Greener Detergents Improvements Possible?

Dr. Hermann Sicius Dr. Thomas Klein Dr. Ralf-Johann Moritz LANXESS Deutschland GmbH

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Introduction:

Detergent ingredients - Changes over time Biodegradable ingredients : Polycarboxylates e.g. polyaspartate Complexing agents e.g. iminodisuccinate Summary and Outlook

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Detergent ingredients and their functions:

Product type Surfactants Builders Bleaching agents Enzymes Others

Function removal of soil from fabrics reduction of water hardness; support of the cleaning effects oxidation of dyes and pigments degradation of protein, starch and fatcontaining soil particles optical brighteners, fragrances, stabilisers (complexing agents) corrosion inhibitors etc.
* typical heavy-duty detergent see : G. Wagner: Waschmittel, Wiley, VCH, 2005

% by weight * approx. 21 approx. 57 max. 18 approx. 1

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Powder detergents - Changes over the course of time: Focus on surfactants

Ingredients / % by weight 1907 1953 1959 1964 1983 2004 Surfactants Soap 32 44 3,5 3 1 Tetrapropylene benzene sulfonate (TPS) 13 Fatty alkohol sulfates (FAS) 2 Linear alkyl benzene sulfonate (LAS) 14 8 12 Nonionic surfactants 2,5 3 3 Builders (softeners) / complexing agents Soda ash 24 12 20 Sodium diphosphate 10 23 Sodium-tripolyphosphate (STPP) 43 24 Pentasodium triphosphate Zeolite A 18 22 Polycarboxylate 1 3 Phosphonate 0,2 0,5 Bleaching agents Sodium perborate or sodium percarbonate 9 6 7 16 22 141 TAED (bleach activator) 1,5 2,5 Enzymes + + see : G. / Wagner: Others water Waschmittel, Wiley-VCH, 2005 to 100 to 100 to 100 to 100 to 100 to 100
1

Sodium percarbonate + = contained

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Powder detergents - Changes over the course of time: Focus on builders and complexing agents
Ingredients / % by weight 1907 1953 1959 1964 1983 2004 Surfactants Soap 32 44 3,5 3 1 Tetrapropylene benzene sulfonate (TPS) 13 Fatty alkohol sulfates (FAS) 2 Linear alkyl benzene sulfonate (LAS) 14 8 12 Nonionic surfactants 2,5 3 3 Builders (softeners) / complexing agents Soda ash 24 12 20 Sodium diphosphate 10 23 Sodium-tripolyphosphate (STPP) 43 24 Pentasodium triphosphate Zeolite A 18 22 Polycarboxylate 1 3 Phosphonate 0,2 0,5 Bleaching agents Sodium perborate or sodium percarbonate 9 6 7 16 22 141 TAED (bleach activator) 1,5 2,5 1 sodium Enzymes + percarbonate + see : G. / Wagner: Others water Waschmittel, Wiley-VCH, 2005 to 100 to 100 to 100 to 100 100 to 100 + =to contained
1 1

Sodium percarbonate + = contained

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Builder*/Cobuilder Systems Replace Triphosphate:

Builder Builder*

Cobuilder Cobuilder
COO COO COO COO

Acrylic acid - homopolymer

-

COO COO COO COO COO COO

Zeolite A

COO

COO

Acrylic / maleic acid copolymer

* in the narrower sense (ion exchanger)

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Ingredients in detergents and cleaners: Consumption in Germany (2003)

Product producttype type

Anionic surfactants Zeolites Polycarboxylates Sodium citrate Phosphonates

Total consumption total consumption [t]

102,300 95,300 12,400 14,100 2,900

in detergents [t]
77,100 95,100 10,900 12,000 2,500

Source: Industrieverband Krperpflege und Waschmittel (IKW), Qquoted from: G. Wagner: Waschmittel, Wiley, VCH, 2005

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Polypeptides: An Active Principle of Nature

High content of aspartic acid

Polypeptides

Polyanionic

Control of

biomineralization

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Sodium Polyaspartate: A Polypeptide Based on Aspartic Acid Units

Idealized structure Peptide bond
OH N H O O O OH O n
n dependent on the synthesis route - and -link polydisperse

O O O OH O H N OH N H O OH O N H O OH OH

H N
2

H N

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Sodium Polyaspartate: Convergent Ways Of Synthesis

O OH OH H2O O

O NH3 OH O H2N O O- NH4+ OH H+ H2N

O OH OH O -H2O

HO

O NaOH N

O O O O OH OH O NH3

O NH2 OH O

-H2O

hydrolysis

Sodium polyaspartate

H2O O O NH4+ OH O -H2O

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Sodium Polyaspartate: Biodegradation

Modified OECD test 301 B

70 60 CO2 dev. [%] 50 40 30 20 10 0 0 5 10 15 Days [d] 20 25 30

Glucose Polyaspartate Polyacrylate

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Sodium Polyaspartate: Stability to Hydrolysis

Stability of a solution containing 1 % polyaspartate in water 100 at 95 C

80 60 40 1 12 24 1 2 4 5 6 8
pH
polyaspartate [%]

time [h]

20 0 10 12 13 14

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Sodium Polyaspartate: Stability to Enzymes

40 30
% by weight

Stability of a polyaspartate solution treated with protease for detergents

20 10 0

38.5

38.6

38.4
Aspartic acid, monomer Polyaspartate

at the beginning

6 weeks

26 weeks

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Results of Washing Trials Made By Using Sodium Polyaspartate: Primary Detergency

Standardized test for the cleaning efficiency of heavy-duty detergents

Remission* [%] Remission* [%] Standard polymer Baypure DS100

Fat Bleachable Fett/Pigmentepigments Bleichmittel75.0 73.0 85.8 84.4

Cosmetic Kosmetika stains 79.5 78.7

Enzymatic Enzymsoil ptl. 79.0 78.0

coloration (gray) of different fibers (25 washing * Degree Gemittelte of Remissionswerte der gewaschenen Gewebestcke unter Normlicht * average remission values of the textile under standard light conditions
Standard polymer Baypure DS100 WFK 1.1 1.7 OG-FT 0.7 0.2 OM-B 0.9 1.4

cycles)
average 0.8 0.7

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Results of Washing Trials With Sodium Polyaspartate: Secondary Detergency

90 85 reflectance (%) 80 75 70 65 60 cotton polyester/cotton unwashed polyacrylate Baypure DS100
Graying effect based on tests for heavy-duty detergents

Conditions: 260 mg/l total hardness (as CaCO3), 60 C, 3 kg of textiles, 15 washing cycles Dosage: 75 g of detergent formulation, powder containing 4.5 % of graying inhibitor

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Trend Towards Liquid Detergent Formulations:

Share of market volume [%]

Heavy-duty detergent Liquid detergent

Tablets Compact heavy-duty detergents

Market volume 2003 (Western Europe): 7.1 billion euros Source: P. Krings, Henkel KGaA, 2005

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Conventional Complexing Agents by Comparison :

400
Calcium binding capacity [mg CaCO 3 /g Na-Salt ]

350 300 250 200 150 100 50 0

Na-citrate EDTA Na-salt NTA Na-salt

Calcium binding capacity at pH 11 and 23 C

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Main Ingredients*: Separate Liquid Water Softener

Function Builder Dispersing agent

Ingredients citrate polyacrylate

Weight in % 10 - 20 5 - 10

* Other ingredients: suspending and binding agent, thickener

Potential for optimization of water softeners : Citrate performance Polyacrylate ecology

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Baypure Products: Builder and Complexing Agent

Baypure DSP
Polysuccinimide

, NH3
O O

NaOH

NaOH, NH3

Baypure DS100
Polyaspartic acid sodium salt

Baypure CX100
Tetrasodium iminodisuccinate

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Iminodisuccinate: A biodegradable complexing agent

O O

C-term polyaspartate

O Na N H O O O Na N O Na O O Na

O O O
H 2O

O OH OH O
C8H7NO8Na4 337.1g/mol

O
NaOH NH 3

Na O Na O O

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Iminodisuccinate: Various Calcium Binding Capacities

400
Calcium binding capacity [mg CaCO 3 /g Na-Salt ]

350 300 250 200 150 100 50 0

Na-citrate IDS Na-salt EDTA Na-salt NTA Na-salt

Conditions : pH 11 and 23 C

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Softening Effect Under Practical Conditions:

50 40

13.8 g Baypure DS 100/40% 25.0 g Baypure CX 100/34% 2.4 g citric acid monohydrate 1.6 g CMC

Inhibition [%]

30 20 10 0 0 1 2 3 4 5 6 7 8 9 10

Brand product

Liquid softener under NACE test conditions: comparison of a polyacrylate/citrate formulation (red, brand product) with a polyaspartate/iminodisuccinate formulation (yellow)

Inhibitor [ppm]

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Iminodisuccinate As A Bleach Stabilizer:

6,6 6,5 6,4 H2O2 [%] 6,3 6,2 without complexing agent 6,1 6,0 5,9 0 2 4 6 8 Period of storage [d] 10 with Baypure CX 100 with phosphonate Example: peroxide-containing liquid detergent

Stabilization of H2O2 at 40 C and pH 4.5

2 % complexing agent (as is)

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Summary

Washing processes have potential for ecological and functional optimization by using biodegradable builders and complexing agents.
The following proposals for substitution are made: Polyacrylate to be replaced by Polyaspartate Citrate to be replaced by Iminodisuccinate Phosphonate to be replaced by Iminodisuccinate

Baypure is a registered trademark of Bayer AG, Leverkusen, Germany

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