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
10
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
11
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
14
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
16
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).
19
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
20
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
21
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
23
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
25
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!
26
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
28
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
29
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
30
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:
32
Production of powder detergents
33
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
34
Production of powder detergents
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