OVERVIEW OF SYNTHETIC DETERGENTS

AND THEIR CHEMICAL STRUCTURES

Roberto Lava, PhD

ARPA Veneto
ITALY

TAIEX Workshop on Production

Technology and Chemical Analysis
of Synthetic Detergents
Cairo (Egypt) 27-28 February 2017
AGENDA
 OUTLINES

-  Introduction and overview

-  Surfactants and their classification

(anionic, cationic, amphoteric, non-ionic, non-hydrocarbon)

-  Builders, bleaching agents

-  Enzymes, minor components

-  References and further readings

3
 INTRODUCTION I

Regulation (EC) 648/2004 of European Parliament and of the

Council of 31 March 2004 on detergents
DETERGENT (art. 2 648/2004)
“any substance or mixture containing soaps and/or other surfactants intended for
washing and cleaning processes. Detergents may be in any form (liquid, powder,
paste, bar, cake, molded piece, shape, etc.) and marketed for of used in
household or institutional or industrial purposes”.

SYNTHETIC DETERGENT (ASTM)

“a detergent produced by chemical synthesis and comprising
an organic composition other than soap”

SOAP (ASTM D459)

“the product formed by the saponification or neutralisation of fats, oils, waxes,
rosins, or their acids with organic or inorganic bases”
4
 INTRODUCTION II

-  household laundry detergents

- Classification according to the uses
- Mechanisms of action of cleaning components
-  dishwashing products
-  hard surface cleaners
-  leather, fabric cleaning and care
-  car wash and care
-  Industrial and Institutional cleaners
-  cosmetic cleaners (PCP)

- Conditions vary from country to country

EUROPE: approach to sustainability

(biodegradation, environmental protection, toxic and harmful,…)

DETERGENTS REGULATION (EC) n. 648/2004

REACH REGULATION (EC) n. 1907/2006
5 REGULATION (EU) n. 259/2012 on phosphates
 INTRODUCTION II

-  household laundry detergents

- Classification according to the uses
-  dishwashing products
-  hard surface cleaners
-  leather, fabric cleaning and care
-  car wash and care
-  Industrial and Institutional cleaners
-  cosmetic cleaners (PCP)

- Mechanisms of action of cleaning components

- Conditions vary from country to country

EUROPE: approach to sustainability

(biodegradation, environmental protection, toxic and harmful,…)

EU JRC-IPTS
DETERGENTS Report 2012
REGULATION (EC) n. 648/2004
6 REACH67
REGULATION
billion € / (EC)
yearn. 1907/2006
 INTRODUCTION II

-  household laundry detergents

- Classification according to the uses
-  dishwashing products
-  hard surface cleaners
-  leather, fabric cleaning and care
-  car wash and care
-  Industrial and Institutional cleaners
-  cosmetic cleaners (PCP)

- Mechanisms of action of cleaning components

- Conditions vary from country to country

EUROPE: approach to sustainability

(biodegradation, environmental protection, toxic and harmful,…)
EU AISE Report 2015
DETERGENTS REGULATION (EC) n. 648/2004
35,7 billion € / year
7 REACH REGULATION (EC) n. 1907/2006
 INTRODUCTION II

-  household laundry detergents

- Classification according to the uses
-  dishwashing products
-  hard surface cleaners
-  leather, fabric cleaning and care
-  car wash and care
-  Industrial and Institutional cleaners
-  cosmetic cleaners (PCP)

- Mechanisms of action of cleaning components

- Conditions vary from country to country

EUROPE: approach to sustainability

(biodegradation, environmental protection, toxic and harmful,…)

DETERGENTS REGULATION (EC) n. 648/2004

8 REACH REGULATION (EC) n. 1907/2006
 INTRODUCTION III

DETERGENT INDUSTRY
Lately, R&D to develop very complex and sophisticated products to deliver the best
performance for more and more demanding consumers (industry, household, PCP)

Consider economic and socio-economic constrains è BIG COMPETITIVE MARKET

REDUCE COSTS
BEST
HIGH QUALITY
PERFORMANCES
PRODUCTS
EFFECTS ON THE
ENVIRONMENT
MINIMUM
AMOUNT OF
INGREDIENTS
Importance to understand the formulations, the chemistry, identify the components
9 through analyses
 CLASSIFICATION

Main classes of components:

- SURFACTANTS

- BUILDERS

- BLEACHING AGENTS

- ENZYMES

- MINOR COMPONENTS

Detergents as combinations of all of them

Most contains all 4 of them, other only 2 (e.g. window cleaners)
10
 CLASSIFICATION

- SURFACTANTS

- BUILDERS

- BLEACHING AGENTS

- ENZYMES

- MINOR COMPONENTS

Detergents as combinations of all of them

Most contains all 4 of them, other only 2 (e.g. window cleaners)
11
 SURFACTANTS

Contraction of the term SURFace - ACTive - AgeNT

Group of chemicals able to modify interfacial properties of the liquids in which
they are present (LIQUID, aqueous or non-aqueous)

SURFACTANT (art. 2, Reg 648/2004)

“ any organic substance and/or mixture used in detergents, which has
surface-active properties and which consists of one or more hydrophilic and one
or more hydrophobic groups of such a nature and size that is capable of
reducing the surface tension of water, and of forming emulsions and/or
microemulsions and/or micelles, and of adsorption at water-solid interface”.

12
 SURFACTANTS

Contraction of the term SURFace - ACTive - AgeNT

Group of chemicals able to modify interfacial properties of the liquids in which
they are present (LIQUID, aqueous or non-aqueous)
HYDROPHILIC HYDROPHOBIC

NON-IONIC

AMPHIPHILIC ANIONIC

character
CATIONIC

AMPHOTERIC

13
 ANIONIC SURFACTANTS I charge

Hydrophobic part (Lipophilic): mainly hydrocarbons (but also PDMS, PFC)

Hydrophilic part is giving the characteristic and classification

ANIONIC
earliest and most common produced in high volume, especially in the past
INEXPENSIVE
excellent cleaning action to remove soils and dirtiness

Activity higher because (-): most of substrates are (-), while dirtiness (+)
Big action of hindering of deposition

HARD WATER
Disadvantage: sensitive to water hardness in general
NO FOAM

14
 ANIONIC SURFACTANTS II

1. CARBOXYLIC ACIDS AND SALTS

-  CARBOXYLIC ACIDS:
Produced by alkaline hydrolysis of an
animal/vegetable glycerides of
by neutralisation of fatty acids (SOAP)

General: higher carbon chain, lower water solubility

Applications: soap bar/liquid soaps (K+), shaving products, deodorant sticks

-  ESTER CARBOXYLIC ACIDS: monoesters of di-tri carboxylic acids, good

foaming properties (shampoo)

-  ETHER CARBOXYLIC ACIDS: by reaction of sodium chloracetate with

ethoxylated alcohol, good wetting, good foam stability, used as emulsion
stabilizers (toilet bowl, creamy foaming, hair conditioning)
15
 ANIONIC SURFACTANTS II

-  ESTER CARBOXYLIC ACIDS: monoesters of di-tri carboxylic acids, good

foaming properties (shampoo)

-  ETHER CARBOXYLIC ACIDS: by reaction of sodium chloracetate with

ethoxylated alcohol, good wetting, good foam stability, used as emulsion
stabilizers (toilet bowl, creamy foaming, hair conditioning)
16
 ANIONIC SURFACTANTS III

2. SULFURIC AND SULFONIC ACIDS AND SALTS

-  ALKYL SULFATES: organic esters of sulfuric acid, (SLS, sodium lauril sulfate).
properties depending by chain length and degree of branching of HC chain,
good foaming also in hard water, C12-C14 more efficient, most used for years in PCP
because cheap/efficient/versatile (SLS >28% from liquid to gel form), cosmetics
-  ALKYL ETHER SULFATES (AES): industrial uses, household cleaners, fabric care
-  ALKYL SULFONATES: C14-C18, used in heavy duty powder detergents, mostly
paraffine sulfonates in Europe, α-olefins in USA, for PCP
-  ALKYL ARYL SULFONATES: good thermal/chemical stability (LAS, linear
alkylbenzene sulfonates), industrial uses, low compatibly with skin (antiseborrheic)
-  SULFOSUCCINATES, SULFO FATTY ACID ESTERS

S-O bond S-C bond

sulfate ≠ sulfonate
17
 ANIONIC SURFACTANTS IV

3. PHOSPHORIC ACID ESTERS AND SALTS

-  ALKYL PHOSPHATES/ ALKYL ETHER PHOSPHATES: their Na salts are readily
water soluble and not affected by water hardness, useful for extreme cleaning
conditions (pH, heat), acidic cleaning products, industrial uses, pre-treatments of
metal surfaces, antistatic effects (to treat textile and plastics)

4. ACYLAMINO ACIDS AND SALTS

- PCP products, tolerant to hardness

18
 CATIONIC SURFACTANTS I charge

-  When dissociated in water the have a positive charged head

AMPHIPHILIC CATION + ANION (mostly halogen)
-  High substantivity (capacity of a colour to fix better at the structure)
-  Change the surface properties è making hydrophilic surface that behave as
it is hydrophobic and vice versa.
-  bactericide action
-  Higher production of nitrogen derivatives (fatty amine salts and
quaternary ammoniums with one long chain alkyl type
-  more expensive than anionic (cost of production) - 5-6 % total surfactants
-  used in case of no cheap substitute and specific uses: needs of strong
bactericides and sterilizers, antistatic surfaces

19
 CATIONIC SURFACTANTS II

1. ALKYL AMINES
Primary, secondary, tertiary, uncharged in neutral solutions (no strictly cationic)
Long chain of fatty amines. Actually fatty amines are non cationic, but anionic. They
are classified as cationic because at acid pH (most of their uses) their salts are cationic.

Fatty chain is normally linear with even number of C (C10 - C16)

20 Uses in textile treatments, conditioning, softeners, antistatic

 CATIONIC SURFACTANTS III

2. QUATERNARY AMMONIUM COMPOUNDS

in this case always (+) charge, no influenced by pH,
laundries uses, softening, strong disinfectants
(C10-C14 alkyldimethylbenzyl ammonium chloride)

3. ALKYL IMIDAZOLINES
incorporated in oil/waxes/paints to improve adhesion of the applied layer substrates.
irritating, for industrial uses

4. ETHOXYLATED ALKYL AMINES

used mainly for their capacity of adsorbing of surfaces (emulsion properties), in
hair conditioners, in fabric, to coat asphalt or bitumen helping to adhere
on wet surfaces

5. ESTERIFIED QUATERNARIES
softener (environmental problems)
21
 AMPHOTERIC SURFACTANTS II charge

-  both charges (+) and (-), change with pH, ZWITTERIONIC form at intermediate pH
-  pH important: anionic at alkaline pH, cationic at acid pH
-  ISOELECTRIC POINT
= both charges, minimum interfacial activity, max water solubility
-  most of them derives from amino acids, biocompatible
-  used in pharma and cosmetic industries

1. ACYL ETHYLENEDIAMINES AND DERIVATIVES

mainly in PCP, pH neutral (baby care products)

2. N-ALKYL AMINOACIDS OR IMINO DIACIDS

PCP products, reduce effect of skin and eye irritation

22
 NON-IONIC SURFACTANTS I NO charge

-  last 35-40 years represented the 40% of the surfactants on the market
-  do not produced ions in aqueous solution
-  compatible with other ingredients, used in complex mixtures
-  less sensitive to electrolyses, used also for waters hard and with high salinity
-  good detergents, wetting agents, emulsifiers
-  toxicity: from low toxicity to EDC

23
 NON-IONIC SURFACTANTS II

1. ETHOXYLATED ALKYL ALCOHOLS AND ALKYL PHENOLS

most used, fatty alcohols not generally considered true surfactants because very
weak soluble in water, but great use as co-emulsifiers and co-surfactants

Linear most used because branched not readily biodegradable

However more expensive to produce and toxic: i.e. elimination of benzene ring and
substitution by linear alcohols (even less efficient)
Used limited or banned for some compounds
because considered EDC (Endocrine Disrupting Compounds)
nonylphenol and nonylphenol ethoxylates restricted uses in EU (Annex XVII REACH)

2. FATTY ACIDS ESTERS

24
 NON-HYDROCARBON SURFACTANTS
By Brocken Inaglory, CC BY-SA 3.0
, https://commons.wikimedia.org/w/
index.php?curid=17769317

Lipophilic chain in more complex

1. SILICON SURFACTANTS
Hydrophobic character of silicon oil in particular poly dimethyl siloxane (PDMS).
Si is heavier than C --- chain shorter for same hydrophobic properties
Textile and fabric uses, lotion

2. FLUORO SURFACTANTS
Unique properties, the perfluoroalkyl chain is AMPHIPHOBIC (repellent to both
polar/non polar parts, not lipophilic neither hydrophilic) --- ABHESIVE SURFACES
-  low surface tension
-  exceptional surface wetting capacity
-  excellent thermal, chemical stability
BUT
-  expensive,
-  resistant to biodegradation
25
 CLASSIFICATION

- SURFACTANTS

- BUILDERS

- BLEACHING AGENTS

- ENZYMES

- MINOR COMPONENTS

Detergents as combinations of all of them

Most contains all 4 of them, other only 2 (e.g. window cleaners)
26
 BUILDERS I

-  30-50 % by weight of a detergent

-  used to enhance the performance of surfactants using

different mechanisms

-  STRUCTURE, CARRIER FOR LIQUID

physically build up the formulation (from solid powders to viscous liquids)

-  AGAINST HARDNESS WATER

water softener

-  PROVIDE ALCALINE BUFFER

-  PREVENT DIRTINESS REDEPOSITION

27
 BUILDERS II

VV.AA. Zeolites for detergents, CEFIC (European Chemical Industry Council) Publication, 2000

28
 CLASSIFICATION

- SURFACTANTS

- BUILDERS

- BLEACHING AGENTS

- ENZYMES

- MINOR COMPONENTS

Detergents as combinations of all of them

Most contains all 4 of them, other only 2 (e.g. window cleaners)
29
 BLEACHING AGENTS I

Often the combination between SURFACTANTS and BUILDERS is no enough

to reach the desired degree of cleanness.
Staining molecules can remain in the substrate and difficult to remove

Stronger action → OXIDATIVE ACTION by specific agent

Germ reduction activity (toilet cleaners, dishwasher, stain removal)

Two classes:

- OXYGEN BLEACHES

- HALOGENATED BLEACHES (HYPOCHLORITE)

30
 BLEACHING AGENTS II

European market:
- for almost a century dominated by SODIUM PERBORATE
TETRAHYDRATE and MONOHYDRATE
-  switch to SODIUM PERCARBONATE (more environmentally friendly, lower
costs)
US market: mostly dominated by chlorine bleach liquor

Tendency to lower the temperature of cleaning (save electricity consume),

makes perborate less effective (> 60-70°C for best bleaching conditions).

OXYGEN BLEACHES ACTIVATORS like

N,N,N’,N’-tetraacetyl etylenediamine
TAED (action at 30°C)

31
 BLEACHING AGENTS III

TAED ACTION WITH OXYGEN BLEACH

from Hautal in Handbooks of Detergents: Part C (2005)

32
 BLEACHING AGENTS IV

Typical composition of bleach system of powder formulations in Western Europe

33 Hirschen in Handbooks of Detergents: Part C (2005)

 BLEACHING AGENTS V

For stronger bleaching action (hygiene cleaners, toilet cleaners) it is

used sodium hypochlorite (active chlorine) or hydrogen peroxide (active
oxygen) with an increase of the second for ecological reasons.

Sodium hypochlorite stable and active in basic conditions:

With pH<7 it breaks down with formation of Cl2

General degradation of bleaching agents with humidity and heavy metals,

while activators can undergo to hydrolysis

34
 CLASSIFICATION

- SURFACTANTS

- BUILDERS

- BLEACHING AGENTS

- ENZYMES

- MINOR COMPONENTS

Detergents as combinations of all of them

Most contains all 4 of them, other only 2 (e.g. window cleaners)
35
 ENZYMES

Modern laundry formulations

ENZYMES: biological catalysis (proteins), faster kinetic of reaction,

to act an active substrate is needed
(30% of enzyme industrial production is for the detergent market)

ENZYMATIC ACTION:
•  function to hydrolase proteins, grease, oil, starch
•  minimise loss of colour from fabric (useful after multiple washing)
•  decrease cotton dinginess

PROTEASE - Removes protein stains and enhances cleaning functions

AMYLASE - Removes starch stains and has whitening boosters
CELLULASE - Brightens clothes by removing natural fibres
MANNANASE - Removes organic stains (guar) and enhances cleaning functions
LIPASE - Removes fatty and oily based stains
36
 CLASSIFICATION

- SURFACTANTS

- BUILDERS

- BLEACHING AGENTS

- ENZYMES

- MINOR COMPONENTS

Detergents as combinations of all of them

Most contains all 4 of them, other only 2 (e.g. window cleaners)
37
 MINOR COMPONENTS I

Can have different active roles:

•  COLORANT, DYES

•  FRAGRANCE, PERFUMES

•  ODOUR ABSORBER

•  PRESERVATIVE AGENTS

•  VISCOSITY REGULATORS

•  RHEOLOGICAL ADDITIVES

•  SOLVENTS

•  ACTIVATORS
38
 MINOR COMPONENTS II

mask unpleasant odour

FRAGRANCE OILS
influence purchasing behaviour

Room freshness, pervading pleasant perfume for sometimes after

fabric or sanitary ceramics are washed

Characteristics:
•  perfume persistent, remains over a long period
•  inexpensive
•  low odour threshold (measured in ng/L ambient air)
•  complex mix of volatile compounds (aroma), normally with MW > 250

39
 MINOR COMPONENTS III

FRAGRANCE OILS

some examples

40 Hauthal in Handbooks of Detergents: Part C (2005)

 MINOR COMPONENTS IV

laundry detergent powder

FRAGRANCE OILS

toilet gel cleaner

41
 CONCLUSIONS

•  SYNDET as mixture of different compounds,

very big analytical challenge

•  European market regulated by specific legislation

FINAL AIM: improve the protection of the human health
and of the environment

•  Importance of analytical protocols to understand the mechanism and

to identify specific properties and components (formulator/inspector)
in compliance with the regulation in force

42
 REFERENCES and USEFUL READINGS

Ed. G. Broze
Handbook of Detergents
Part A: Properties
Vol. 82, CRC Press (1999)

Regulation (EC) 648/2004 of European

Parliament and of the Council of
31 March 2004 on detergents

43
 ANY QUESTIONS….?

THANK YOU FOR

YOUR ATTENTION
‫شكرا‬
Contact:
LAVA ROBERTO, PhD
email: roberto.lava@arpa.veneto.it

44