Chemical Technology of

Organic Materials II

Univ.-Prof. Dipl.-Ing. Dr. Christian Paulik

SS 2011

Detergent ingredients
1. Surfactants
2. Builders
3. Bleaches
4. Further ingredients

Detergent ingredients
Detergents for household and institutional use are complex
formulations containing up to more than 25 different ingredients
Each individual component of a detergent has its own very specific
functions in the washing process

Surfactants
Most important group of detergent components
Surfactants are water-soluble surface-active agents
Hydrophobic portion
(usually a long alkyl chain)
Hydrophilic or solubility enhancing
functional groups

Surfactants
4 classes:
Depending on what charge is present in the chain-carrying portion of
the molecule after dissociation in aqueous solution:
1. Anionic surfactants
2. Nonionic surfactants
3. Cationic surfactants
4. Amphoteric surfactants

Surfactants
1. Anionic surfactants
R-SO3-Na+ "

"

"Alkylsulfonates

2. Nonionic surfactants:
RO-(CH2-CH2-O)nH

"

"Alkyl

poly(ethylene glycol) ethers

3. Cationic surfactants
"R

H3C

CH3

Cl

"

"

"Dialkyldimethylammonium chlorides

4. Amphoteric surfactants
R

CH3
H2
N C

"

CH3

"

"

"Betaines

Surfactants
Surfactants with little branching in their alkyl chains generally
show a good cleaning effect but relatively poor wetting
characteristics
More highly branched surfactants are good wetting agents but
have unsatisfactory detergency performance

Surfactants
The principal criteria for judging surfactant suitability are:
Performance
Toxicological and
Ecological characteristics

Despite the wide choice of possibilities only few surfactants account

for the major share of the market

Surfactants
Anionic surfactants are the most common ingredients in detergents
designed for laundry, dishwashing, and general cleansing
Nonionic surfactants such as alcohol ethoxylates have acquired
great importance during the last decades
Cationic surfactant use is largely restricted to fabric softeners
because of the fundamental incompatibility of these materials with
anionic surfactants and their poor cleaning efficiency
Amphoteric surfactants still lack a significant place in the market

Anionic surfactants
Alkylbenzenesulfonates (LAS and TPS):

Until the mid-1960s, this largest class of synthetic surfactants was most
prominently represented by tetrapropylenebenzenesulfonate (TPS)

Linear alkylbenzenesulfonates (LAS)

n + m = 7-10
High foaming ability

SO3Na
H2
H3C C
n

H2
C CH3
m

LAS are sensitive to water hardness

SO3Na

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Anionic surfactants
Secondary Alkanesulfonates (SAS):

Sodium alkanesulfonates are specialty anionic surfactants for consumer

products

SAS feature high solubil- ity, fast wetting properties, chemical stability
to alkali, acids, and strong oxidants including chlorine

Sodium alkanesulfonates are produced by photochemical sulfoxidation or

sulfochlorination of C12C18 paraffins
R2
R1

SO3Na

R1 + R2 = C11-17

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Anionic surfactants
-Olefinsulfonates (AOS):

AOS are produced commercially starting from -olefins

AOS show little sensitivity to water hardness

Alkenesulfonates: R1CH2CH=CH(CH2)nSO3Na
Hydroxyalkanesulfonates:

SO3Na
CH2

R2

R1 = C8C12

OH

R2 = C7C13
n, m = 1, 2, 3

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Anionic surfactants
Alkyl Sulfates (AS):

Alkyl sulfates are produced either from natural fatty alcohols derived
from palm oil, palm kernel oil, or coconut oil, or from oxo alcohols, i.e., of
petrochemical origin

They are characterized by desirable detergency properties

Application not only in specialty products, but also in heavy-duty

detergents
R

SO3Na

R = C11-17

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Anionic surfactants
Alkyl Ether Sulfates (AESs):

Alcohol ether sulfates, are obtained by ethoxylation and subsequent

sulfation of alcohols derived from natural feedstocks or of synthetic
alcohols

The optimal carbon chain length has been established to be C12-14 with ca.
2 mol of ethylene oxide

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Anionic surfactants
Alkyl Ether Sulfates (AESs):
Unique characteristics relative to alkyl sulfates:

Low sensitivity to water hardness

High solubility

Good storage stability at low temperature in liquid formulations

AESs are preferred constituents of

Detergents for delicate or wool washables

As well as foam baths, hair shampoos, and manual dishwashing agents

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Anionic surfactants
Alkyl Ether Sulfates (AESs):
Unique characteristics relative to alkyl sulfates:

Low sensitivity to water hardness

High solubility

Good storage stability at low temperature in liquid formulations

AESs are preferred constituents of

Detergents for delicate or wool washables

As well as foam baths, hair shampoos, and manual dishwashing agents

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Surfactants
1. Anionic surfactants
R-SO3-Na+ "

"

"Alkylsulfonates

2. Nonionic surfactants:
RO-(CH2-CH2-O)nH

"

"Alkyl

poly(ethylene glycol) ethers

3. Cationic surfactants
"R

H3C

CH3

Cl

"

"

"Dialkyldimethylammonium chlorides

4. Amphoteric surfactants
R

CH3
H2
N C

"

CH3

"

"

"Betaines

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Detergent ingredients
1. Surfactants
2. Builders
3. Bleaches
4. Further ingredients

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Builders

Detergent builders play a central role

Their function is largely that of supporting detergent action and of water

softening, i.e., eliminating Ca and Mg ions, which arise from the water and
from soil

The category of builders is comprised of several types of materials:

Specific precipitating alkaline materials such as sodium carbonate and sodium
silicate
Complexing agents like sodium triphosphate or nitrilotriacetic acid (NTA)
Ion exchangers, such as water-soluble polycarboxylic acids and zeolites (e.g.,
zeolite A).

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Builders
Complexing agents:

Temperature and complexing agent concentration are generally the

decisive factors in successful elimination of polyvalent metal ions

The resulting complexes are chelates

Sodium triphosphate forms a stable water-soluble complex with calcium

when their stoichiometric ratio is 1:1

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Builders
Complexing agents:

When a substoichiometric quantity of sodium triphosphate is present, the

water-insoluble di-calcium triphosphate is formed

Precipitates on textile fibers and washing machine parts

Can be impeded by adding small amounts of hydroxyethanediphosphonate

and/or special polycarboxylates to the detergent formulation

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Builders
Ion exchangers:

Ion ex changers generally have a high binding capacity for calcium but
that this usually decreases with increasing temperature

Among the many known types of sodium aluminum silicates, those with a
regular crystalline form are appropriate for use in the washing process

Zeolite A, manufactured under the name Sasil (sodium aluminum silicate)

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Builders
Calcium binding capacity of selected ion exchangers

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Builders
Builder combinations:
Since the beginning of the 1980s, ternary builder combinations are used:

Zeolite Apolycarboxylatesoda ash

Polycarboxylatespolyacrylate and poly(acrylate-co-maleinate) have

out-standing function

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Bleaches

The induction of any change toward a lighter shade in the color of an

object

Bleaching effects can occur through mechanical, physical, and/or chemical

means, specifically through change or removal of dyes and soil adhering to
the bleached object

Only oxidative bleaches are used in laundry products to a great extent:

peroxide bleaching and hypochlorite bleaching

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Bleaches

The dominant bleaches in Europe and many other regions of the world are
of the peroxide variety

The most frequently encountered source is sodium perborate (sodium

peroxoborate tetrahydrate, NaBO3.4 H2O)

Bleachable soils consist of a broad spectrum of diverse materials!

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Bleaches

Vegetable origin: contain primarily polyphenolic compounds

anthocyanin dyes derived from, e.g., cherries, blueberries, and currants,
and curcuma dyes from curry and mustard

The brown tannins found in, e.g., fruit, tea, and wine stains arise from
condensation of polyphenols with proteins

Other brown organic polymers include acids present, for example, in

coffee, tea, and cocoa

The green dye chlorophyll and the red betanin from beets are pyrrole
derivatives

Blood is also a bleachable soil, but its removal can sometimes present
problems
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Further ingredients

Surfactants, builders, and bleaches are quantitatively the major

components of modern detergents

The auxiliary "agents are introduced only in small amounts, each to

accomplish its own specific purpose

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Further ingredients

Enzymes

Soil anti-redeposition agents, soil repellent/soil release agents

Foam regulators

Corrosion inhibitors

Fluorescent whiteners

Dye transfer inhibitors

Fragrances

Dyes

Fillers and formulation aids

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Further ingredients
Enzymes:

Stains derived from sources such as milk, cocoa, blood, egg yolk, and grass
are resistant to removal from fibers by enzyme-free detergents,
particularly when stains have dried-on

The effectiveness of detergent enzymes is based on enzymatic hydrolysis

of peptide, glucosidic, or ester linkages, respectively

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Further ingredients
Fluorescent whiteners:

Properly washed and bleached white laundry, even when clean, actually
has a slight yellowish tinge

For this reason, as early as the middle of the 19th century, people began
treating laundry with a trace of blue dye

Modern detergents contain fluorescent whitening agents

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Further ingredients
Fluorescent whiteners:

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Production of powder detergents

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Production of powder detergents

Spraying tower:

Traditional manufacturing process comprising slurry drying of most

detergent components in a spray tower

And postaddition of temperature-sensitive components by an additional

densifying step

Process of mixing of compounds:

In this process each raw material or part of it is separately agglomerated

to dense particles

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Production of powder detergents

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