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Us5952290 PDF
Us5952290 PDF
R O Rs
R O R4
55 R-C-C-N-R-YZ.
X
R O Rs
R-C-C-N-R-YZ.
R. O. Rs
60
wherein R-R, have been hereinbefore defined and Y is
wherein R, R, R2, and R are Selected from the group SO and Z is Na"
consisting of Straight or branched chain C to C alkyl, aryl
or hydrogen and each R-R of the moieties can be the same
or different; R and Rs are Selected from the group com 65 A fourth anionic gemini Surfactant falling within the
prising a Straight or branched chain C to C alkyl with the Scope of the present inventors is represented by the Struc
further proviso that when either is a C it may exist as a tural formula:
5,952.290
IV
R O R4
NH 1N1 SONa+ HO ( ) OH
Br
S
sco
R.----R-yz 1O
NH 1N1 SONa
R O Rs
HoC
19V-9 CI a)
He
b) ch
S
Br
O H19C9 NH
50 n1N SONa
H19C9 NH 1N-SONa O
Br
a) NaOSCHCH-NH, 55 Intermediate A compound (8.0 gm., 19.6 mmol) was
b) Na2CO3 dissolved in methanol and this was added to a Solution of
ethylenedithiol 1.0 gm., 9.6 mmol in methanol. Excess
C-Bromolauric acid chloride (20gm., 67.3 mmol) was Sodium carbonate was added to the Solution. The reaction
added dropwise to a Saturated Sodium taurinate/sodium was refluxed for a few hours and then Stopped by cooling it
carbonate solution at 5 C. The solution became cloudy 60 to room temperature. The crude product was extracted twice
immediately. The reaction temperature was allowed to warm with m-butanol, followed by the collection of the organic
up to room temperature and the reaction was stirred for 5 layer which was then rotoevaporated under reduced pres
hours. The final white powder product was collected by Sure. The remaining material was washed with ethanol once.
filtration. After drying under vacuum, the final product was The final powder material was collected by filtration and
taken for Nuclear Magnetic Resonance (NMR) analysis. The 65 then taken for NMR analysis. The NMR results agreed with
NMR spectrum generated agreed with the expected Structure the expected structure of the product. The yield was about
of the final product. The yield of the reaction was about 95%. 82%.
5,952.290
9 10
EXAMPLE 3 Distilled water Solutions at different concentrations were
Preparation of Ether Linked Derivative III prepared for each of the test Surfactants in 100 mL amounts.
The mixtures were Stirred until homogeneous Solutions were
obtained. The Surface tensions of these Solutions were then
O measured.
SONa + From the Surface tension data, the area/molecule area at
H19C9 NH1N1 the interface and efficiency of adsorption were computer by
use of the appropriate Gibb's Adsorption Equation:
Br
A 1O -dy
O a logCT / 2.303RT
DMF
HO OH Na2CO3
where
O 15
p=Surface excess concentration mol/cm)
dy=change in Surface or interfacial tension of the Solvent
H19Co NH 1.N- SONa dyne cm)
R=8.31x107 erg mol' K'
O C=molar concentration of Solution
T=absolute temperature IK
pC-20 at the Solution/air interface is defined as the nega
tive logarithm of the Surfactant concentration required
to lower surface tension by 20 dyne/cm.
The results obtained for the Surfactants alone are reported
O 25 in Table I.
HoC NH TABLE I
19V-9 N1NsoNa
Surface Activity
O
III. Surfactant cmc M
Example 1 3.98 x 10
Example 2 1.99 x 10
Intermediate compound A 16.0 gm., 39.2 mmol and N-Methylcocotaurinate* 3.16 x 10
hydroquinone 2.0 gm., 18.2 mmol) were dissolved in dry 35 (Coco N(CH)CHCHSONa)
dimethyl formamide DMF) at room temperature. Excess
Sodium carbonate was then added to the Solution. The *Conventional anionic single chain surfactant - Geropon (E) TC42.
reaction was stirred for 15 hours at 85 C. and then stopped
by cooling to room temperature. The crude product was When the surface properties for the anionic sulfonate
extracted twice with m-butanol and the organic layer was compounds of the present invention are compared to the
collected and rotoevaporated under reduced pressure. The 40 corresponding conventional anionic Species Such as
remaining material was washed with methanol and the N-methylcocotaurinate as shown in Table I, the novel com
organic layer was collected and evaporated under reduced pounds of the present invention show unexpected Surface
preSSure. The final remaining material was dried under active properties and unusually low critical micelle concen
vacuum and then analyzed by NMR. NMR results agreed tration cmc values in aqueous media. This property is a
with the expected structure of the product while the yield 45 measure of the tendency of the Surfactant to form micelles,
was about 70%. and adsorb at the interface, and consequently, to reduce
EXAMPLE 4 Surface tension. The values shown in Table I demonstrate
Surfactant Surface Properties that the Sulfonates are one to two orders of magnitude or 10
to 100 times more effective at forming micelles. This
The Surfactants of the invention were measured for criti 50 unusually high Surface activity for these molecules is a result
cal micelle concentration and their ability to reduce Surface of their unique structure; the presence of two optimally
tension. Spaced hydrophobic moieties and hydrophilic groups. This
The test methods utilized are described as follows: molecular Structure provides energetically favorable
Critical Micelle Concentration (CMC) decreases in the free energy of adsorption and micellization
Aqueous Solutions of each Surfactant were prepared at 55 through favorable distortion of the water structure, while
varying concentrations. The Surface tension at 20° C. were Simultaneously providing a “closed packed' arrangement at
measured by the Wilhelmy plate method and plotted vs. the the interface as reflected by the unusually low area per
logarithm of the concentration. The critical micelle concen molecule compared to that which would be expected from
tration was determined as the value at which the Slope of the the molecular dimensions. The ability of the compounds of
line changed abruptly. 60 the invention to distort water structure through inhibition of
Surface Tension Reducing Ability gamma CMC crystalline or liquid crystalline phase formation in the bulk
The Surface tension reducing ability was determined from phase and at the same time to pack closely on adsorption at
the Surface tension of the Surfactant that exists at the critical the interface is contrary to conventional wisdom. This again
micelle concentration. demonstrates the uniqueness of the molecular design for
Surface tension measurements were made for each of the 65 these compounds which is very critical to providing
referenced Surfactants, using a KruSS K-12 Tensiometer unexpected, exceptional Surface and performance proper
plate method. Each experiment was carried out as follows: ties.
5,952.290
11 12
Exceptional Surface activity and unique Structural features the further proviso that when either is C, it can be a
for the compounds of the invention provide two other cyclohexyl ring; R and R, are Selected from the group
important performance properties that can have immense consisting of Straight or branched chain C to C alkyl or
practical application in industry. They are hydrotropicity, aryl with the further proviso that R and R, may be the same
which is the ability of organic Substances to increase the 5 or different, X is Selected from the group comprising-S-,
Solubility of other, insoluble organic Substances in water and S-S-, -D-Rs D-, or -R-D-Rs wherein
Solubilization, the dissolving of water insoluble organic Rs is a Straight or branched chain C to Co alkylene or
compounds into aqueous Surfactant Solutions above their arylene and D is selected from the group consisting of
critical micelle concentrations. The compounds of the -O-, -S-, -S-S-, -SO; Y is OPO - or -SO
and can be the same or different and Z is selected from the
invention, because of their very low cmc values, are efficient 1O group comprising Na, K, alkali or alkaline earth metals,
solubilizers. This latter property will not only allow the ammonium, their Salts and mixtures thereof.
formulation of homogeneous water insoluble materials, but
also will enhance the Surface activity of other Surfactants ing2.the The Surfactant composition of claim 1 further compris
Structure:
whose low water solubility restricts their use. These novel
Surfactants of the invention are far better than comparable 15 R2 O R4
conventional Surfactants in hydrotroping and Solubilizing
properties. R-C-C-N-R-YZ
Because of their unusually high Surface activity coupled
S
with their hydrotropicity and Solubilization properties, com
pounds of this invention will provide exceptionally high 2O R-C-C-N-R-YZ
performance properties, at very low concentration, in prac
tical applications Such as detergency emulsification, R O Rs
Solubilization, disperSancy, hydrotropicity, foaming and
wetting. Because of their greater Surfactant efficiency as
indicated by the extremely low cmc and pC-20 values, from 25 wherein R, R, R2, R., R., Rs. R and R7 have been
10 to 100 times lower concentrations of the compounds of hereinbefore defined and Y is SO and Z is Na
the invention can be used compared to the invention than ing3.the The surfactant composition of claim 1 further compris
Structure:
conventional Surfactants, Substantially reducing the need for
the Surfactant component to achieve equivalent results and
thus reducing the amount of Surfactant released into waste 3O R O R4
treatment facilities. Additionally, Since the cmc is the maxi
mum free Surfactant concentration that is, uncomplexed in
micelles under use conditions, this lower level of the active S
Species should result in a much lower level of irritancy, even CH2
essentially none, if as is likely, it is below the irritancy 35
threshold concentration. CH2
Surface Activities of Mixtures
S
The unusually high Surface activity of the anionic Surface
active agents of the invention make them the Surfactants of
choice in enhancing the Surface activity of mixtures con 40
taining other conventional, Significantly leSS Surface active R O Rs
Zwitterionic, amphoteric, nonionic and cationic Surfactants.
The anionic gemini Surfactant compounds of the invention
provide Significant, unexpected improvement in the Surface wherein R, R, R2, R., R., Rs. R and R7 have been
activity of blends of these compounds with the above types 45 hereinbefore defined and Y is SO and Z is Na
of Surfactants, even when used in very Small amounts. The ing the Structure: composition of claim 1 further compris
4. The Surfactant
improvement is beyond that which would be estimated from
an average of the properties of the components of the
Surfactant mixture, hence showing positive Synergism. R O R4
What we claim is:
1. An anionic Surfactant composition comprising one or 50 R--c-N-R-yz
more compounds of the formula: O
R O R4
55
R-C-C-N-R-Y-Z
X
O
R-C-C-N-R-Y-Z
60 R-C-C-N-R-YZ
R. O. Rs
R3 O Rs
wherein R, R, R2, and R are Selected from the group
consisting of Straight or branched chain C to C alkyl, aryl wherein R, R., R., R., R., R., R and R, have been
or hydrogen and each of the respective R moieties can be the 65 hereinbefore defined and Y is SO and Z is Na'
Same or different; R and Rs are Selected from the group 5. The surfactant composition of claim 1 further compris
comprising a straight or branched chain C to C alkyl with ing the Structure:
5,952.290
13 14
group consisting of anionic Surfactants, nonionic
R2 R4 Surfactants, cationic Surfactants, amphoteric Surfactants, and
mixtures thereof.
10. A Surfactant blend comprising the compound of claim
S 5 and one or more additional compounds Selected from the
group consisting of anionic Surfactants, nonionic
S Surfactants, cationic Surfactants, amphoteric Surfactants, and
mixtures thereof.
11. A cleaning composition comprising compounds of
R. O. Rs claim 1.
12. A cleaning composition comprising the compounds of
claim 2.
wherein R, R, R2, R., R., Rs. R and R7 have been 13. A cleaning composition comprising the compounds of
hereinbefore defined and Y is SO and Z is Na' claim 3.
6. A Surfactant blend comprising one or more of the 15 14. A cleaning composition comprising the compounds of
compounds of claim 1 and one or more additional com claim 4.
pounds Selected from the group consisting of anionic 15. A cleaning composition comprising the compounds of
Surfactants, nonionic Surfactants, cationic Surfactants, claim 5.
amphoteric Surfactants, and mixtures thereof. 16. A cleaning composition comprising the Surfactant
7. A Surfactant blend comprising the compound of claim blend of claim 6.
2 and one or more additional compounds Selected from the 17. A cleaning composition comprising the Surfactant
group consisting of anionic Surfactants, nonionic blend of claim 7.
Surfactants, cationic Surfactants, amphoteric Surfactants, and 18. A cleaning composition comprising the Surfactant
mixtures thereof.
8. A Surfactant blend comprising the compound of claim blend of claim 8.
25
3 and one or more additional compounds Selected from the 19. A cleaning composition comprising the Surfactant
group consisting of anionic Surfactants, nonionic blend of claim 9.
Surfactants, cationic Surfactants, amphoteric Surfactants, and 20. A cleaning composition comprising the Surfactant
mixtures thereof. blend of claim 10.
9. A Surfactant blend comprising the compound of claim
4 and one or more additional compounds Selected from the