Note: Descriptions are shown in the official language in which they were submitted.
20~2~6~
C6167 (C)
STRUCTURE3D I~IOaIDS CONTAINI~G AMIDO
AND IMIDO_PEROXYACIDS
The invention concerns a detergent composition which is a
structured liquid comprising amido and imido peroxy acid
; bleaches.
It is well-known in the art that stable suspensions of
organic peroxyacids in agueous liquids can be formed.
One of the earliest reports is in U.S. Patent 3, 996,152
(Edwards et al) which discloses a suspension of
diperoxyacids through non-starch thickening agents such as
Carbopol 940 in an aqueous media at low pH. Suitable
actives were diperazelaic, diperbrassylic, dipersebacic
and diperisophthalic acids. U.S. Patent 4,017,412
(Bradley) reports similar systems except that starch-based
thickening agents were employed. From later
investigations it became evident that the thickener types
mentioned in the foregoing patents formed gel-like
matrices which exhibited instability upon storage at
elevated temperatures. At high concentrations they caused
difficulties by uncontrollably raising viscosity to levels
which were too high.
-
'' ' ''
2 ~
- 2 - C~167 (C)
U.S. Patent 4,6~2,19~ (Humphreys et al) describes a
variety of water-insoluble organic peroxyacids intended
for suspension in an aqueous, low pH li~uid. This patent
discloses the use of surfactants, both anionic and
nonionic, as suspending agents for the peroxyacid
particles. The preferred peroxy material was 1,12-
diperoxydodecanedioic acid (DPDA).
EP 176 124 (de Jong) discloses a pourable bleach
composition containing peroxycarboxylic acid in an aqueous
suspension with 0.5 to 15% alkylbenzene sulphonic acid and
low levels of sulphate salt.
The aforementioned patents have all emphasized optimizing
the suspending or thickening chemical components of the
liquid bleach to improve physical stability. None of the
above patents, however, suggests a system which will allow
the compositions to be used as effective heavy-duty liquid
detergents in the main wash.
A possible approach to this problem was recently disclosed
in ~.S. Patent 4,992,194 (Liberati et al). Therein it was
reported that water-insoluble organic peroxyacids such as
N-phthaloyl aminoperoxycaprioc acid, referred to in the
industry as "P~P", could be suspended in a surfactant
pro~ided a pH-adjusting jump system and a deflocculating
polymer were also present. A combination of polyol and
; borate were utilised for the pH-adjusting jump system.
The deflocculating polymer was in the form of a copolymer
of hydrophilic and hydrophobic monomers. While the system
of Liberti et al represented a significant step forward
towards achieving a commercially acceptable, fully-
formulated heavy-duty laundry detergent, there remains
considerab]e room for improvement.
!
209~
- 3 - C6167 (C)
The present invention seeks to provide a fully formulated,
aqueous-based heavy-duty liquid laundry detergent
composition containing a stably suspended peroxy bleach
which has a viscosity and bleaching and cleaning
properties which are acceptable to the consumer.
It has been found that certain amido or imido peroxyacids
can be successfully suspended, i.e. they do not decompose
or undergo phase separation, for extended periods of time
in an aqueous surfactant structured liquid. These
peroxyacids are characterised by having a particular water
solubility.
Accordingly, the invention provides a cleaning composition
comprising:
i) an amido or imido organic peroxyacid having a water
solubility of less than 1 x 10-4M, present in
effective amount for bleaching;
ii) a surfactant present in an effective amount for
suspending the peroxyacid; and
iii) a pH-adjusting system present in an effective amount
for maintaining pH from 3.5 to ~.5 during storage
and, upon dilution with a wash water, causing pH to
rise by at least 0.5 pH units.
It is believed, the pH-adjusting system assists in the
stabilisation of the peroxyacids.
.
Preferably, the amido or imido organic peroxyacid has a
water solubility of less than 5 x 10-sM.
The compositions of the invention find particular
application as heavy duty laundry detergent liquids.
2~28~;4
: - 4 - C6167 (C)
Peroxyacids of the present invention are preferably
selected from mono- or dl- percarboxylic amido or imido
acids. Mono-percarboxylic acids are of the general
formula:
R ( RlN ) nC ( NR2 ) m--R3 ~ CIOOM
wherein:
R is selected from the group consisting of C1-Cl6 alkyl,
0 Cl-cl6 cycloalkyl and C6-Cl2 aryl radicals;
R1 is selected from the group consisting of hydrogen, C1-C16
alkyl, Cl-Cl6 cycloalkyl and C6-Cl2 aryl radicals;
R2 is selected from the group consisting of hydrogen, C1-C16
alkyl, Cl-C16 cycloalkyl and C6-Cl2 aryl radicals and a
carbonyl radical that can form a ring together with R when
R3 is arylene;
.~ 20 R3 is selected from the group consisting of Cl-Cl6 alkylene,
~ Cs-Cl2 cycloalkylene and C6-C12 arylene radicals;
`~ n and m are integers whose sum is 1; and
~'
:~ 25 M is selected from the group consisting of hydrogen,
;, alkali metal, alkaline earth metal, ammonium and
~ alkanolammonium cations and radicals.
"
Di-percarboxylic acids of the present invention may be of
the general formula:
O O O O
MOOeR4 (RsN) n~ e (NR6) n.--R3--(R6N) m.C (NFcs) m,R4CooM
2~28~
- 5 - C6167 (C)
wherein:
R4 is selected from the group consisting of C~-C12 alkylene,
Cs-C12 cycloalkylene, C6-C12 arylene and radical combinations
thereof;
Rs is selected from the group consisting of hydrogen, Cl-Cl6
alkyl and C6-C12 aryl radicals and a carbonyl radical that
can form a ring together with R3;
R6 is selected from the group consisting of hydrogen, Cl-Cl6
alkyl and C6-Cl2 aryl radicals and a radical that can form
a C3-Cl2 ring together with R3;
R3 is selected from the group consisting of Cl-CI2 alkylene,
Cs-Cl2 cycloalkylene and C6-Cl2 arylene radicals;
; n' and n" each are an integer chosen such that the sum
thereof is 1;
m' and m" each are an integer chosen such that the sum
thereof is 1; and
M is selected from the group consisting of hydrogen,
alkali metal, alkaline earth metal, ammonium and
alkanolammonium cations and radicals.
Particularly preferred materials are:
N,N'-di(4-percarboxybenzoyl)-1,4-butanediamine;
N,N'-di(4-percarboxybenzoyl)-1,2-phenylenediamine;
N,N'-succinoyl-di(4-percarboxy)aniline;
4-percarboxybenzoyl aniline;
N,N-phthaloyl-4-aminoperbenzoic acid;
.
.
2~2~
- 6 - C6167 (C)
N,N'-di(4-percarboxybenzoyl)ethylenediamine;
N,N'-di(4-percarboxyaniline) terephthalate;
N,N,M~,M'-1,2,4,5-tetracarboxybenzoyl-di(6-
aminopercarboxycaproic acid);
S N,N'-di(4-percarboxybenzoyl)piperazine;
N,N'-di(4-percarboxybenzoyl)-1,4-diamine-cyclohexane;
N,N'-di(percarboxyadipoyl)phenylenediamine; and
N,N'-di(percarboxyadipoyl)ethylenediamine.
N,N'-terephthaloyl-di(6-aminoperoxycaproic acid) is
especially preferred.
Another material which may be used in the compositions of
the invention i5 the monononylamide of peroxyadipic acid,
the preparation of which is described in US patent A686063
Amounts of the amido or imido peroxyacids of the present
invention may range from about 0.1 to about 40%,
preferably from about 1 to about 10% by weight.
,~
Another component of the present invention will be that of
a surfactant. The surface-ac~ive material may be
naturally derived, such as soap or a synthetic material
selected from anionic, nonionic, amphoteric, zwitterionic,
cationic actives and mixtures thereof. Many suitable
actives are commercially available and are fully described
in the literature, for example in "Surface Acti~e Agents
and Detergents", Volumes I and II, by Schwartz, Perry and
Berch. The total level of the surface-active material may
range up to 70% by weight, preferably being from about 1~
to about 50% by weight of the composition, most preferably
4 to 45%.
Synthetic anionic surface-actives are usually water-
soluble alkali metal salts of organic sulphates and
sulphonates having alkyl radicals containing from about 8
2~92~
- 7 - C6167 (C)
to 22 carbon atoms, the term alkyl being used to include
the alkyl portion of higher aryl radicals.
.
Examples of suitable synthetic anionic detergent compounds
are sodium and ammonium alkyl sulphates, especially those
obtained by sulphating higher (C8-C18) alcohols produced
for example from tallow or coconut oil; sodium and
ammonium alkyl (C9-C20) benzene sulphonates, particularly
sodium linear secondary alkyl (C1o-Cls) benzene sulfonates;
sodium alkyl glyceryl ether sulphates, especially those
ethers of the higher alcohols derived from tallow or
coconut oil and synthetic alcohols derived from petroleum;
sodium coconut oil fatty acid monoglyceride sulphates and
sulphonates; sodium and ammonium salts of sulfuric acid
esters of higher (C9-C18) fatty alcohol-alkylene oxide,
particularly ethylene oxide reaction products; the
reaction products of fatty acids such as coconut fatty
acids esterified with isethionic acid and neutralized with
sodium hydroxide; sodium and ammonium salts of fatty acid
amides of methyl taurine; alkane monosulphonates such as
those derived by reacting alpha-olefins (C8-C20) with
sodium bisulphite and those derived by reacting paraffins
with SO2 and Cl2 and then hydrolysing with a base to
produce a random sulphonate; sodium and ammonium C7-C12
dialkyl sulphosuccinates; and olefinic sulphonates, which
term is used to describe the material made by reacting
olefins, particularly C10-C~O alpha-olefins, with S03 and
then neutralizing and hydrolysing the reaction product.
The preferred anionic detergent compounds are sodium (C11-
C1s) alkylbenzene sulphonates; sodium (C16-Cl8) alkyl
sulphates and sodium (C16-C18) alkyl ether sulpha~es.
Examples of suitable nonionic surface-active compounds
which may be used preferably together with the anionic
surface active compounds, include in particular, the
2~9286~
- 8 - C~167 (C)
reaction products of alkylene oxides, usually ethylene
oxide, with alkyl (C6-C22) phenols, generally 2-25 EO, i.e.
2-25 units oE ethylene oxide per molecule; the
condensation products of aliphatic (C8-Cl~) primary or
secondary linear or branched alcohols with ethylene oxide,
generally 2-30 EO, and products made by condensation of
ethylene oxide with the reaction products of propylene
oxide and ethylene diamine. Other so-called nonionic
surface-actives include alkyl polyglucosides, esters of
fatty acids and glucosides, long chain tertiary amine
oxides, long chain tertiary phosphine oxides and dial~.yl
sulfoxides.
Amounts of amphoteric or zwitterionic surface-active
compounds can also be used in the compositions of the
invention but this is not normally desired owing to their
relatively high cost. If any amphoteric or zwitterionic
detergent compounds are used, it is generally in small
amounts in compositions based on the much more commonly
used synthetic anionic and nonionic actives.
; The detergent compositions of the invention will normally
also contain a detergency builder. Builder materials may
be selected from (1) calcium sequestrant materials, (2)
precipitating materials, (3) calcium ion-exchange
materials and (4) mixtures thereof.
Examples of calcium ion-exchange builder materials include
the various types of water-insoluble crystalline or
amorphous aluminosilicates, of which zeolites are the best
known representatives, e.g. zeolite A, zeolite B (also
known as Zeolite P), zeolite C, zeolite X, zeolite Y and
also the zeolite P type as described in EP-A-0,384,070.
2~2~
` - 9 - C6167 (C)
.~ ,
` In particular, the compositions of the invention may
contain any one of the organic or inorganic builder
materials, such as sodium or potassium tripolyphosphate,
sodium or potassium pyrophosphate, sodium or potassium
orthophosphate, sodium carbonate, the sodium salt of
` nitrilotriacetic acid, sodium citrate,
carboxymethylmalonate, carboxymethyloxysuccinate, tartrate
mono- and di-succinates, oxydisuccinate, crystalline or
amorphous aluminosilicates and mixtures thereof.
Polycarboxylic homo- and copolymers may also be included
as builders and to function as powder structurants or
processing aids. Particularly preferred are polyacrylic
acid (available under the trademark Acrysol from the Rohm
and Haas Company) and acrylic-maleic acid copolymers
(available under the trademark Sokalan from the BASF
Corporation) and alkali metal or other salts thereof.
These builder materials may be present at a level of, for
example, from 1 to 80% by weight, preferably from 3 to 30%
by weight.
Upon dispersal in a wash water, the initial amount of
peroxyacid should range in amount to yield anywhere from
about 0.05 to about 250 ppm active oxygen per litre of
water, preferably between about 1 to 50 ppm. Surfactant
should be present in the wash water from about 0.05 to 3.0
grams per litre, preferably from 0.15 to 2.4 grams per
litre. When present, the builder amount will range from
about 0.1 to 3.0 grams per litre.
It is well-known that organic peroxyacid bleaches are most
stable at a low pH (3-6), whereas they are most effective
as bleaches in moderately alkaline pH (7-9) solution. To
achieve the required pH regimes, a pH jump system is
21D~2~6~
- 10 - C6167 (C)
employed to ~eep the pH of the product between 3 and 8.5
for peracid stability during storage, yet allow it to
become moderately high (pH 7-9) in a wash water for
bleaching and detergency efficacy. Most important is that
there is obtained a pH jump of at least 0.5 units,
preferably 1.0 units, optimally about 1.5 units. One pH
jump system is borax 10H20/polyol. Borate ion and certain
cis-1,2-polyols complex when concentrated cause a
reduction in p~. Upon dilution, the complex dissociates,
liberating free borate to raise the pH. Examples oE
polyols which exhibit this complexing mechanism with
borate inc;ude catechol, galactitol, fructose, sorbitol
and pinacol. For economic reasons, sorbitol is the
preferred polyol. To achieve the desired concentrate pH
of less than 7, ratios greater than about 1:1 of polyol to
borax are usually required. Therefore, the preferred
ratio of polyol to borax should range anywhere from about
1:1 to about 10:1, although the range may be as broad as
1:10 to 10:1. Borate compounds such as boric acid, boric
oxide, borax with sodium ortho- or pyroborate may also be
suitable as the borate component.
Preferably, the pH jump system is present in an amount
; from about 1 to about 40 by weight.
An advantageous optional component in the compositions of
the invention is a deflocculating polymer. Copolymers of
hydrophilic and hydrophobic monomers usually are employed
to form the deflocculating agent. Suitable polymers are
obtained by copolymerizing maleic anhydride, acrylic or
methacrylic acid or other hydrophilic monomers such as
ethylene or styrene sulphonates and the like with similar
monomers that have been functionalized with hydrophobic
groups. These include the amides, esters, ethers of fatty
alcohol or fatty alcohol ethoxylates. In addition to the
2~9~
- 1~ - C6167 tC)
fatty alcohols and ethoxylates, other hydrophobic groups,
such as olefins or alkylaryl radicals, may be used. What
is essential is that the copolymer have acceptable
oxidation stability and that the copolymer have
hydrophobic groups that interact with the lamellar
droplets and hydrophilic groups of the structured liquid
to prevent flocculation of these droplets and thereby,
prevent physical instability and product separation. ~n
practice a copolymer of acrylic acid and lauryl
methacrylate (molecular weight 3800) has been found to be
effective at levels of 0.5 to 1.5~. These materials are
more fully described in U.S. Patent 4,992,194 (Liberati et
al) herein incorporated by reference.
Apart from the components already mentioned, the detergent
compositions of the invention can contain any of the
` conventional additives in the amounts in which such
materials are normally employed in detergent compositions.
Examples of these additives include lather boosters such
; 20 as alkanolamides, particularly the monoethanolamides
derived from palmkernel fatty acids and coconut fatty
acids, lather depressants such as alkyl phosphates and
silicones, antiredeposition agents such as sodium
carboxymethylcellulose and alkyl or substituted
alkylcellulose ethers, other stabilizers such as ethylene
diamine tetraacetic acid, fabric softening agents,
inorganic salts such as sodium sulphate and, usually
present in very small amounts, fluorescent whitening
agents, perfumes, enzymes such as proteases, cellulases,
lipases and amylases, germicides and colorants.
The compositions of the invention may be used to clean a
wide of substrates, including hard surfaces, and
especially fabrics.
. : j .
'
2~9~8~;~
- 12 - C6167 (C)
The following non-limiting examples will more fully
illustrate the embodiments of this invention. All parts,
percenta~es and proportions referred to herein and in the
appended claims are by weight unless otherwise stated.
~xam~le 1
Monomethyl mono~otassilm tere~hthalate
A solution of 87.5~ KOH (143 g, 2.24 moles) in 870 ml of
methanol was added to group dimethylterephthalate (434 g,
2.24 moles) in 2,420 ml toluene at room temperature over a
period of 45 minutes. The reaction mixture was heated at
65C for three hours with stirring and then allowed to
cool to room temperature. The solids were filtered,
washed with 3500 ml of warm toluene, and dried to yield
464,08 grams (95% yield) of a white solid. IR (nujol)
1735, 1600, 1550, 1410, 1290, 730 cm~l.
~
Monomethyl monopotassium terephthalate (175.8 g, 0.8056
mol) was suspended in toluene (2000 ml) in a 5 litre, 3-
~` necked flask equipped with an overhead stirrer, a
condenser, and an addition funnel. Thionyl chloride(58.76 ml, 0.8056 mol) was added dropwise to the rapidly
stirred suspension and the mixture was heated at 67C for
three hours. After stirring overnight at room
temperature, the reaction was filtered on a Buchner funnel
through a bed of celite and the filtrate containing 4-
carbomethoxybenzoyl chloride was retained. At this point
the acid chloride can be isolated by addition of an equal
volume of diethyl ether, filtration of the potassium
chloride by-product and removal of the solvent in vacuo.
For most procedures the toluene solution is used directly.
- 13 _ 2 0 9 2 ~ 6 ~ C6167 (C)
In a 5 litre Morton flask, potassium carbonate (266.2 g,
1.61 mol) and piperazine (34.69 g, O.gOZ7 mol) were
dissolved in 1000 ml of water. The toluene solution of 4-
carbomethoxybenzoyl chloride was added dropwise while the
internal reaction temperature was maintained at 25C. The
mixture was stirred overnight, filtered and washed with
toluene, water~ lN HCl and wat:er to provide 127 g (77%) of
N,N'-di(4-carbomethoxybenzoyl) piperazine as a white
solid. mp. 234-237C; IR (nujol) 1730, 1630, 1610, 1510,
; 10 1290, 1260, 1010, 730 cm~'.
H NMR (200MHz, CDCl3/CD3COCD3) ~ 7.48-R.11 (8H, m), 3.93
(6H, s), 3.81 (4H, br s), 3.56 (4H, br s); 13C NMR
(CDCl3/CD3COCD3) ~ 169.51, 166.05, 139.19, 131.50, 129.89,
126.98, 52.31, 43.80, 41.10; IR (nujol) 2920, 2840, 1720,
1620, 1605, 1455, 1430, 1370, 1360, 1275, 1260, 1100, 1000
cm~1; low res. MS (CI, isobutane) 411 (MH+).
N,M~-Di(4-Percarboxybenzoyl)piperazine (pcspIp)
N,N'-Di(4-percarboxybenzoyl) piperazine (4.07 g, 0.0099
mol) was dissolved in methanesulphonic acid (14 ml) and
was treated with hydrogen peroxide (3.37 ml of a 70%
solution, 0.0891 mol) at 0C. The mixture was stirred at
room temperature for 5 hours, then poured onto ice-water.
The solids were collected on a Buchner funnel, washed with
water until the pH was 5, then allowed to air dry
overnight. Yield 3.91 g (95%) of a white powder; m.p. 268
(decomposed prior to melting (dec)). Iodometric
tritration indicated 65% peracid. IR (nujol) 3100
(hydroxyl), 1760 (peracid carbonyl) cm~l.
,
2~920~;~
- 14 - C6167 (C)
~xam~le 2
N~N~-Di(4-carbomethoxybenzoyl- ~=bL~
Prepared using the procedure described for M,N'-
di(carbomethoxybenzoyl) piperazine and substituting
ethylenediamine (26.9 ml, 0.4028 mol) for piperazine and
using 400 ml of water instead of 1000 ml. Yield 88.6 g
(57%); mp. 297-299C; lH NMR (200 MHz, DMSO-d6) ~ 8.82 (2
H, br s), 8.06-7.94 (8 H, m), 3.88 (6 H, s), 3.47 (4 H,
s); IR (nujol) 3300, 1730, 1640, 1550 cm~l.
N,N'-Di~4-Percarboxvbenzoyl) ethylene_iamine (PCB~
N,N~-Di(4-carbomethoxybenzoyl) ethylenediamine (5.0 g,
0.0129 mol) was dissolved in 30 ml of methanesulphonic
acid and treated with hydrogen peroxide (4.4 ml of a 70%
solution) at 0C. The mixture was allowed to warm to room
; temperature and was stirred for 5 hours. It was poured
onto ice and saturated ammonium sulphate, the solids were
filtered and washed with water to a pH of 5. The activity
was 78% by iodometric titration.
Exam~?le 3
; N,N~-Di l4-CarbomethoxvbenzoYl~ 4-phenylenediamine
4-Carbomethoxybenzoyl chloride (9.32 g, 0.046 mol) in
chloroform (95 ml) was added to 1,4-phenylenediamine
30 (2.59 g, 0.023 mol) in triethylamine (4.81 ml, 0.035 mol)
and chloroform (250 ml) at 4C. The reaction was allowed
to warm to room temperature overnight. The chloroform was
removed in vacuo. The solid was poured onto cold 5% HCl,
filtered and washed with dilute HCl. Recrystallization
35 from DMF yielded 6.16 g (62%) of a pale yellow powder; mp
.
209~86~
- 15 - C6167 (C)
>345C. lH MMR (DMSO~d6) ~ 8.06 (8H, s), 7.74 (4~, s),
3.88 (6H, s); 13C NMR (H2SO4/CD3COCD3) (dec. to acid) ~ 205,
196, 169.77, 167.10, 132.56, 130.95, 128.16, 127.79,
127.03, 122.85, 119.82, 52.02; IR (nujol) 3330, 2900,
2840, 1720, 1640, 1550, 1455, 1410, 1375, 1280, 1190, 1110
cm~'; low res. MS(CI, isobutane) 433 (MH~), 271, 257, 223.
N,N~-Di~4-Percarbox_benzoyl)phenYlenediamine ~1,4-PCBPD)
., 10
N,N'-Di(4-carbomethoxybenzoyl)phenylenediamine (3.07 g,
0.0071 mo].) was dissolved in methanesulfonic acid (40 ml)
and treated with hydrogen peroxide (2.42 ml of a 70%
solution, 0.0639 mol) at room temperature. After stirring
at room temperature for 6 hours, the reaction was kept at
3C for 12 hours. The mixture was poured onto saturated
ammonium sulphate solution and ice and then isolated as
before to yield 1.85 g (59~) of an orange powder;
mp>315C. Iodometric titration indicated 60% peracid. IR
(nujol) 3230 (hydroxyl), 1755 (peracid carbonyl) cm~l.
~xam~le 4
;
N,N'-di(4-CarbomethoxvbenzoYl)-1,4-diaminoc~clohexane
4-Carbomethoxybenzoyl chloride (9.057 g, 0.0456 mol) was
dissolved in chloroform (180 ml) in a 500 ml 3-necked
flask equipped with a mechanical stirrer and an addition
funnel. To this solution was added trans-1,4-
diaminocyclohexane (2.60 g, 0.0228 mol), triethylamine
(7.5 ml, 0.0535 mol) and chloroform (80 ml) at 0C over a
period of 30 minutes. The reaction was stirred for 2.5
hours and the product filtered from the chloroform. The
wet solid was washed with 10% HCl and saturated aqueous
MaCl. The product was dissolved in concentrated sulfuric
2092~
- 16 - C6167 (C)
acid at 0 and then crashed out from ice water to give a
white powder in about 80~ yield; m.p. >350C. lH NMR (200
MHz, D2SO4) ~ 8.30-7.94 (8H, m), 4.27-4.37 (8H, m), 2.34-
1.80 (8H, br m), 13C NMR (200 MHz, H2SO4/CD3COCD3) ~ 170.92,
132.32, 129.92, 129.25, 127.61, 55.04, 51.83, 24.07; IR
(nujol) 3295, 2920, 2850, 1720, 1630, 1530, 1460, 1375,
1285 cm~l.
N,N'-Di(4-Percarboxvbenzoyl)-1(4-diaminocyclohexane
(PCB EX)
N,N'-D:i(4-percarboxybenzoyl)-1,4-diaminocyclohexane (1,63
g, 0.0037 mol) was dissolved in methanesulphonic acid (10
ml) and treated with hydrogen peroxide (1.26 ml of 70%
solution, 0.0333 mol) at room temperature. After 7 hours,
the reaction was worked-up with ice water and dried in a
vacuum oven at 25C to give 1.57 g (95%) of a white
powder; m.p. >310C. Iodometric titration indicated 79%
peracid. lH NMR (200 MHz, DMSO-d6) ~ 8.47-8.44 (m, ester),
8.03-7.91 (m, peracid and ester), 3.88 (s, ester), 3.79
(br s, ester and peracid), 1.94-1.91 (m, ester and
peracid), 1.52-1.43 (m, ester and peracid; IR (nujol) 3295
(broad, hydroxyl), 1730 (peracid carbonyl) cm~l.
~xam~le 5
CarboethoxyadiPoyl_Chloride
Adipic acid monoethyl ester 125.63 g, 0.147 mol) was
combined with thionyl chloride (34.98 g, 0.293 mol) in a
round-bottomed flask equipped with a condenser and heated
at 37C for 3 hours. The condenser was replaced by a
modified still head and excess thionyl chloride removed at
5 mm Hg. The product (26.84 g, 95%) was distilled as a
clear liquid (59C/about 0.1 mm Hg). I~ 3550, 3420, 2950,
2~92(,~
~ - 17 - C6167 (C)
,
2910, 2840, 1785, 1715, 1455, 1360, 1230, 1170, 1140,
1080, 1010, 940 cm~l.
N,N'-Di(Carboethoxyadi~oyl)-1,4-Phenylenediamine
Carboethoxyadipoyl chloride (13.74 g, 0.071 mol) in
, chloroform (40 ml) was added to 1,4-phenylenediamine (3.89
g, 0.036 mol) in chloroform (330 ml) and triethylamine
(7.53 ml, 0.054 mol) at 4C. The reaction medium was
allowed to warm to room temperature over the course of 5
hours. Recrystallization from ethyl acetate gave 6.30 g
(42%) of a white fluffy solid; m.p. 156-160C. lH MMR
; (DMSO-d6) ~ 9.81 (2H, s, NH), 7.49 (4H, s), 4.04 (4H, q),
1.57 (8H, m), 2.34 ~8H, m), 1.18 (6H, t); 13C NMR ~ 173.65,
171.25, 134.38, 120.74, 50.39, 36.90, 33.98, 25.01, 24.42,
14.23; IR (nujol) 3290, 2920, 2840, 1720, 1645, 1540,
1455, 1370, 1370, 1290, 1255, 1170 cm~l; low res MS(CI,
isobutane) 421 (MH+).
N,N'-Di(Percarboxvadi~ovl)~henylenediamine (DPAPD~
N,N'-Di(carboethoxyadipoyl)-1,4-phenylenediamine (~.00 g,
0.0143 mol) was dissolved in methanesulphonic acid (21 ml)
and was treated with hydrogen peroxide (4.87 ml of a 70%
solution, 0.1287 mol) at room temperature. The product
was isolated from ice water after 2 hours to give 4.97 g
(88~) of a pale orange powder; m.p. 210-212 (dec).
Iodometric titration indicated 87% peracid. lH NMR (200
MHz, DMSO-d6) ~ 11.97 (2H, br, s), 9.83 (2H, s) 7.49 (4H,
m), 4.10 (trace, q, ester), 2.49-2.00 (8H, m), 1.57 (8H,
br s), 1.17 trace, t, ester); IR (nujol) 3100 (hydroxy),
1750 (peracid carbonyl) cm~1.
. ' .
20~28~
.
18 - C6167 (C)
Exam~le 6
N,N'Di(4-CarbomethoxYbenzovl)-1~ 4-butanediamine
4-Carbomethoxybenzoyl chloride (19.07 g, 0.096 mol) was
dissolved in toluene (380 ml) in a 3-necked, 1000 ml
round-bottomed flask equipped with mechanical stirrer,
thermometer, and addition funnel. A solution of 1,4-
butanediamine in water (80 ml) was added dropwise over a
period of 40 minutes while the temperature of the reaction
mixture was maintained at 25C by a water bath. A white
solid formed immediately and the reaction rnixture stirred
for an additional 2 hours. The solid was collected on a
frit and washed with toluene, water, 5% HCl, and water.
Recrystallization from DMF gave white crystals which were
dried in a vacuum oven at 60C; yield 17.91 g (90%); m.p.
260-~61C. lH NMR (200 MHz, DMSO-d6) ~ 8.70 (2H, m), 8.05-
7.93 (8H, m) 3.88 (6~, s) 3.34 (4H, s), 1.58 (4H, s); IR
(nujol) 3300, 1720, 1625, 1530, 1275, 1105, 860, 730 cm~l;
low res. MS (CI, isobutane) 413 (MH+); 13C NMR (75 MHz,
DMSO-d6) ~ 166.9, 165.7, 165.4, 165.2, 138.7, 131.6, 129.0,
127.5, 127.2, 52.3, 26.5.
N,N'-Di(4-Percarbox~enzo~l)-1,4-butanediamine ~PCBBD)
N,N~-Di(4-carbomethoxybenzoyl)-1,4-butanediamine (3.00 g,
0.007 mol) dissolved in methanesulfonic acid (25 ml) was
treated with hydrogen peroxide (2.50 ml of a 70~ solution,
0.066 mol) according to the aforedescribed method. After
5 hours at room temperature and 16 hours at 3C, the
peracid was precipitated over ice water, washed with water
and dried to give 1.8 g (60%) of a white powder; m.p. 180
(dec). Iodometric titration indicated 74% peracid, 5.7%
a.o. (theory: 7.7% a.o.). IR (nujol) 3320-3100
(hydroxyl), :L745 (peracid carbonyl) cm~l; IH NMR (200 MHz,
20~g~
- 19 ~ C6167 (C)
,.
DMSO-d6) ~ 8.65 (2H, m), 8.03-7.90 ~8H, m), 3.87 (starting
material, 7%), 3.29 (4H, s), 1.58 (4H, s).
~xam~le 7
N~N=Dl(4-CarbomethoxYbenzoYl1-1,2-Phenylenediami-e
4-Carbomethoxybenzoyl chloride (18.5 g, 0.093 mol) was
dissolved in chloroform (100 ml) under nitrogen and cooled
to 0C. A sol-ltion of 1,2-phenylenediamine (5.00 g, 0.046
mol) and triethylamine (12.8 ml, 0.092 mol) in chloroform
(350 ml) was added dropwise. After 16 hours at room
temperature, triethylammonium chloride was removed by
filtration on a frit containing filter paper. The organic
layer was washed with cold 5% HCl (3 x 200 ml), saturated
NaCl solution (2 x 150 ml), and dried over magnesium
sulfate. The product was isolated by removal of
chloroform under reduced pressure. Recryallization from
ethanol yielded 12.19 g (61%) of a white powder; m.p. 211-
216C. lH NMR (200 MHz, DMSO-d6) ~ 10.24 (2H, s), 8.09-
8.07 (8H, 2s), 7.69 (2H, s), 7.33 (2H, s), 3.90-3.88 (6H,
2s); 13C NMR (50 MHz, DMSO-d6) ~ 165.29, 164.37, 138.13,
131.82, 130.94, 128.94, 127.69, 125.79, 125.42, 52.08; IR
(nujol) 3380, 3280, 1720, 1645, 1540, 1290, 1275, 1100 cm~
1; low res. MS (CI, isobutane) 433 (MH~) 271, 165.
N.N~ i(4-Percarboxybenzoyl ? -1/ 2-phenylenediamine Ll, 2-
PCBP~)
N,N'-Di(4-carbomethoxybenzoyl)-1,2-phenylenediamine (2.75
g, 0.0064 mol) was dissolved in methanesulphonic acid (25
ml) and cooled to 0C. Hydrogen peroxide (1.57 ml of a
; 90% solution, 0.058 mol) was added dropwise. After 16
hours at room temperature, the reaction was worked-up as
described above.
- ~ .
:
. . .
2~9~,G~
- 20 - C6167 (C)
:~ .
` Idometric titration indicated 70% peracid, 5.2% a.o.
(theory: 7.3% a.o.) IR ~nujol) 3160 (hydroxyl), 1740
(peracid carbonyl) cm~l; 1H NMR (200 MHz, D~SO-d6) ~ 10.20
(2H, s), 8.09-8.07 (8H 2s), 7.73-7.52 (2H, m), 7.39-7.22
(2H, m), 3.89 (ester about 7%); 13C NMR (50 MHz, DMSO-d6)
166.58, 164.76, 137.95, 133.37, 131.19, 129.30, 127.76,
126.01.
;
Exam~le 8
N,N'-Succinoyl-di(4-carbomethoxY)aniline
Succinyl chloride was distilled under reduced pressure
prior to use. To a 1000 ml round-bottomed flask under
nitrogen, methyl-4-aminobenzoate (20 g, 0.132 mol),
pyridine (10.7 ml, 0.133 mol~, and chloroform (250 ml)
were combined and cooled to 0C. A chloroform solution of
succinoyl chloride (7.5 ml, 0.068 mol) was added dropwise.
A lavender precipitate was observed upon addition. After
2 hours at room temperature, the product was filtered on a
frit, washed with 5% HCl (2 x 400 ml) then with water (600
ml) and then allowed to air dry on the frit. The product
was recrystallized from DMF and dried in a vacuum oven at
60C to afford 16.09 g (62%) of white crystals; m.p. 284-
285C. lH NMR 200 MHz, DMSO-d6) ~ 10.42 (2H, s), 7.96~7.74
(8H, s), 3.85 (6H, s), 2.75 (4H, s); IR (nujol) 3340,
3320, 1710, 1690, 1675, 1610, 1595, 1530, 1295, 1270,
1175, 1160, 1105, 770 cm~1; low res. MS (CI, isobutane)
385 (MH+), 234, 152; 13C MMR (75 MXz, DMSO-d6) ~ 170.9,
165.7, 143.6, 130.2, 123.6, 118.2, 51.7, 31Ø
N,N'-Succinoyl-di(4-percarboxy)aniline (SDPCA)
N,N'-Succinoyl-di(4-carbomethoxy)aniline (5.02 g, 0.013
mol) was dissolved in methanesulfonic acid (30 ml) and
`` 2~9~8~
- 21 - C6167 (C)
:; .
cooled to 0C. Hydrogen peroxide (4. 43 ml of a 70%
solution, 0.117 mol) was added dropwise. After 6 hours at
room temperature, the product was worked-up as usual to
give a light tan powder; m.p. 201C. Iodometric
tritration indicated 72% peracid, 6.0~ a.o. (theory: 8. 2%
a.o.). IR (nujol) 3200 (hydroxyl), 1750 (peracid
carbonyl) cm~l; lH NMR (200 MHz, DMSO-d6) ~ 10.37, 10.34 (2H
each, s, one for peracid OH, one for amide -NH), 7.92 -7.68
(8H, m), 3.81 (s, ester), 2.72 (4H, s, ester and peracid).
Example 9
N,N'-Di(Carboethoxy dipo~l)ethYlenediamine
lS Ethylenediamine (1.17 g, 0.0195 mol) in water (5 ml) was
added dropwise to a solution of carboethoxyadipoyl
chloride (2.5 g, 0.013 mol) in toluene (36 ml) at room
temperature. After stirring for an additional 2.5 hours,
the white solid was filtered, washed with toluene, water,
20 0.1 N HCl and water and dried in a vacuum oven at 63C .
In an attempt to eliminate an impurity evident in the IR
spectrum (3080 cm~l), the material was taken up in toluene,
the insolubles removed by filtration, and the toluene
removed in vacuo to yield a white powder (0.31 g, 13%);
m.p. 117-120C (white residue remained after most melted).
H NMR (200 MHz, DMSO-d6) ~ 7.83 (2H, br s), 4.05 (4H, q)
3.37 (H20), 3.07 (5H, br s), 2.28-2.02 (lOH, br s), 1.49
(9H, br s), 1.18 (6H, t); relative to the ethoxy protons,
the integration of peaks at 3. 07 and 1.49 is high by one
proton each, and at 2.28-2.02 by two protons; IR (nujol)
3300, 2920, 2850, 1725, 1640, 1550, 1460, 1375, 1270,
1245, 1180, 730 cm~l.
Since the toluene purification did not eliminate the
35 unidentified impurity, the method described for the
.i
20~28~A
- 22 - C6167 (C)
,
preparation of N, N'-(4-carbomethoxybenzoyl) piperazine
was used. Carboethoxy-adipoyl chloride (1.0 g, 0.0052
mol) in chloroform (12 ml) was added dropwise to a
solution of ethylenediamine (0.16 g, 0.0026 mol),
triethylamine (0.54 ml, 0.0039 mol), and chloroform (5 ml)
at 4C under nitrogen. The mixture was stirred for 5.5
hours and worked up as usual to give 0.60 g (62%) of a
solid. This product was recrystalli~ed from toluene to
give 0.20 g (21~) of a white powder which still contained
the impurity by IR and NMR; m.p. 120-122C.
Recrystallization from ethyl acetate also did not
eliminate the impurity. 13C MMR (200 MHz, CDCl3/CD3COCD3)
207.44, 173~87, 60.38, 40.07, 36.08, 33.90, 25.12, 24.39,
14.33, 14.25; low res. MS(CI, isobutane) 373 (MH~).
N,N'-Di(PercarboxYadi~ovl)eth~lenediamine
N,N'-Di(carboethoxyadipoyl)ethylenediamine (0.023 g,
0.00055 mol) was dissolved in methanesulfonic acid (1.4
ml) and treated with hydrogen pero~ide (0.19 ml of a 70~
solution, 0.00495 mol) at room temperature and stirred for
18 hours. The product, which was difficult to isolate
from ice water, was a flaky material (0.0088 g, 46%) which
turned black <220C but did not melt before 350C.
Iodometric titration indicated 55~ peracid. lH NMR (200
MHz, DMSO-d6, ~ 7.81 (br s, ester and peracid), 4.10 ~,
ester), 3.06 (H2O), 2.22 and 2.19 (m, ester and peracid),
1.48 (m, ester and peracid), 1.19 (t, ester). IR (nujol)
3200 (hydroxyl) 1755 (peracid carbonyl) cm~1.
2a~2~
.
- 23 - C6167 (C)
,
~xam~le 10
N-BenzoY1~4-aminobenzoic acic!
Sodium carbonate ~26.5 g, 0.25 mol) was dissolved in 200
ml of water in a 500 ml Morton flask e~uipped with a
mechanical stirrer and an additional funnel. 4-
Aminobenzoic acid (13.71 g, 0.10 mol) was added
portionwise and the mixture was stirred until fully
soluble. The mixture was cooled to 0C and benzoyl
chloride (13.92 g, 11.50 ml, 0.099 mol) was added
dropwise. A thick, white precipitation soon formed and
after stirring for 2 hours at room temperature, the
mixture was poured onto cold, dilute HCl. The solid was
filtered and washed with dilute HCl and water.
Recrystallization from ethanol and water yielded 11.69 g
(49%) of the desired product; mp 284-288C; IR (nujol)
3340, 1680, 1665, 1650, 1515 cm~l; lH NMR (200 MHz, DMSO-d6)
~ 12.40 (lH, s), 10.55 (lH, s), 8.~0-7.45 (9H, m).
N-Benzoyl-4-aminoperoxybenzoic acid (BP-PABA1
N-Benzoyl-4-aminobenzoic acid (5.0 g, 0.0207 mol) was
dissolved in 20 ml of methanesulfonic acid. The mixture
was cooled to 0C and concentrated hydrogen peroxide (2.43
ml of a 70% solution, 0.0634 mol) was added dropwise. The
mixture was allowed to stir for 3 hours at room
temperature after which time it was poured onto a large
amount of ice water. The precipitate ~as filtered on a
Buchner funnel and washed with water until the pH of the
filtrate was 4.5. The activity was 79% (4.9% a.o., 5.22%
theory) as indicated by iodometric titration; mp 140 (dc)i
IR (nujol) 3450 (hydroxy), 3340, 1740, 1655, 1530 cm~l. lH
MMR (300 MHz, DMSO) ~ 8.05-7.50 (9H, m).
209286~
- 24 - C6167 (C)
4-CarbomethoxYbenzoyl aniline
4-Carbomethoxybenzoyl chloride (11 g, 0.055 mol) dissolved
in chloroform (200 ml) was stirred under nitrogen by a
mechanical stirrer. The flask was cooled to 0C, and a
solution of aniline (20.64 g, 0.222 mol) in chloroform (35
ml) was added dropwise. A white precipitate formed during
addition. After 2 hours at room temperature, the
chloroform was removed by rotary evaporation. The product
was washed with 10% HCl, filtered on a frit, washed
several times with water, and washed with chloroform.
Recrystallization from toluene gave 5.02 g (34%) of a
white powder; m.p. 194-195C. lH NMR (200 MHz, DMSO-d6)
10.45 (lH, s), 8.09-7.34 (9H, M), 3.91-3.90 (3H, m); IR
(nujol) 3380, 1720, 1665, 1605, 1540, 1330, 1285, 1170,
1120, 760, 730 cm~l; 13C NMR (50 MHz, CDC13/CD3COCD3) ~
166.3, 165.2, 139.2, 138.5, 132.7, 129.6, 128.9, 127.6,
124.4, 120.5.
4-Percarboxvbenzoyl aniline (PCBA)
(4-Carbomethoxybenzoyl)aniline (4.78 g, 0.0187 mol) was
dissolved in methanesulfonic acid (25 ml). Hydrogen
peroxide (2.13 ml of a 70% solution, 0.056 mol) was added
dropwise. After 5 hours at room temperature, the reaction
was worked-up as usual to give 3.86 g (80%) of a pale
yellow powder. Iodometric titration indicated 66%
peracid, 4.1% a.o. IR (nujol) 3320 (hydroxyl), 1750
(peracid carbonyl) cm~l, lH NMR (200 MHz, DMSO-d6) ~ 11.90
(lH, br s), 10,42 (lH, s), 8.11-7.09 (9H, m), 3.90 (ester,
20%).
2~9~
.
- 25 - C6167 (C)
.:
Exam~le 12
N, N, N' c N' -1, 2L4,5-tetracarboxybenzoyl-d ~6-aminocaproic
acid)
1,2,4,5-tetracarboxybenzene dianhydride (20 g, 0.0917 mol)
and 6~aminocaproic acid (24.6 g, 0.188 mol) were suspended
in 200 ml of DMF and heated to 120C. The solids
dissolved when heated. After 3 hours, the solution was
cooled, poured onto ice-water and filtered. The solids
were purified by stirring in 500 ml of hot methanol and
allowing to cool; yield 30 g (74%) of a white solid; IR
(nujol) 1770, 1705 (br), 1055 cm~l; lH NMR (200 MHz, DMSO-
d6) ~ 12.0 (2 H, s), 8.15 (s, 2 H), 3.61 (2 H, t), 2.2 (2
H, t), 1.8-1.2 (6 H, m); 13C NMR (50 MHz, DMSO-d6) ~ 175.0,
166.6, 137.2, 118.0, 38.1, 33.7, 27.8, 26.0, 2~.3.
; N,N,N' ,N' -1, 2,4,5-tetracarboxybenzoyl-di(6-
; aminoPercarboxYcaProic acid) (DIPAP)
The dimide dicarboxylic acid (7.0 g, 0.0224 mol) above was
` dissolved in 55 ml of methanesulphonic acid and treated
`~ with 70% hydrogen peroxide (5.0 ml, 0.134 mol). After a
short time, the reaction mixture became very thick and it
was necessary to use a mechanical stirrer. The mixture
was poured onto ice-water after 5 hours at room
temperature and isolated as described previously. The
activity was 98%; IR (nujol) 3270, 1760, 1740, 1710, 1155,
1055 cm~l.
.
20928~
- 26 - C6167 (C)
~xample 13
N,N'-Tere~hthalo~l-di(6-amino~eroxyca~roic acid) ~TPCAP
N,N'-Terephthaloyl-di~6-aminocaproic acid)* (5.01 g,
0.0127 mol) was dissolved in 30 ml of methanesulfonic acid
and treated with hydrogen peroxide (4.33 ml of 70%, 0.114
mol) at 0C. The mixture was stirred at room temperature
for S.5 hours then worked-up as usual. Yield 4.91 g
(92~); activity 88% (6.7% a.o., theory 7.6%); IR (nujol)
330, 3200, 1760, 1740, 1630, 1545 cm~l.
*zinner, H.; Sych, G.; Ludwig, W. J. Prakt. Chem. 17, 147-
153 (1962).
Exam~le 14
N,N'-Di(4-carboxvaniline~ter~hthalate
4-Aminobenzoic acid (2.1 eq, 14.11 g, 0.103 mol) and
sodium carbonate (5 eq, 25.92 g, 0.245 mol) were stirred
rapidly in 4000 ml water. Ground terephthaloyl chloride
was added portionwise at room temperature. After stirring
for 72 hours, the solution was poured onto 10% HCl. The
solids were collected by filtration and washed with water
to give 16.6 g (83% yield) of a white powder. An impurity
in this product is N-(4-carbox~benzoyl)4-aminobenzoic
acid, which is the monoaddition adduct (less than 3%). lH
NMR (200 MHz, DMSO-d6) ~ 10.74 (2 H, s), 8.15-7.90 (12 H,
m), 3.4 (2H, br s); IR (nujol) 3360, 1690, 1660, 1610 cm~l.
N~N'-Di(4-Percarboxyaniline)terephthalate (DPCAT)
N,N'-Di(4-carboxyaniline)terephthalate (4.98 g, 0.012 mol)
was suspended in 60 ml of methanesulfonic acid and treated
~'
~- .
2~2~fi4
- 27 - C6167 (C)
with hydrogen peroxide (4.09 ml of a 70% solution, 0.108
mol). The mixture was heated at 30C for 4.5 hours, then
isolated as usual. Activity 91%, 6.7% a.o. (theoretical
7.3% a.o.). IR (nujol) 3380, 3200, 1740, 1660, 1600 cm~'.
Exam~le 15
N/N-PhthaloYl-4-aminobenzoic acid
Phthalic anhydride (10.0 g, 0.0675 mol) and 4 aminobenzoic
acid (9.35 g, 0.0682 mol) were dissolved in 100 ml of
anhydrous DMF and heated to 120C for 4.5 hours. The
mixture was cooled, poured onto ice water and filtered.
Recrystallization from ethanol-water provided 6.6 g (37%)
of a fluffy white solid; mp 189-190; IR (nujol) 1780-1745,
1725, 1695, 1605 cm~l; lH NMR (200 MHz, DMSO-d6) ~ 13.1 (lH,
s), 8.2-7.58 (4H, aa'bb'), 8.06-7.9 (4H, m); 13C NMR (50
MHz, DMSO-d6) ~ 166.69, 166.65, 135.81, 134.82, 131.48,
129.88, 129.82, 126.99, 123.54.
N,N-Phthaloyl-4-aminoperbenzoic acid (PhenY1 PAP)
To a suspension of N,N-phthaloyl-4-amino-benzoic acid
(4.03 g, 0.0151 mol) in 60 ml methanesulfonic acid was
added 70% hydrogen peroxide (2.29 ml, 0.0605 mol) at room
temperature. After 6 hours the reaction was worked-up as
usual and stored as a wet filter cake (6.23 g). A dried
sample contained 84% peracid; mp 173 (discolour); IR 3305,
1785, 1760, 1730, 1700, 1600, 1510, 1075 cm~l; 1H NMR (200
MHz, DCDl3) ~ 11.7 (lH, s) 8.4-7.55 (8~, m).
20~2~6l~
- 2~ - C6167 (C)
xam~le 16
Peracid Stabilitv_in a Heavv-Dutv Li~uid
The formulation used for this study contained 35% surface-
actives and had a pH of 4.5 which was obtained with a
borax/sorbitol pH jump system. The peracid was dosed at
2,500 ppm. Table I contains the base formulation. The
tested formulations (base including peracid) were stored
at 40C and aliquots were removed periodically and
titrated for the percent of remaining peracid. Half-lives
of the tested fonnulations are reported in Table II.
?able 1
--~1
BASE FORMULATION OF PH-JUMP LIQUIDS*
___ ~
Water 38.1
: _ _
Sorbitol (100%) 19.6
. __ . _ _ .
Borax 10 aq 5.0
NaOH (100%) 2.9
_
Decoupling polymer (100%) 1.0
. ... ~
Neodol 25-9 10.5
LAS-acid (96%) 22.9
_~ ~
*Initial pH = 4.5
2~92~6~
- 29 - C6167 (C)
able II
PERACID STABILITY IN A HEAVY-DUTY LIQUID
_~ ___
.. tl/s
Peracid 4QC (davs)
_--___
PCBPIP 79
DPCAT 65
Phenyl PAP 48
SDPCA
PCBED 34
_
1,2-PCBPD . _ _ _ _ _ _
: DPAPD 32
DIPAP 29
_
TPCAP 25
_
PCBBD 15
SBPB 11
_ _ , . .. _~
PCBA
DPDA 5
~A
All the amido peracids were more stable than DPDA in the
heavy-duty liquid. Five of these had half-lives of
greater than 30 days. PCBPIP had a remarkable 79-day
half-life at 40~C.
: 25 * 4, 4'-sulfonylbisperoxybenzoic acid described in
EP 267 175.
209~
- 30 - C6167 (C)
For purposes of the present invention, it is advantageous
to achieve a peroxide stability half-life at 40C of at
least 10 days, preferably at least 15 days, more
preferably at least 30 days, and optimally beyond 50 days.
Exam~e 17
Water Solubilitv
A basic premise of this invention is that the solubility
of a peracid affects its stability in a formulation.
Consequently, the water solubility value of various
peracids has been rneasured and these values correlated
with peroxide stability.
The solubility experiments were conducted by rapidly
stirriny 0.2 g of the finely ground peracid in 50 ml of
Milli-Q water containing 0.01 gl~l of a phosphonic acid
Dequest 2041. The solution was heated to 40C for 15
minutes then equilibrated to 25.0C(+~C) using a water
circulating bath. After 2 hours, the stirring was stopped
and the solids were allowed to settle. An aliquot was
filtered using a polypropylene disposable syringe fitted
with a Millex-HA 0.45 ~m filter unit. The pH of the
filtrate was between 4.5 and 5Ø The clear filtrate was
treated with potassium hydrogen phthalate buffer and
potassium iodide and the concentrate of triiodide
determined spectrophotometrically according to the method
of Davies (Davies, D.M.; Deary, M.E. Analyst {1988}, 113,
1477-1479.) This procedure was repeated one hour later to
be sure an equilibrium value had been obtained. The
reproducibility of the method was found to be ~10%.
~'
:
:
.... ~ .
- 2~928fi~
.
- 31 - C6167 (C)
The results are presented ln Table III. The monoperacids
and diperacids are listed separately because the errors in
measuring the two types are believed to be different. The
analysis of the solubility of the diperacids may be
dependent on the purity of the sample used for the
measurement, but the analysis of the solubility of the
monoperacids should be independent of purity. This is
because the measurement is an active oxygen determination.
Whereas contaminants such as unreacted carboxylic ester or
acid will not interfere in the measurement of a
monoperacid, a low purity diperacid will contain species
with one carboxylic ester (or acid) group and one peraci.d
group. These molecules may have different solubility
properties than the desired molecule and the active oxygen
content per molecule will be only half of that for the
diperacid.
Thus, two concentrations are listed in Table III, the
titratable percarboxyl groups and the concentration of the
molecule.
2092~
- 32 - C6167 (C)
Table III
_~____.
SOLUBILITY OF SELECTED PERACIDS IN WATER
(pH 4.5 to 5.0)
___ __~ __
Concentration Concentration % Peracid
of a.o. inof Molecule
solutionin solution
_-- (10 sM)(10-sM) . _ _
Monoperacids
Phenyl PAP 1.2 1.2 84
_ ___ .
PCBA 6.8 6.8 65
BP-PABA 8.8 8.8 79
PAP 62.0 62.0 89
_
Diperacids
PCBBD 1.9 0.9 68
PCBED 1.9 0.9 69
1,2-PCBPD 2.0 1.0 70
15 DIPAP 2.2 1.1 98
PCBPIP 2.3 1.2 e 79
SBPB 4.8 2.4 61
; DPAPD . 7.4 3.7 92
TPCAP 9.0 4.5 88
20 DPDA _ 95
