Laundry Detergent Formulations 63

Preformed peracids are also known. They offer a weight efficiency advantage
since
no hydrogen peroxide is required and there is no “wasted” leaving group. The
main issue
with preformed peracids is stability—both of the raw material itself and in finished
product.
Phthalimidoperoxycaproic acid (PAP) is probably the best known. Metal bleach
catalysts
also offer great promise of weight efficiency. Bleach catalysts are transition metal
compounds,
typically Mn, Fe, Cu, or Co, with various chelating organic ligands. They react
with appropriate oxygen sources to form high valent metal oxides that are potent
oxidizing
agents. Most are designed for use with hydrogen peroxide, but the obvious goal is
to
develop a catalyst that works with molecular oxygen. To date there is no
successful
commercial example, but the search continues within many academic and
corporate labs.
In some regards photobleaches (normally metal phthalocyanines) could be
considered as
bleach catalysts. They generate singlet oxygen, a powerful bleaching species, on
exposure
to light and air. Because of the need for sunlight, and because the bleach is only
really
effective while the clothing is still wet, the utility of photobleach is greatest in
areas where
consumers air dry their laundry outside. Figure 4 presents the exemplary
structure of
common bleaches and chelants.
F. Chelating Agents
Chelants are often formulated in detergents because metal ions in the wash are
almost
always a detriment to end performance. Many highly colored stains incorporate
metals.
Removal of the metal can often decolorize the stain and/or make it easier to
remove by
destabilizing its structure. Examples include porphyrins found in blood and
tannins in tea.
Metal ions can also catalytically decompose bleach in a formulation, leading to
significantly
reduced performance. Finally, metals often find their way onto fabric surfaces,
either
as insoluble salts as with calcium or magnesium fatty acids, or as metal oxides.
Both lead
to a multicycle dinginess and fabric feel issues.
What chelant is used depends largely on local environmental regulations.
Diethylene
triamine pentaacetic acid (DTPA) is commonly used in North America. It’s an
analog of
the more well-known ethylenediaminetetraacetate (EDTA), but has a better
environmental
profile. In Europe, however, DTPA is banned due to concerns with aquatic toxicity.
As a
result, European formulations rely more on phosphonate-based chelants such as
diethylene
triamine penta(methylene phosphonic) acid (DTPMP) or ethylene diamine
tetra(methylene
phosphonic) acid (DDTMP). In an interesting twist, these materials cannot be used
in
North America due to bans on phosphorous in laundry detergents.
In environmental terms, ethylene diamine disuccinic acid (EDDS) represents the
best achievement thus far. The molecule has two chiral centers and only the S,S-
isomer
is fully biodegradable. This makes it a more expensive chelant than the
phosphonate
chelants mentioned previously. It is used in some European granules today. HEDP,
1-
hydroxyethyidene-1,1-diphosphonic acid, is not truly a chelant in the sense of the
materials
mentioned above, but because it also helps control deposition of metals on fabrics
it
deserves mention in the same section. HEDP works more by inhibiting crystal
growth.

Liquid Bleach Formulations 195

Radical scavengers work against the same type of decomposition process as
chelants,
i.e. radical decomposition, but they do it through a different mechanism. Chelants
try to
occupy active sites in the coordination sphere of transition metals, thus making
them
unavailable for interaction with hydrogen peroxide and preventing the formation
of OH.
radicals. Instead radical scavengers perform the function of stopping OH. radicals
once
they have been formed. Typical radical scavengers are molecules that can donate
a hydrogen
atom to a reactive radical, such as OH., thus transforming it into a nonradical
species
with lower reactivity. The radical scavenger molecule, after donating its hydrogen
atom,
becomes itself a radical, however, the new radical formed is a more stable one
with low
reactivity, so the original radical chain reaction is terminated or significantly
slowed down.
Usually the stable radical obtained from the scavenger is an oxygen-centered
radical
derived from a phenolic structure. The phenolic structure allows to delocalize the
unpaired
electron on the aromatic ring, which results in lower energy, higher stability and
lower
reactivity of the radical molecule (see Fig. 9). Well-known examples of radical
scavengers
are butylated hydroxy toluene (BHT), mono-tert-butyl hydroquinone (MTBHQ)
[81,82],
and other phenolic compounds. Primary or secondary aryl amines have also been
proposed
as effective radical scavengers [83].
According to some authors, the amine oxide functionality may perform a radical
scavenging action too. Thus the effectiveness of amino phosphonates as
stabilizers may
be related not only to their chelating ability, but also to the formation of amine
oxide
functionalities upon oxidation of their tertiary amine sites [79].
The possibility of synergisms between different stabilizers combined together in
the
same formulation has been highlighted by several authors [84]. The most
frequently
exploited combination is the one between a chelant and a radical scavenger [81–
83],
however, the combination of chelants with other classes of compounds, e.g.,
polyacrylates,
has also been mentioned as synergistic [80].
Hydrogen peroxide solutions are not significantly affected by exposure to visible
light, while they are decomposed by radiation in the ultraviolet region, particularly
between
380 and 200 nm as mentioned above. The rate of decomposition is directly
proportional
to the concentration of hydrogen peroxide and to the square root of radiation
intensity.
Unfortunately, the reproducibility of UV light-induced decomposition experiments
is low
and strongly dependent on the particular grade of hydrogen peroxide used, so
specific
decomposition data as a function of UV frequency and intensity are not very
reliable.
However, what’s most important for the formulator from a practical standpoint is
that
ordinary plastic bottles usually provide a sufficient light barrier for storage on
indoor
shelves. It may be required to add to the plastic a charge of a UV absorber, if the
product
needs to be sold in countries where storage conditions are such that prolonged
exposure
to direct sunlight is likely to occur.
Figure 9 Stabilization of oxygen-centered radical through delocalization of the unpaired
electron
on the aromatic ring, in a typical radical scavenger with phenolic structure.

D. Phosphonates and Thiophosphonates

Phosphonates and thiophosphonates were introduced as lubricant detergent
additives
in 1943 by Loane and others in Standard Oil Company of Indiana [26–29]. Both
phosphonates and thiophosphonates are the reaction products of liquid
polyolefins such
as polyisobutene with phosphorus pentasulfide. The reaction products were found
to
consist of a mixture of phosphonate, thiophosphonate, and thiopyrophosphonate
[30].
The commercial products are generally called either phosphonates or
thiophosphonates
depending on the extent to which sulfur has been remove by steam treatment
and the
length of hydrolysis. When the detergent was first introduced into the market, it
was
supplied as a normal potassium salt. Later, it was changed to a barium salt [31].

The chemical structures of normal phosphonate, thiophosphonate, and

thiopyrophosphonate
are shown below:
R has a molecular weight (MW) ranging from 500 to 2000. Typically, the alkyl
group is a Friedel-Crafts reaction product of isobutylene.
Overbased metal salts have been prepared using the same overbasing process for
the
other detergents such as sulfonates, phenates, and salicylates. The processes
developed for
production of overbased phosphonates or thiophosphonates include the use of
methanol [32]
and phenol [33] as the promoter. An overbasing ratio of at least 4:1 has been
reported [34]