCE - Google Patents

Description

Washing and cleaning agents containing a phosphorus-free carburetor substance

The invention relates to detergents and cleaning agents, the usual detergents and additives and a phosphorus' contain free structural substance.

It is known that the cleaning power of surfactants in Detergents and cleaning agents through the addition of certain substances is increased. Such substances are referred to as structural substances, building blocks or builders.

The mode of action of such structural substances is so far, not yet fully clarified in detail. It is generally believed, however, that a variety of individual effects will affect you determine the special properties of the structural substances:

Increasing the washing power of surfactants, dispersing dirt to avoid redeposition,

Solubilization or emulsification of poorly soluble components,

Prevention of the separation of sparingly soluble salts, especially calcium and magnesium salts, Buffer effect against acidic substances, regulation of the foaming power of the wash liquor,

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Compatibility with the other detergent components, especially with the bleaching agents, low corrosion effect.

The good biolocjj / see may also be an important property Degradability cannot be ignored.

So far, d.io. are particularly known as structural substances inorganic, alfoil acting substances:

) Alkali bicarbonates, carbonates, borates, phosphates, polyphosphates and silicates.

In the most common detergents and cleaning agents But almost exclusively polyphosphates, in particular pentanate triurn triphosphate, are present as structural substances, used. The polyphosphate content of detergents and cleaning agents is based on washing habits of the individual countries, up to 70 percent by weight, based on the total mixture. Despite many advantages however, the use of phosphates also has serious disadvantages.

For some years now, limnologists have been observing more and more Concern about eutrophication, i.e. overfertilization of water bodies and lakes due to excessive concentration Nutrients that lead to a sensitive disturbance of the biological equilibrium as a result of strong algae growth led. The result is a rapid decrease in the oxygen content, primarily in the depths of the lakes and one with it associated increase in putrefaction processes, which ultimately cause the death of plant and animal life. The detergents are partly used for this damage

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phosphate blamed / Tenside £ 3 '(2) ", 82 (19712 /.

It is also known that polyphosphates are also mixed with arm endings Show disadvantages. So they easily failed to hydrolyze with the formation of meta- and orthophosphates represent inferior equipment substances.

The corrosive properties of polyphosphates in relation to metals and alloys must also be mentioned remain (K. Lindner, Tenside-Textilhilfsrnittel-Waschrohstoffe, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart 1964, Volume II, pages 1189 and 1195).

In order to circumvent the stated disadvantages of the polyphosphates, many attempts have already been made to use phosphate-free cooking substances to be used in detergents and cleaning agents. In the USA, for example, nitrilotriacetate (NTA) was used in detergent formulations used. However, it has now been recognized as a disadvantage that the NTA is not under all conditions is readily biodegradable. Furthermore, the nitrogen interferes with a factor promoting eutrophication. Dubious the excellent complex-forming ability is also correct against mercury and arsenic, which can lead to an undesirable accumulation of these substances. Finally it was found that NTA and perborate mutually inactivate one another, with consumption of the perborate NTA is degraded with the formation of amine oxides and other oxidation products (Tenside .8 (1), 2 (1971)).

The invention was therefore based on the object of overcoming these disadvantages of the relevant prior art.

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The detergents according to the invention are characterized by a content of water-soluble salts of sulfonic acid groups containing polybutadiene, the molecular weights of the underlying polymers 500 to 10,000, preferably 1,500 to 3,500 as a structural substance.

The degree of substitution of the sulfonated polybutadiene is 0.17 to 1.0, preferably 0.22 to 0.7, especially 0.33 to 0.5.

The compounds to be used according to the invention can be prepared by methods known per se.

The polybutadienes with average molecular weights of 500 to 10,000 can be prepared, for example, by polymerization in inert organic diluents in the presence of alkyl aluminum halide and compounds of nickel such as nickel acetylacetonate. It can be advantageous to add electron donors such as ethers or amines in small amounts (B. Schleimer and H. Weber, Angew. Makromol. Chemie 16/17 , 253-269 (1971)).

"The polybutadienes produced in this way contain 30 to 90 %, preferably 50 to 85 % 1,4-cis double bonds, 65 to 10 %, preferably 50 to 15 % 1,4-trans double bonds and 5 to 0 %, preferably less than 1 % vinyl double bonds.

The sulfonates according to the invention are prepared by sulfonation with SO ₃ , which is used with advantage in the form of a complex, for example an etherate such as SQ ₃ -dioxane. One lets the liquid polymer, expediently

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wise dissolved in an organic solvent (possibly also dissolved in the solvent from the production process) with 1.0 to 1.5 mol, preferably 1.25 mol per basic mole (= monomer unit) of the polybutadiene, of S0_ or S0 ₃ ~ complex, react at temperatures of 25 to 30 C, followed by neutralization with alkali. After working up, the main builders according to the invention are the alkali metal salts of sulfonated polybutadiene, optionally in a mixture with alkali metal sulfate, which in general does not have to be separated off.

The sulfonation of polybutadiene is explained using the following example:

60 g of polybutadiene with a molecular weight of 1,500 and a content of 75% 1,4-CiS, 24 % 1,4-trans double bonds and less than 1 % vinyl double bonds (1.11 mol monomer unit) are in 1,000 ml Dissolved cyclohexane and at 25 to 30 ⁰ C within 15 to 20 minutes in portions with a suspension of an SO ^ -dioxane complex (1.25 mol) in methylene chloride. The mixture is then allowed to react for a further 10 minutes, the acid is filtered off with suction, washed with ethanol and neutralized with an aqueous solution of 42 g of sodium hydroxide while cooling. The sulfonate solution is brightened at 70 ⁰ C with 75 ml of 30% hydrogen peroxide and heated for 10 minutes under a reflux condenser to boiling. After removing the water by means of a rotary evaporator, 161 g of polybutadiene sulfonate with a content of 13 % sodium sulfate are obtained. The degree of substitution of the sulfonated polybutadiene is 0.42. ·

Although every water-soluble sulfonate of the polybutadienes with molecular weights from 500 to 10 000 as the structural substance

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can be used, the alkali salts are particularly preferred.

The structural substances according to the invention should be in an amount of 10 to 70 percent by weight, preferably 20 to 60, in particular 35 to 60% by weight, based on the total mixture of the detergent and cleaning agent. The ratio of structural substance to surfactant is included generally 1: 3 to 10 s 1.- They can also be used in combination with other builders or replace some of the phosphates in detergents, but are preferably used as the only structural substance.

The washing-active substances and additives are added in the usual proportions,

for example;

O/

Washing active substance 5 to 30 γ _ο

Sodium perborate 0 to 20%

Sodium sulfite 0 to 40 %

Soda 0 to 20%

Silicates. 0 to 15 %.

The what ': h ~ and cleaning agents according to the invention can contain all common anionic and nonionic detergents and additives.

The following are examples of anion-active detergents:

Alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, Alkyl sulfates, alcohol oxyethylate sulfates, etc.

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Examples of non-ionic surfactants include: Alkyl polyglycol ethers, alkylphenol polyglycol ethers, acyl polyglycol ethers, oxethylated fatty acid amides, polyaddition products from ethylene oxide and propylene oxide, etc.

The following relevant recipes for some heavy-duty detergents and mild detergents are intended to provide further explanation serving the invention

Example A: 8.0 % n-dodecylbenzenesulfonate

3.5% palmityl alcohol oxyethylate (15 mol

Ethylene oxide)

4.0 % sebum soap

48.6 % sodium salt of sulfonated polybut

tadiens 1500, produced according to the production example given on page 5

10.7 % sodium sulfate

1.0 % sodium toluenesulfonate 1.0 % carboxymethyl cellulose (CMC) 20.0 % sodium perborate «4 H ₃ O 3.0% sodium silicate
0.2 % optical brightener

Example B: 11.5 % ^ -olefin sulfonate (C ₁₄ -C ₁₈ )

3.0 % sperm oil alcohol oxyethylate (2 5 mol ethylene oxide)

60.0 % sodium salts of sulfonated poly

iDutadiens 1500, manufactured according to the Preparation example given on page 5

5 _f 5 % sodium silicate

1.0 % sodium cumene sulfonate

1.0% carboxy methyl cellulose (CMC)

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17.8 % sodium perborate x 4 0.2 % optical brightener

Example C: 16.0 % ii-dodecylbenzenesulfonate

4.0

C, g-C

Fettal3coho loxäthylat

'16 "^ 1S

(11 moles of ethylene oxide)

2.5 % sebum soap

53.2% of the sulfonated ITatriuiiisalz Polybüta ¹ · 3500 diene, prepared according to Preparation Example is stated on page 5

6.4 % sodium carbonate 0.7 % sodium chloride 1.0 % sodium hydroxide sulfonate 1.0 % carboxymethyl cellulose (CMC) 15.0 % sodium oxyborate 0.2 % optical brightener

4 H ₂ O

Example D:

18.0 % n-dodecyl benzosulfonate

6.8 % palmityl alcohol (15 mol ethy

lelioxid)

3.0 %. Tallow split soap

45.0 % sodium salt of sulfonated polybutadiene 1500, produced according to the production example given on page 5

25.0 % sodium sulfate, 1.0 % carboxymethyl cellulose (CMC), 1.0 % sodium toluene sulfonate O, 2 % optical brightener

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Example E: 16.0 % c-oiefinsulfonate (C _1. -C-- _o )

5.6 % palmityl alcohol oxyethylate (15 mol ethylene oxide.)

3.9 % sebum soap

57.5 % sodium salt of the sulfonated polybutadiene 1500, prepared according to the I-Ierstollungsbeispiel given on page 5

13.0 % sodium sulfate ·. ■ 1.0 % sodium toluene sulfonate 1.8% sodium carbonate 1.0 % carboxymethyl cellulose (CMC) 0.2 % optical brightener

The washing power of the anion-active and nonionic detergents mentioned is noticeably increased by adding the builder substances according to the invention. In addition, these structural substances help to avoid the excretion of detergent substances as poorly soluble salts, for example calcium salts, so that encrustation of the tissue is prevented. The substances according to the invention are also characterized by a very good suspension capacity (tested on iron oxide), which is a measure of the dirt- carrying capacity , very good compatibility with perborate bleaches and a comparatively low corrosive effect on metals.

The framework substances to be used according to the invention can So in the detergents and cleaning agents the phosphates previously mainly used as structural substances, In particular, not only replace pentasodium triphosphate, but even show it against it

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an overall better property profile.

In order to determine the washing power of detergents in which the phosphate content has been replaced by the cxndurigsgeraßen structural substances, test-soiled WFK cotton fabric is placed in a Launder-O-Hater, a standardized laboratory washing machine, at SO ⁰ C Washed for 30 minutes in aqueous liquor. For the washing tests, drinking water with a hardness of 12 ° German hardness is used. By comparison with ■ the test-soiled unwashed and the non-soiled fabric, the percentage wash value is calculated according to the following equation:

% Washing value = ~ · ~ Ξ ~] ~ * 100

Therein mean:

a = remission of the washed fabric b = remission of the test soiled fabric c = remission of the unpolluted tissue.

The remission is a measure of that achieved through the washing process conditional lightening and is dried and ironed-P ten tissue using an Elrephc photometer from the company Zeiss measured, whose filter B 5 "is calibrated against the standard no. 20707". For the tuning of the percentage The washing value is based on 24 individual measurements on the test fabrics.

To further explain the subject matter of the invention and the achievable technical progress the following examples and test results are used:

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^ Example e 1 to 3

The following table shows the percentage Vfaseh values applied with 1 g / l sodium dodecyl benzenesulfonate as a detergent substance (WAS) and 1 or g / l scaffolding in the wash liquor was achieved

example

Wasehgang L ·. 45 39 .48 42 46 35

g / l pentasodium triphosphate

(for comparison)

g / l pentasodium triphosphate

(for comparison)

g / l Na-Sa3 ζ of the sulfonated poly

butadiene (molecular weight 1500), produced analogously to the one on page 5 entered manufacturing " example

g / l ^ a salt of the sulfonated poly 27 43

biitadiens (molecular weight 1500), Manufactured analogously to the manufacturing example given on page 5

g / l Na salt of sulfonated poly-12 32

butadions (molecular weight: -3-500hr— ■ herger; iel3-t analogous to your on page 5 specified Hers'toi l * boa sp.i el

cj / 1 Na-SaIκ dos sulfonated poly- 17 37

butadions (molecular weight 3500), prepared analogously to the one on page Li i; specified

B ice piele 4 am 6

To determine the hardness resistance is verfanren in such a way that solutions of different concentrations of

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Sodium dodecylbenzenesulfonate and builder in water with different degrees of hardness can be examined for their cloudiness. Obtained from a series of measurements Then the total value, which can be between 15 with poor and 75 with very good hardness resistance. To Using a certain key, the stability numbers, which vary between 1 and 5, can be determined from this. In the ideal case, the greatest insensitivity to the hardness components of the water, this value is 5. Further details can be found in DIN regulation 53 905. As can be seen from the following compilation, show the builder substances according to the invention in conjunction with sodium dodecylbenzenesulfonate clearly have better hardness resistance as Pentanatrxumtrxphosphat.

example

Framework

Pentanatrxumtrxphosphat (for comparison)

Na salt of sulfonated polybutadiene 1500, production see page 5

Na salt of sulfonated polybutadiene 3500, production see page 5

Hardness resistance according to DIN 53 905

Total stability number worth

3 37

57

63

In all other examples, builders according to the invention were used used, which were shown analogously to the production example on page 5.

Examples 7 to 9

The compatibility of the builder substances according to the invention with the other detergent components became special

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for sodium perborate, which is often used as a bleaching agent. The perborate stability was determined in such a way that first the active oxygen content of a solution of 0.004 mol / l perborate in distilled water without the addition of foreign substances was determined iodometrically and set equal to 100 % . A solution which contained 0.004 mol / l perborate and 0.004 mol / l builder and 10 mg / l iron (III) chloride was then heated to 90 ° and the decrease in active oxygen content was measured after 30, 60 and 150 minutes. The values obtained were put in relation to the comparison solution they indicate the increased stabilizing effect of the builder substances according to the invention compared to perborate compared to phosphate.

15, 5 4.5 55, Ό 36.0 57, 5 43.0-

. , Structural substance% active oxygen according to game

30 min 60 min 150 min

7 Pentanatrxumtriphphsphat 29.0 (for comparison)

8 I'.a salt of sulfonated 66.0 Polybutadiene 1500

9 Nc salts of the sulfonated 65.0 polybutadiene 3500

Examples 10 to 12

As a measure of the dirt-carrying capacity of a structural substance their ability to suspend, e.g. towards powdered iron oxide, can be viewed. A test method was used for this worked out, which consists in the fact that red AK F iron oxide pigment with a shaking cylinder an aqueous solution of the builder with the addition of sodium dodecylbenzenesulfonate intense for a minute

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shakes and after 24 hours the strength of the then still closes observed turbidity determined photometrically. Give the relative numbers obtained by measuring the absorbance the suspending capacity of the structural substances, with values from 100 being good.

Example of the structural substance, extinction in 1 cm

Layer thickness

10. Pentasodium triphosphate 160

(for comparison)

11 Na salt of sulfonated 211 polybutadiene 1500

12 Na salt of sulfonated 129 polybutadiene 3500

Examples 13-15

The following procedure was used to determine the corrosive properties of the structural substances according to the invention in relation to steel: Degreased steel sheets made of St 37 were placed in a glass flask with a reflux condenser in such a way that they were half immersed in a 5% aqueous solution of the structural substances adjusted to pH 10 immerse. The solution was alternately refluxed for 8 hours and left at room temperature for 16 hours. When the apparatus was switched off, air could get to the test panels. After a test duration of 8 days, the adhering rust was removed by treatment with 2N hydrochloric acid which still contained 0.25% lauryldimethylbenzylammonium chloride for 30 minutes. The sensing plates were then washed with water, acetone and benzene and dried. The total weight loss of the sheets during the treatment, that of the

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corresponds to the amount of iron removed, was determined. Pentasodium triphosphate shows - as shown in the following compilation evident - the strongest corrosive effect compared to the structural substances according to the invention.

Example of framework substance removal in g / m

13 Pentasodium triphosphate 61.4 (for comparison)

14 Na salt of sulfonated poly-22.1 butadiene 1500

15 Na salt of sulfonated poly-23.8 butadiene 3500

Based on the examples and comparative examples mentioned, M.e showed that high-quality detergents and cleaning agents through the use of the structural substances according to the invention can be obtained.

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Claims (9)

O.Z. 2 8.Ϊ2.1971 Godfather ta nsprüche ■. (I. Detergents and cleaning agents, containing common detergents and additives and a phosphorus-free builder substance characterized by a content of water-soluble salts of polybutadienes containing sulfonic acid groups, the molecular weights the underlying polymers are 500 to 10,000, as structural substances * 2. Washing and cleaning agent according to claim 1, · characterized in that the molecular weights of the underlying polymers 1,500 to 3,500. 3. washing and cleaning agent according to claim 1 and 2, thereby ge k e η η ζ e i c h η e t that the water-soluble salts of sulfonated polybutadienes Are alkali salts. 4. washing and cleaning agents according to claim 1 to 3, k characterized by a content of water-soluble salts sulfonic acid groups containing polybutadienes with a degree of substitution from 0.3 7 to 1.0, preferably 0.22 to 0.7, per monomer unit. . - 5. washing and cleaning agents according to claim 1 to 4, marked by a content of 10 to 70 percent by weight, preferably 20 to 60, in particular 30 to 60 percent by weight, based on the total amount of the detergent and cleaning agent of the water-soluble salts ripening to sulfonic acid groups contains? cr polybutadienes. 3Ü982Ö / 0943 O.Z. 2599 December 8, 1971 6. detergent and cleaning agent according to claim 1 to 4, characterized in that no other structural substances are present. 7. Use of mixtures prepared by adding polybutadienes with molecular weights of 500 to 10000.0 / preferably 1500 to 3500, and 1.0 to 1.5 mol of SO ₃ , based on the monomer unit of the polybutadiene, at temperatures of 25 to 30 ^{Allow 0} C to act on one another, neutralized with alkali and worked up in the customary manner, preferably without separating off the alkali metal sulfate obtained, as a phosphorus-free structural substance in detergents and cleaning agents. 8. Use of mixtures made by adding polybutadienes with molecular weights of 500 to 10,000, preferably 1,500 to 3,500, with 1.0 to 1.5 mol, preferably 1.25 moles of a dioxane-sulfur trioxide complex at room temperature reacted, neutralized with alkali and worked up in the usual way, as a phosphorus-free structural substance in detergents and cleaning agents. 9. Use of mixture according to claim 7, characterized in that in the case of neutralization as an alkali, sodium or potassium hydroxide is used. ^ 309825/0943