Download Harmful influence of cyclic compound ingredients in detergents

Harmful influence of cyclic
compound ingredients in
detergents
Semira Hajrlahović Mehić, M. Sc.
Inspector counselor
Ministry of Health of Republic of Slovenia
Chemicals Office of the Republic of Slovenia
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Synthetic detergent : Compositions
Constituent
Composition (%)
Sodium tripolyphosphate (water softener, loosens dirt) a
38.0
Sodium alkane sulphonate (surfactant)
25.0
Sodium perborate tetrahydrate (oxidising agent)
25.0
Soap (sodium alkane carboxylates)
3.0
Sodium sulphate (filler, water softener)
2.5
Sodium carboxymethyl cellulose (dirt-suspending agent)
1.6
Sodium metasilicate (binder, loosens dirt)
1.0
Bacillus protease
0.8
Fluorescent brighteners
0.3
Foam-controlling agents
Trace
Perfume
Trace
Water
to 100%
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Surfactant
• The term comes from the words surface active
agent
• One of many compounds in detergent
• In detergents are added to remove dirt
• Also used extensively in industry
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Surfactant function
• To breaking down the interface between water and
oils and/or dirt
• To hold oils/dirt in suspension, and allow their
removal
• Contain both:
– a hydrophilic („water loving“) group, such as an acid
anion, (-CO2- or SO3-) and
– a hydrophobic („water hating“) group, such as an alkyl
chain
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Action of a surfactant
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Soaps
• The earliest surfactants
• Process known as saponification
– The glycerides are hydrolyzed by heating with sodium
hydroxide solution to form soaps, the sodium salts of the
acids, and propane-1,2,3-triol
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Soaps in water
• Soaps form insoluble calcium and magnesium
salts with the Ca and Mg ions in hard water
→ much of the soap is wasted forming an
insoluble scum
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Syntethic surfactants
• Synthetic surfactants have one very important
advantage over soaps: solubility
• This is avoid by using a synthetic surfactant
– where e.g. the carboxylate group in soap is
replaced by a sulfonate/sulfate group as the
hydrophilic part
→ Ca and Mg salts are more soluble in
water
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Syntethic surfactants
• The glycerides used to make surfactants contain
saturated and unsaturated carboxylic acids
• No. of carbon atoms within the range 12-20
• Octadecanoic acid (Stearic acid; C18)
(saturated)
• Dodecanoic acid (Lauric acid; C12)CH3
(saturated)
• Tetradecenoic acid (Miristoleic acid;
C14:1) (unsaturated)
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Syntethic surfactants;
classification
• Based upon the nature of the hydrophilic
"head-groups" as:
• Anionics
• Nonionics
• Cationics
• Amphoterics
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Anionics
• The hydrophilic group is negatively charged
• The most widely used type of surfactants for
laundering, dishwashing liquids and shampoos
• They are particularly good at keeping the dirt,
once dislodged, away from fabrics.
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Anionics types
•
•
•
•
4 anionic groups are used:
Alkylbenzene sulfonates
Alkyl sulfates
Alkyl ether sulfates
Soaps
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Anionics: Alkylbenzene sulfonates
• The most common synthetic anionic
surfactants are based on the straight chain
alkylbenzene sulfonates (LAS; LABSA, ABS)
• Benzene is mixed with an alkene or
chloroalkane in the presence of an acid
catalyst
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Anionics: Alkylbenzene sulfonates
• Most sodium dodecylbenzenesulfonates are a
member of the linear alkylbenzenesulfonates
– the dodecyl group (C12H25) is unbranched
– 4-(5-Dodecyl) benzenesulfonate
(4 indicating the position of the benzene ring, 5 indicating the position on the
dodecane chain)
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Anionics: Alkylbenzene sulfonates
• Branched isomers (derived from tetramerized
propylene) are also known but are not as
widely used because they biodegrade too
slowly
– And lead to foaming in rivers
and sewage plants
• In EU the surfactant must have unbranched
side chains which degrade more rapidly
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Harmful hazards of Alkylbenzene sulfonates
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Anionics types
•
•
•
•
Alkylbenzene sulfonates
Alkyl sulfates
Alkyl ether sulfates
Soaps
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Anionics: Alkyl sulfates
• Are in many detergents, particularly liquids
• Alkyl sulfates = esters of linear alcohols (C10C18) and sulfuric acid
– manufactured by treating the alcohol with SO3
• Also used in personal care products
(toothpaste)
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Alkyl sulfates v.s. Alkylbenzene sulfonates
• Sodium dodecyl sulfate (Sodium lauryl sulfate)
• Sodium dodecylbenzenesulfonate
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Anionics types
•
•
•
•
Alkylbenzene sulfonates
Alkyl sulfates
Alkyl ether sulfates
Soaps
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Anionics: Alkyl ether sulfates
• More widely used than alkyl sulfates are
sodium alkyl ether sulfates (e.g.SLES)
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Anionics: Alkyl ether sulfates
• Preferred by product formulators for many
applications (dishwashing liquids, shower gels,
shampoo, etc)
• Are milder to the skin than alkyl sulfates
• Also generate less foam
– an advantage in the formulation of laundry
machine products
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Anionics types
•
•
•
•
Alkylbenzene sulfonates
Alkyl sulfates
Alkyl ether sulfates
Soaps
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Syntethic surfactants;
classification
• Based upon the nature of the hydrophilic
"head-groups" as:
• Anionics
• Cationics
• Nonionics
• Amphoterics
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Cationic
• Hydrophilic head is positively charged
• Produced in much smaller quantities than the
anionics,
• Several types, each used for a specific purpose
– Mono alkyl quaternary systems
– Esterquats
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Cationic
Mono alkyl quaternary systems
• Alkyl quaternary nitrogen system has alkyl groups
attached to the nitrogen atom
• Used as fabric softeners with anionic
surfactants, helping them to break down the
interface between the dirt/stain and the water
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Cationic: Esterquats
• Give detergents their fabric softening qualities
• Are ester linkage between the alkyl chains and
the quaternary head-group as these are more
biodegradable and less toxic
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Syntethic surfactants;
classification
• Based upon the nature of the hydrophilic
"head-groups" as:
• Anionics
• Cationics
• Nonionics
• Amphoterics
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Nonionics
• Do not bear an electrical charge and are often used
together with anionics
• An advantage: do not interact with Ca and Mg ions in
hard water
• Nearly 50% of surfactant production (excluding soap)
• The major group: ethoxylates made by
condensing long chain alcohols with ethylene
oxide to form ethers
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Nonionics
• More surface active and better emulsifiers than
anionics at similar concentrations
• Less soluble than anionics in hot water and produce
less foam
• They are also more efficient in removing oily and
organic dirt than anionics.
• Used in fabric washing detergents (both powders and
liquids)
• Active in cold solution and useful:
– where is a lack of hot water supplies
– where a desire to lower the wash temperatures
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Nonionic
Nonylphenol ethoxylates (NPE)
• The restrictions on the marketing and use of
NP and NPE are described in Annex XVII, no.
46 to the REACH ( Reg. (EC) No 1907/2006):
• NP and NPE shall not be placed on the market,
or used, as substances or in mixtures in
concentrations equal to or greater than 0,1%
by weight for the certain purposes:
– also industrial and institutional
– domestic cleaning
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Nonionic
Nonylphenol ethoxylates (NPE)
• The restrictions of NP and NPE are based on a
need to limit the use of these substances as:
– NPE are degraded to nonylphenols, which
are considered to be endocrine disrupters
– NPE are not degradable rapidly in the
environment
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Syntethic surfactants;
classification
• Based upon the nature of the hydrophilic
"head-groups" as:
• Anionics
• Cationics
• Nonionics
• Amphoterics
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Amphoterics
• Amphoteric (or zwitterionic) „head-group“
carries both a negative and positive charge
• A range of methods to produce amfotercs ,
almost all contain a quaternary ammonium
ion (a cation)
• The negatively charged group can be:
– carboxylate ( -CO2-)
– sulfate ( -OSO3-) or
– sulfonate (-SO3)
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Amphoterics: Betaines
• A well-used class is the alkyl betaines with carboxyl group
• Betaines are neutral compounds with a cationic and an
anionic group which are not adjacent to one another
• Betaines are neutral compounds with a cationic and an
anionic group which are not adjacent to one another
• Very mild and used in shampoos and other cosmetics
• pH balanced
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Synthetic detergent : Compositions
Constituent
Composition (%)
Sodium tripolyphosphate (water softener, loosens dirt) a
38.0
Sodium alkane sulphonate (surfactant)
25.0
Sodium perborate tetrahydrate (oxidising agent)
25.0
Soap (sodium alkane carboxylates)
3.0
Sodium sulphate (filler, water softener)
2.5
Sodium carboxymethyl cellulose (dirt-suspending agent)
1.6
Sodium metasilicate (binder, loosens dirt)
1.0
Bacillus protease
0.8
Fluorescent brighteners
0.3
Foam-controlling agents
Trace
Perfume
Trace
Water
to 100%
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Sodium perborate tetrahydrate
• Oxidising agent
– It serves as a source of active oxygen in many
laundary detergents,cleaning agents….
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Classification according to part 3 of Annex VI, Table 3.1 of Regulation (EC)
No 1272/2008
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Conclusions
• Not many cyclic compound are ingredients in
detergents/ cleaning agent
• Concentrations: low
• However substances as such have hazardous
properties
– human health
– environment
• Restrictions in force for some surfactants in EU
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Thank you for your attention
[email protected]
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