US 20070220803A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2007/0220803 A1
Henry, JR. (43) Pub. Date: Sep. 27, 2007
(54) ENHANCED ANTISTATIC ADDITIVES FOR Publication Classification
HYDROCARBON FUELS & SOLVENTS
(51) Int. Cl.
(76) Inventor: Cyrus Pershing Henry JR. Avondale, CIOL I/24 (2006.01)
PA (US) CIOL L/22 (2006.01)
(52) U.S. Cl. ................................................. 44/370; 44/432
Correspondence Address:
BURNS & LEVINSON, LLP (57) ABSTRACT
125 SUMMER STREET
BOSTON, MA 02110 (US) Described herein are enhanced performance of antistatic
additive compositions for hydrocarbon fuels, the composi
(21) Appl. No.: 11/389,607 tions comprising olefin-sulfur dioxide copolymers in com
bination with polymeric polyamines prepared using an
(22) Filed: Mar. 24, 2006 ortho-xylene solvent.
US 2007/0220803 A1 Sep. 27, 2007

ENHANCED ANTISTATIC ADDITIVES FOR having from about 4 to 24 carbon atoms, and from about 0
HYDROCARBON FUELS & SOLVENTS to 10 mol percent of units derived from an olefinic com
pound having the formula ACH=CHB wherein A is a group
FIELD OF THE INVENTION having the formula—(CH) COOH wherein X is from 1
to about 23, and B is hydrogen or carboxyl, with the proviso
0001. This invention concerns an improved two-compo that when B is carboxyl, X is 1, and wherein A and B together
nent antistatic additive for hydrocarbon fuels and solvents to can be a dicarboxylic anhydride group, the antistatic com
render them electrically conductive. One component is an position comprises, in combination with said polysulfone
olefin-sulfur dioxide copolymer (polysulfone copolymer) component, a polymeric polyamide of the formula

prepared in orthoxylene, and the other component is a 0007) R' is an aliphatic hydrocarbyl group of 4 to 24
particular polymeric polyamine. carbon atoms,
BACKGROUND OF THE INVENTION 0008 R is an alkylene group of 2 to 6 carbon atoms,
0002 Hydrocarbon fuels normally are very poor conduc 0009 R is R', or, an N-aliphatic hydrocarbyl alkylene
tors of electricity. Electrical charges, therefore, tend to group of the formula R'NHR,
accumulate in the fuel and can be discharged as sparks thus 0010) a is an integer of 0 to 20,
creating the danger of an explosion or fire should such
charges ignite hydrocarbon-air admixtures that may be 0011 b is an integer of 0 to 20,
present.
0012 c is an integer of 0 to 20, and
0003) Numerous materials have been suggested in the art
to increase the electrical conductivity of hydrocarbon fuels. 0013 x is an integer of 1 to 2,
Suggested materials include two-component additives
where one component is a polysulfone and the other is a 0014) with the proviso that when R is R' then a is an
quaternary ammonium compound. Another Suggested two integer of 2 to 20 and b=c=0, and when R is R'NH R then
component additive comprises polysulfone as one compo a is 0 and b+c is an integer of 2 to 20.
nent and polyvalent metal organic compounds of metals 00.15 Particular embodiments of this invention are those
having an atomic number of from 22 to 29 as the other wherein the polysulfone is composed solely of units derived
component. from sulfur dioxide and units derived from at least one
0004 An important aspect is the solvent used for the 1-alkene of from 4 to 24 carbon atoms. A particular embodi
polymerization of the poly Sulfone component. Typically, ment is that wherein the 1-alkene is 1-decene and is prepared
Solvents such as benzene, toluene, et al. have been in an ortho-Xylene solvent.
employed. These solvents contain impurities which may 0016 One embodiment, with reference to the polyamine
result in a potentially toxic situation. Thus, there is a clear component, is that where R=R', wherein R' is an aliphatic
need to employ a safer solvent. hydrocarbyl group of 4 to 24 carbon atoms, especially where
BRIEF SUMMARY OF THE INVENTION
R" is the aliphatic hydrocarbyl group of tallowamine.
0017 Also, with reference to the polyamine component,
0005 The two-component antistatic additives of this are embodiments where R is R'NHR, wherein R' is an
invention are characterized by being highly effective at low aliphatic hydrocarbyl group of 8 to 22 carbon atoms and R'
levels of usage and by being ashless upon burning. These is an alkylene group of 3 carbon atoms, especially where R'
two-component antistatic additives are so efficient that even is the aliphatic hydrocarbyl group of tallowamine.
at relatively low concentrations they provide the desired
conductivity (measured in picomhos per meter, or picoSi 0018. In one aspect of the invention, a polysulfone
emens/meter) in nearly all hydro-carbon fuels. This perfor copolymer of the invention is 1-decene polysulfone having
mance is enhanced when the solvent for polymerization of an molecular weight in the range of 10,000 to 1,500,000 amu
the olefin and sulfur dioxide is ortho-xylene. and in a particular aspect, the polymeric polyamine is the
polymeric 1:1.25 mol ratio reaction product of N-tallow-1,
0006. In the antistatic additive of this invention wherein 3-diaminopropane with epichlorohydrin.
the components are presented in a weight ratio of 100:1 to
1:100, and wherein one component is a polysulfone copoly 0019. The weight ratio of polysulfone copolymer to poly
mer prepared in ortho-Xylene solvent comprising about 50 meric polyamine in the invention composition ranges from
mol percent of units from sulfur dioxide, about 40 to 50 mol about 100:1 to 1:100, in one aspect from about 50:1 to 1:1,
percent of units derived from one or more 1-alkenes each and in another aspect from about 20:1 to 1:1.
US 2007/0220803 A1 Sep. 27, 2007

0020. This invention also concerns the two-component carboxyl, with the proviso that when B is carboxyl, X is 0.
additive as heretofore described together with a strong acid and wherein A and B together can be a dicarboxylic anhy
(oil-soluble Sulfonic acid is Suitable). Thus, a polyamine dride group and
sulfonic acid salt will be formed which has an improved 0030 (ii) a quaternary ammonium compound having the
resistance to precipitate-formation during long storage peri formula:
ods. This invention also concerns the additives in concen
trate form in a solvent. One composition containing the
antistatic additive, an acid to enhance precipitate-free
storability, and a solvent, comprises, based on total weight: Alk?

OO21 1. ffrom about

bout 1 to
tO 50percent off the polysulf
poly Sulfone, Alk-N-Alk' A,
prepared in an ortho Xylene solvent, Alk
0022 ii. from about 1 to 50 percent of the polymeric
polyamine,
wherein
0023 iii. from about 1 to 30 percent of oil-soluble
Sulfonic acid, and Alk' and Alki are the same or different alkyl groups having
from 1 to 22 carbon atoms, Alk is selected from the group
0024 iv. from about 3 to 97 percent of solvent. consisting of alkyl groups of 1 to 22 carbon atoms and
0025. A suitable sulfonic acid (iii) is mono and disul
fonates of alky benzenes, and in one aspect is dodecylben Alk
Zene Sulfonic acid, or dinonylnaphthyl Sulfonic acid.
- (CHCHO).H.
0026. This invention also concerns a composition com
prising a liquid hydrocarbon fuel boiling in the range of from
about 20° to 375° C., and from about 0.01 ppm to 40 ppm
of the two-component polysulfone-polyamine antistatic where Alk is hydrogen or methyl and n is 1 to 20,
additive composition and the additive composition stabi Alk' is selected from the group consisting of (a) an alkyl
lized with a strong acid as described herein. Although more group having 1 to 22 carbon atoms, (b) an aralkyl group
than 40 ppm of the additive can be used, no significant having from 7 to 22 carbon atoms, (c) a
benefit is thereby derived. The additive composition can also
be used in solvents, oils, and other mixtures such as paints
and other formulations where improved conductivity is Alk
desired.
-(CH2CHO). H
0027 Certain co-additives which are known to provide
good initial electrical conductivity in cooperation with the
polysulfone copolymer component can also be included in group as defined above, (d) a
the present invention composition. Included are quaternary
ammonium compounds which are more fully described in
coassigned U.S. Pat. No. 3,811,848 (the entire teaching of O
which is herein incorporated in its entirety by reference).
-CHCH-O-P-OCHCH(OCOAlk)CHOCOAIk
0028. It has been found that improved three-component
antistatic compositions can be obtained by combining the O
polymeric polyamine described herein with a two-compo
nent antistatic additive comprising:
group wherein
0029 (i) a polysulfone copolymer prepared in ortho
xylene comprising about 50 mol percent of units derived Alk' and Alk" are the same or different alkyl groups having
from sulfur dioxide from about 40 to 50 mol percent of units from 11 to 19 carbon atoms, and (e) an—Alk—CO, group
derived from 1-alkene of 4 to 24 carbon atoms and from 0 wherein Alk' is a hydrocarbyl group having from 1 to 17
to about 10 mol percent of units derived from an olefin carbon atoms, with the proviso that when Alk', Alk, Alk
having the formula and Alk' are each alkyl groups, at least one of them is an
alkyl group having at least 8 carbon atoms,
A B 0031) A is an anion,
0032) Z is 0 or 1, Z is 0 when Alk" is (d) or (e), and
H H 0033 y is at least 1, y is equal to the ionic valence of
anion A when Z is 1.

wherein 0034. The ratio of the components are such that for each
part of polysulfone there is 0.01 to 100 parts of each of the
A is a group having the formula —(CH)—COOH polymeric polyamine and the quaternary ammonium com
wherein X is from about 0 to about 17, and B is hydrogen or pound.
US 2007/0220803 A1 Sep. 27, 2007

0035) A suitable quaternary ammonium compound is Viscosity are deciliters per gram (dl/g). The inherent vis
dicocodimethyl ammonium nitrite wherein “coco refers to cosities of olefin poly-sulfones are conveniently measured in
a mixture of Cs to Cs alkyl radicals of cocoamine. The toluene at 30° C. as 0.5 weight percent solutions. It has been
quaternary ammonium compound can be present in the found by comparison with molecular weight determinations
amounts of from about 1 part to 25 parts per 100 parts of that polysulfones with inherent viscosities of between about
polysulfone copolymer. The presence of a quaternary 0.1 dl/g to 1.6 dl/g correspond to weight average molecular
ammonium compound further enhances the electrical con weights in the range of about 50,000 to 900,000.
ductivity of the present invention composition in many
hydrocarbon fuels and maintains the composition ash-free. 0042. The control of the molecular weights of the olefin
polysulfones in the desired range is readily accomplished by
0036) Another embodiment of the present invention is those skilled in the art of polymer science by controlling the
directed to a fuel oil composition. This fuel composition can polymerization conditions such as the amount of initiator
comprise a Suitable fuel component and a suitable additive used, polymerization temperature and the like or by using
component. In one aspect, the composition comprises from molecular weight modifiers such as dodecyl mercaptan. The
about 99.99% fuel and about 0.01% of additive to about amount of molecular weight modifier required to obtain the
99.9999% fuel to about 0.0001% of additive. A Suitable desired molecular weight range will depend upon the par
additive includes those described herein. ticular 1-olefin being polymerized with sulfur dioxide, and
0037. The term “hydrocarbyl” employed herein refers to can be determined easily with few experiments. Generally,
straight and branched-chain groups containing only carbon the amount of modifier, Such as dodecyl mercaptan, used to
and hydrogen. Such groups can be saturated, unsaturated or obtain the molecular weights in the range of 50,000 to
aromatic. 900,000 is in the range of up to about 0.007 mole per mole
of 1-olefin.
0038 For a better understanding of the present invention,
together with other and further objects thereof, reference is 0043. The 1-alkenes useful for the preparation of the
made to the accompanying drawings and detailed descrip polysulfones are available commercially as pure or mixed
tion and its scope will be pointed out in the appended claims. olefins from petroleum cracking processes or from the
polymerization of ethylene to a low degree. Included, but
DETAILED DESCRIPTION OF THE not limited to, are 1-hexene, 1-heptene, 1-octene, 1-nonene,
INVENTION 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tet
radecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
The Polysulfones: 1-octadecene, 1-nonodecene, 1-eicosene, 1-heneicosene,
0.039 The polysulfone compolymers often designated as 1-docosene, 1-tricosene and 1-tetracosene. Poly unsaturated
olefin-sulfur dioxide copolymer, olefin polysulfones, or olefins such as butadiene and its analogs, and branched
poly(olefin sulfone) are polymers wherein the structure is olefins and internal olefins are also utilizeable in the inven
considered to be that of alternating copolymers of the olefins tion. Although branched-chain alkenes are useful, the
and Sulfur dioxide, having a one-to-one molar ratio of the straight-chain 1-alkenes are also useful whether pure or in
comonomers with the olefins in head to tail arrangement. admixture with other straight-chain 1-alkenes.
The polysulfones used in this invention are readily prepared 0044) When the polysulfone copolymer contains up to 10
by the methods known in the art (cf. Encyclopedia of mol percent of the olefin AHC=CHB, as defined above. A
Polymer Science and Technology Vol. 9, Interscience Pub and B can together form a dicarboxylic anhydride group.
lishers, page 460 etc., the entire teaching of which is incor The dicarboxylic anhydride group is readily converted to
porated herein by reference). two carboxyl groups by simple acid hydrolysis. The olefin,
0040. The weight average molecular weights of the AHC=CH, is a terminally unsaturated alkenoic acid rep
polysulfones are in the range from about 10,000 to about resented by CH=CH-(CH) COOH. The alkylene
1,500,000, in one aspect the range is from about 50,000 to group bridging the vinyl and the carboxyl groups can have
about 900,000, and in another aspect the molecular weights from 1 to 24 carbon atoms or it can be absent, and Such
range from about 100,000 to about 500,000. Olefin polysul alkylene group when present can be a straight chain group
fones whose molecular weights are below about 10,000, or branched chain. The useful acids are alkenoic acids of 3
while effective in increasing conductivity in hydrocarbon to 20 carbon atoms wherein the olefinic group is a terminal
fuels, do not increase the conductivity values as much as group. Representative but nonlimiting examples of alkenoic
olefin polysulfones of higher molecular weights. Olefin acids with a terminal olefinic group include acrylic acid,
polysulfones whose molecular weights are above about 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-hep
1,500,000 are difficult to produce and are more difficult to tenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic
handle. acid, 10-undecenoic acid, 11-dodenoic acid, 13-tetrade
cenoic acid, 15-hexadecenoic acid, 17-octadecenoic acid as
0041. The molecular weights of the olefin polysulfones well as branched chain alkenoic acids with terminal olefinic
can be determined by any of the well-known methods, such groups such as 2-ethyl-4-pentenoic acid, 2,2-dimethyl-4-
as the light scattering method. It is generally more conve pentenoic acid, 3-ethyl-6-heptenoic acid, 2-ethyl-6-hep
nient, however, to determine the inherent viscosity of the tenoic acid, 2,2-dimethyl-6-heptenoic acid, and the like. It
polymer to derive the approximate molecular weight range should be understood that a mixture of alkenoic acids can be
of the polysulfones therefrom. Inherent viscosity is defined used.
as mil-ln.m/C wherein In is the natural logarithm, me is
a relative viscosity, i.e., ratio of the viscosity of the polymer 0045. The reaction leading to polysulfone formation is
solution to the viscosity of the polymer solvent and C is the art-known free-radical polymerization process. Nearly
concentration of polymer g/100 mL. The units of inherent all types of radical initiators are effective in initialing
US 2007/0220803 A1 Sep. 27, 2007

polysulfone formation. Radical initiators such as oxygen, being independent of the pressure. The polymerization tem
oZonides, t-butylperoxy-pivalate, hydrogen peroxide, ascari perature can be any convenient temperature below the
dole, cumene peroxide, benzoyl peroxide, azobisisobuty ceiling temperature of the particular 1-alkene employed.
ronitrile are examples of some of the useful initiators. Ceiling temperature is the temperature at which the rates of
Free-radicals are generated from Such radical initiators polymerization and depolymerization are equal so that no
either thermally and/or by light activation in the presence of polymer formation takes place. The above mention “Ency
a mixture of sulfur dioxide and 1-alkene. The polymeriza clopedia of Polymer Science and Technology' on page 466
tion can be carried out in liquid phase, conveniently in a lists ceiling temperatures for various 1-alkenes. Generally,
solvent such as benzene, toluene or xylene to facilitate the the convenient polymerization temperature range is from
reaction. In one aspect of this invention, ortho-Xylene ("o- about 0° to about 50° C.
xylene') is the solvent employed. Such solvent can be The Polymeric Polyamines:
removed, e.g., by distillation, if desired, but it is generally
more the convenient to use the polysulfone copolymer as a 0049. The polyamine component of the antistatic com
concentrate in Such solvent. Generally, it is typical to use an position of the present invention is a polymeric reaction
excess of sulfur dioxide since any unreacted sulfur dioxide product of epichlorohydrin with an aliphatic primary
is readily removed as by passing nitrogen gas into the monoamine or N-aliphatic hydrocarbyl alkylene diamine.
polymer Solution. An exess of 1-alkene can be used, how The polymeric reaction products are prepared by heating an
ever, and the excess Subsequently removed as by distillation. amine with eipchlorohydrin in the molar proportions of from
0046. Using ortho-xylene has several advantages. For about 1:1-1.5 in the temperature range of about 50° to about
example, the use of o-Xylene as a solvent leads to increased 100° C. Generally, with aliphatic monoamines, R'NH2, the
conductivity, an increase of approximately 15% was molar ratio is about 1:1. The initial reaction product is
observed when o-xylene was used (See Tables I and II, believed to be an addition product as illustrated below with
infra.) Ortho-xylene also facilitates the removal of toxins, a primary momoamine, R'NH2,
e.g., ethylbenzene. One also observes an increase in flash
point using o-Xylene, as compared to tolene. This is mainly
due to the difference in the flash points between o-xylene
(86°C.) and Toluene (40° C.)
TABLE I
Comparison of the conductivity enhancement of a Static Dissipater 0050. The aminochlorohydrin (I) upon reaction with an
formulation where the poly Sulfone polymer in the formulation was inorganic base then forms an aminoepoxide.
Drepared in oxylene, to that which was prepared in Toluene.
Formulation Conductivity pSim Conductivity pSim
1 PSI wo-xylene 369 425
2 PSI w/o-xylene 342 388
3 PSI Witoluene 303 345

0047 0051. The aminoepoxide (II), which contains a reactive

epoxide group and a reactive amino-hydrogen, undergoes
TABLE II polymerization to provide a polymeric material containing
several amino groups. The ratio of epichlorohydrin to amine
Conductivity of a Static Dissipater formulations where the poly and the reaction temperature used are such that the poly
Sulfone polymer in the formulation was prepared in Toluene. meric reaction product contains from 1 to 20 recurring units
Formulation Conductivity derived from the aminoepoxide represented by II.
361 pS/m 0052 The polymeric reaction product derived from
338 pS/m epichlorohydrin and an aliphatic primary monoamine as
287 pS/m defined is represented by Subgeneric formula (A),
347 pS/m
296 pS/m
274 pS/m
272 pS/m (A)
242 pSim R1
300 pS/m
RN(CH-CH-CHN).HH
OH
0.048. The particular ratio of 1-alkene to sulfur dioxide
appears to be immaterial since the resultant polysulfone
copolymer contains 1-alkene and Sulfur dioxide in 1:1 molar 0053 where a is an integer from 1 to 20 and X is an
ratio regardless of the particular ratio used. However, for integer of 1 to 2.
efficiency in utilization of the reactants and of the equip
ment, a slight excess of Sulfur dioxide is often employed. 0054 The aliphatic primary monoamines that can be used
The polymerization can be carried out at atmospheric or to prepare the polymeric reaction products with epichloro
Super-atmospheric pressures, the polymerization reaction hydrin can be straight chain or branched chain and include,
US 2007/0220803 A1 Sep. 27, 2007

inter alia, octylamine, nonylamine, decylamine, undecy 0059 When IIa undergoes further condensation, the
lamine, dodecylamine, tridedecylamine, tetadecylamine, recurring units in the product may be
pentadecylamine, hexadecylamine, heptadecylamine, octda
decylamine, nonadecylamine, eicosylamine, heneicosy
lamine, docosylamine, tricosylamine, tetracosylamine and RI
the corresponding alkenyl analogs. The aliphatic primary
amine should have at least about 4 carbon atoms, in one -CH-CH-CH-N-R2-NH-,
aspect, about 12 to 24 carbon atoms to provide polymeric OH
reaction products of sufficient solubility in hydrocarbon HNR
fuels. While aliphatic primary amines containing more than
about 24 carbon atoms are useful. Such amines are of limited R2
availability. -CH-CH-CH-N-
0.055 Mixtures of aliphatic primary amines can also be OH
used, and are typical since mixtures of primary amines
derived from tall oil, tallow, soybean oil, coconut oil, cotton
seed oil and other oils of vegetable and animal origin are or both, since (IIa) contains two reactive secondary amino
commercially available and at lower cost than individual hydrogens. Thus, in Subgeneric formula (B), above, b is
amines. The above mixtures of amines generally contain from 0 to 20, c is from 0 to 20 and b--c is from 2 to 20.
alkyl and alkenyl amines of from about 12 to 18 carbon 0060 Illustrative examples of useful N-aliphatic hydro
atoms, although sometimes an individual amine mixture, carbyl alkylene diamines include, but not limited to, N-oc
depending upon the source, contains Small amounts of tyl, N-nonyl, N-decyl, N-undecyl N-dodecyl N-tridecyl,
primary amines having fewer or more carbon atoms. An N-tetradecyl, N-pentadecyl N-hexadecyl N-heptadecyl,
example of a commercially available mixture of primary N-octadecyl, N-nonadecyl N-eicosyl, N-uneicosyl, N-doco
monoamines is hydrogenated tallow amine which contains Syl. N-tricosyl, N-tetracosyl, as well as the corresponding
predominantly hexadecyl- and octadecylamines with N-alkenyl derivatives of ethylenediamine, propylenedi
Smaller amounts of tetradecylamine. amine, butylenediamine, pentylenediamine and hexylenedi
0056. When the amine reacted with epichlorohydrin is an amine. In one aspect, the N-aliphatic hydrocarbyl-alkylene
N-hydrocarbylalkyl-enediamine as defined, the polymeric diamine is N-aliphatic hydrocarbyl-1,3-propylenediamine.
reaction product is represented by Subgeneric formula (B), The N-aliphatic hydrocarbyl-1,3-propylenediamines are

(B)

RI
R-NH-R-N(CH-CH-CHN-R-NH)(CH-CH-CHN).HH
OH OH

0057 where R' is an aliphatic hydrocarbyl group of 4 to commercially available and are readily prepared from ali
24 carbon atoms, R is an alkylene group of 2 to 6 carbon phatic primary monoamines Such as those described above
atoms, b and c are integers of 0 to 20 and b+c is an integer by cyanoethylation with acrylonitrile and hydrogenation of
of 2 to 20 and X is 1 to 2. the cyanoethylated amine. Mixtures of N-aliphatic hydro
carbyl-1,3-propylenediamines can also be advantageously
0.058. In the reaction of epichlorohydrin with an N-ali used. A typical mixture is N-tallow-1,3-propylenediamine
phatic hydrocarbylalkyl-enediamine, it is believed (because which is commercially available as “Duomeen T” wherein
of the known greater reactivity of primary amino hydrogen “tallow represents predominantly mixtures of alkyl and
over secondary amino hydrogen) that the initially formed alkenyl groups of 16 to 18 carbon atoms which can contain
aminochlorohydrin is of the formula Small amounts of alkyl and alkenyl groups of 14 carbon
atOmS.

(Ia) 0061 The reaction between the amines (as defined) and
R-NH-R2-N-CH-CH-CH epichlorohydrin is advantageously carried out in the pres
OH Cl ence of a solvent Such as benzene, toluene, Xylene, ortho
Xylene, or other higher boiling mixtures of aromatic Sol
vents, such as Aromatic 100 or Aromatic 150 which can also
and the Subsequently formed aminoepoxide is of the formula contain some hydroxylic component such as ethanol, pro
panol, butanol and the like.
(IIa) 0062. After the initial reaction between the amine and
RI-NH-R2-N-CH-CH-CH epichlorohydrin to form an aminochlorohydrin intermediate
N/ as illustrated above by Products I and Ia, the reaction mass
is treated with an inorganic base. Such as Sodium, potassium
US 2007/0220803 A1 Sep. 27, 2007

or lithium hydroxide, to form an aminoepoxide as repre Any oil-soluble Sulfonic acid such as an alkanesulfonic acid
sented by Products II and IIa above, which under continued or an alkary Sulfonic acid can be used. A useful Sulfonic acid
heating undergoes polymerization to yield the desired prod is petroleum Sulfonic acid resulting from treating oils with
uct represented above by the generic formula and Subgener Sulfuric acid.
ics A and B. Inorganic chloride formed in the reaction is 0066 Generally, the amount of sulfonic acid incorporated
removed by filtration. The solvent used to facilitate the in the concentrate is an equivalent amount, that is, Sufficient
reaction can be removed if desired, e.g., by distillation, but amount of Sulfonic acid to neutralize all the amine groups of
generally it is more convenient to use the polymeric the polymeric polyamine, although lesser or greater than the
polyamine as a solution. equivalent amount can be used. Thus, one form of the
0063. The above-described reactions of epichlorohydrin concentrate of the present invention will contain from about
with amines to form polymeric products are well known and 5 to 25% by weight of polysulfone copolymer, from about
find extensive use in epoxide resin technology (cf. "Epoxy 5 to 30% by weight of polymeric polyamines, from about 5
Resins”, Henry Lee and Kris Neville, The McGraw-Hill to 30% by weight of, say, dodecylbenzenesulfonic acid, and
Book Co., 1957, the entire teaching of which is incorporated from about 20 to 85% by weight of solvent. Typically an
herein by reference). The polymeric reaction products of equivalent amount of dodecylbenzenesulfonic acid or
epichlorohydrin and amines are complex mixtures but it is dinonylnaphthyl Sulfonic acid is used.
believed that the above formulas of the polymeric 0067. When a three-component additive is employed
polyamines fairly represent the composition and structures (where a quaternary ammonium compound is the third
that are obtained.
component), the concentrate composition will comprise,
0064. The normally liquid hydrocarbon fuels to which the based on total weight of the composition: from about 5 to
additives are added to render such hydrocarbon fuels elec 25% of polysulfone, from about 5 to 25% of polyamine,
trically conductive are those boiling in the range of about from about 0.5 to 5% of quaternary ammonium compound,
20° to about 375° C. and include such commonly designated from about 5 to 25% of a sulfonic acid, say, dodecylbenzene
fuels as aviation gasoline, motor gasoline, jet fuels, naphtha, sulfonic acid, and from about 20 to 84.5% of solvent.
kerosene, diesel fuel and distillate burner fuel oil. The 0068 The utility of the present invention composition as
additive composition can be added in any conventional a highly effective antistatic additive for hydrocarbon fuels is
manner. Each individual component of the composition can demonstrated by the fact that the incorporation into hydro
be added to the hydrocarbon fuel separately or the compo carbon fuels of as little as 0.00003% by weight (0.3 part per
sition can be added as a simple mixture or as a solution in million, ppm) of polysulfone copolymer and 0.00002% by
a solvent, such as benzene, toluene, Xylene, o-Xylene, iso weight (0.2 ppm) of polymeric polyamine is sufficient, in
propanol, cyclohexane, Aromatic 100 and Aromatic 150 fuel nearly all hydrocarbon fuels investigated, to provide elec
oil, or in a mixture of Such solvents. It is convenient to trical conductives of at least 100 C.U. (conductivity units).
prepare both the polysulfone copolymer and the polymeric In certain responsive fuels, as little as 0.0000018 weight %
polyamine in a solvent, such as one or more of those (0.018 ppm) polysulfone copolymer and 0.0000013 weight
mentioned above. Thus, it is typical to use such solutions of % (0.013 ppm) polymeric polyamine provide a conductivity
polysulfone and polymeric polyamine and to combine them. of at least 100 C.U. Thus, the present invention provides a
The combination, which can be termed a concentrate, can highly effective ashless antistatic additive composition
then be added to the hydrocarbon fuel. Such concentrate which confers increased electrical conductivity to hydrocar
conveniently contains from about 1 to 40% by weight of bon fuels at very low usage levels.
polysulfone copolymer, from about 1 to about 40% by
weight of polymeric polyamine and from about 20 to 98% 0069. The antistatic effectiveness of the present invention
by weight of a solvent or a mixture thereofas described. In composition is unexpected as the polysulfone product pre
one aspect, the concentrate will contain from about 5 to 25% pared in o-Xylene and the correspondent composition
by weight of polysulfone copolymer, from about 5 to 25% derived from said polysulfone is Superior to a similar
by weight of polymeric polyamine and from about 50 to composition derived from polysulfone prepared from tolu
90% by weight of solvent. CC.

0065. When formulating concentrates, it is typical that 0070 The hydrocarbon fuels into which the present com
the polymeric polyamine be present as a salt, particularly a position is incorporated exhibit satisfactory water interac
Sulfonic acid salt, for improved resistance to precipitate tion properties as evidenced by satisfactory results in the
formation in storage. For example, when a concentrate as water separation test according to ASTM D-2250-66T. The
described comprising polymeric polyamine in the free base hydrocarbon fuel composition containing the composition of
form is stored at elevated temperatures of about 44° C. for the invention can also contain conventional additives used in
a period of time of about 4 weeks, a small amount of hydrocarbon fuels such as antiknock compounds, antioxi
precipitate sometimes forms. The presence of small amounts dants, corrosion inhibitors, metal deactivators, rust preven
of precipitate in the concentrates have little or no effect on tatives, dyes, anti-icing agents and the like.
the usefulness of the present compositions as antistatic 0071. The polysulfones, and polyamines evaluated in the
additives but are undesirable if only from an aesthetic point present invention were prepared according to procedures
of view. It has been found that strong acids such as hydro outlined in U.S. Pat. No. 3,917,466. The examples cited
chloric, sulfuric or a sulfonic acid can be used to limit therein are not intended to be a limit of the scope of the
precipitate formation in the concentrates. Oil-soluble sul invention.
fonic acids are typical because they effectively inhibit pre
cipitate formation without substantial deleterious effect 0072 Another embodiment of the present invention is
upon the electrical conductivity property of the composition. directed to a fuel oil composition. This fuel oil composition
US 2007/0220803 A1 Sep. 27, 2007

can comprise a suitable fuel oil component and a suitable units derived from one or more 1-alkenes each having
additive component. In one aspect, the composition com from about 4 to 24 carbon atoms, and from about 0 to
prises from about 99.99% fuel and about 0.01% additive to 10 mol percent of units derived from an olefinic com
about 99.9999% fuel to about 0.0001% additive. In one
aspect, a suitable additive includes those described herein. pound having the formula ACH=CHB wherein A is a
The fuel oil can be a petroleum-based fuel oil, suitably a group having the formula —CH2)—COOH wherein
gasoline or middle distillate fuel oil. The fuel oils can X is from about 0 to about 17, and B is hydrogen or
comprise atmospheric or vacuum distillate, contain cracked carboxyl, with the proviso that when B is carboxyl, X is
gas oil in or a blend of any proportion of straight run or 0, and wherein A and B together can be a dicarboxylic
thermally or catalytically cracked distillates, and in many anhydride group,
cases are hydrogen-treated or otherwise processed to
improve properties. said polymeric polyamine of (ii) having the formula

0.073 Gasolines are low boiling mixtures of aliphatic, wherein

olefinic, and aromatic hydrocarbons, and optionally alcohols R" is an aliphatic hydrocarbyl group of 8 to 24 carbon
or other oxygenated components, boiling in the range from atoms,
room temperature up to 225°C. Other fuel oils are kerosine,
jet fuels, diesel fuel oils and home heating fuel oils (such as, R is an alkylene group of 2 to 6 carbon atoms,
middle distillate heating fuels), generally having flash points R is R', or, an N-aliphatic hydrocarbyl alkylene group of
greater than 380° C. These fuels are higher boiling mixtures the formula R'NHR,
of aliphatic, olefinic, and aromatic hydrocarbons having a
boiling point up to 350° C. a is an integer of 0 to 20,
0074 Conductivity of fuels and solvents comprising b is an integer of 0 to 20,
static dissipators are commonly measured using ASTM D
2624 or IP 274, a technically equivalent method. See, ASTM c is an integer of 0 to 20, and
D 2624-02, the entire teaching of which is incorporated X is an integer of 1 to 2,
herein by reference. For comparative purposes, composi
tions can be tested according to the method described in with the proviso that when R is R' thena is an integer of
ASTM in fuels, or in a standard solvent such as Isopar M. 2 to 20 and b=c=0, and when R is R'NH R then a is
Isopar M is a high-flash solvent marketed by ExxonMobil 0 and b--c is an integer of 2 to 20,
and is highly paraflinic. Results from testing in this solvent said oil-soluble sulfonic acid of (iii) being dodecylben
are directionally similar to those obtained in fuels such as Zenesulfonic acid, and
motor gasoline, aviation gasoline, aviation turbine fuel,
diesel fuels of various Sulfur contents, and home heating said solvent of (iv) being ortho-xylene.
fuels. 2. The composition of claim 1, wherein said polysulfone
0075 Although the invention has been described with has an molecular weight ranging from about 10,000, to
respect to various embodiments, it should be realized this about 1,500,000 amu.
invention is also capable of a wide variety of further and 3. The composition of claim 1, wherein said polysulfone
other embodiments within the spirit and scope of the is selected from the group consisting of 1-hexene, 1-heptene,
appended claims. 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
What is claimed is: 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene,
1. An antistatic additive composition for hydrocarbon 1-heneicosene, 1-docosene, 1-tricosene, and 1-tetracosene.
fuels comprising, based on total weight, 4. The composition of claim 3, wherein said polysulfone
is 1-decene.
i. from about 1 to 50 percent of polysulfone, 5. The composition of claim 1, wherein said polymeric
ii. from about 1 to 50 percent of polymeric polyamine, polyamine is a polymeric reaction product of epichlorohy
drin with an aliphatic primary monoamine or N-aliphatic
iii. from about 1 to 30 percent of oil-soluble sulfonic acid, hydrocarbyl alkylene diamine.
and 6. The composition of claim 5, wherein said aliphatic
iv. from about 3 to 97 percent of solvent, primary monoamine is selected from the group consisting of
octylamine, nonylamine, decylamine, undecylamine, dode
said polysulfone of (i) comprising about 50 mol percent of cylamine, tridedecylamine, tetadecylamine, pentadecy
units from sulfur dioxide, about 40 to 50 mol percent of lamine, hexadecylamine, heptadecylamine, octdadecy
US 2007/0220803 A1 Sep. 27, 2007

lamine, nonadecylamine, eicosylamine, heneicosylamine, wherein

docosylamine, tricosylamine, and tetracosylamine.
7. The composition of claim 5, wherein said N-aliphatic R" is an aliphatic hydrocarbyl group of 8 to 24 carbon
hydrocarbyl alkylene diamine is selected from the group atoms,
consisting of N-octyl, N-nonyl, N-decyl, N-undecyl
N-dodecyl, N-tridecyl N-tetradecyl, N-pentadecyl N-hexa R is an alkylene group of 2 to 6 carbon atoms,
decyl N-heptadecyl N-octadecyl N-nonadecyl, N-eicosyl, R is R', or, an N-aliphatic hydrocarbyl alkylene group of
N-uneicosyl, N-docosyl, N-tricosyl, N-tetracosyl, as well as the formula R'NHR,
the corresponding N-alkenyl derivatives of ethylenedi
amine, propylenediamine, butylenediamine, pentylenedi a is an integer of 0 to 20,
amine, and hexylenediamine
8. The composition of claim 1, wherein a weight ration of b is an integer of 0 to 20,
said polysulfone to said polyamine ranges from about 100:1
to about 1:100. c is an integer of 0 to 20, and
9. The composition of claim 1, wherein a weight ration of X is an integer of 1 to 2,
said polysulfone to said polyamine ranges from about 50:1
to about 1:1. with the proviso that when R is R' thena is an integer of
10. The composition of claim 1, wherein a weight ration 2 to 20 and b=c=0, when R is R'NH R thena is 0 and
of said polysulfone to said polyamine ranges from about b+c is an integer of 2 to 20, and
20:1 to about 1:1.
11. The composition of claim 1, wherein said sulfonic acid said solvent of (iii) being ortho-xylene.
is either a mono or disulfonate of alkylbenzene. 15. An antistatic additive composition comprising, based
12. The composition of claim 11, wherein said sulfonic o total weight,
acid is either dodecylbenzene Sulfonic acid or dinonylnaph i. from about 1 to 50 percent of polysulfone,
thyl sulfonic acid.
13. A hydrocarbon fuel boiling range of from about 200 ii. from about 1 to 50 percent of polyamine,
to about 375° C. having from about 0.01 ppm to about 40
ppm of said composition defined in claim 1. iii. from about 0.5 to 5 percent of quaternary ammonium
14. An antistatic additive composition comprising, based compound,
on total weight,
iv. from about 1 to 30 percent of oil-soluble sulfonic acid,
i. from about 1 to 50 percent of polysulfone, and
ii. from about 1 to 50 percent of polymeric polyamine, and V. from about 3 to 97 percent of solvent,
iii. from about 3 to 97 percent of solvent, said polysulfone of (i) comprising about 50 mol percent of
said polysulfone of (i) comprising about 50 mole percent units derived from sulfur dioxide, from about 40 to 50
of units from sulfur dioxide, about 40 to 50 percent of mol percent of units derived form 1-alkene of 4 to 24
units derived from one or more 1-alkenes each having carbon atoms and 0 to about 10 mol percent of units
from about 4 to 24 carbon atoms, and from about 0 to derived from an olefin having the formula,
10 mol percent of units derived from an olefinic com ACH=CHB, wherein A is a group having the formula
pound having the formula ACH=CHB wherein A is a —(CH)—COOH wherein
group having the formula —CH2)—COOH wherein
X is from 0 to about 17, and B is hydrogen or carboxyl, X is from 0 to about 17, and B is hydrogen or carboxyl,
with the proviso that when B is carboxyl, X is 0, and with the proviso that when B is carboxyl, X is 0, and
wherein A and B together can be a dicarboxylic anhy wherein A and B together can be a dicarboxylic anhy
dride group, dride group,
said polymeric polyamine of (ii) having the formula said polyamine of (ii) having the formula

NHR
R2
12 a
RN OH R1
fr
OH. R.
2n-n -H-I-H.
OH

RN
US 2007/0220803 A1 Sep. 27, 2007

wherein (c) a
R" is an aliphatic hydrocarbyl group of 8 to 24 carbon Alk
atoms, - (CHCHO).H.
R is an alkylene group of 2 to 6 carbon atoms,
R is R', or, an N-aliphatic hydrocarbyl alkylene group of group as defined above,
the formula R'NHR, (d) a
a is an integer of 0 to 20, O

b is an integer of 0 to 20, -CHCHO-P-OCHCH(OCOAlk)CHOCOAlk

c is an integer of 0 to 20, and O
X is an integer of 1 to 2.
group, wherein
with the proviso that when R is R' then a is an integer of
2 to 20 and b=c=0, and when R is R'NH R then a is Alk' and Alk" are the same or different alkyl groups
0 and b+c is an integer of 2 to 20, the quaternary having from 11 to 19 carbon atoms, and
ammonium compound of (iii) having the formula (e) an—Alk. CO. group wherein Alk is a hydrocarbyl
group having from 1 to 17 carbon atoms, with the
proviso that when Alk', Alk, Alk and Alk' are each
Alk?
alkyl groups, at least one of them is an alkyl group
having at least 8 carbon atoms,
Alk-N-Alk' A, A is an anion,
Alk Z is 0 or 1, Z is 0 when Alk" is (d) or (e), and
y is at least 1, y is equal to the ionic valence of anion A
when Z is 1,
wherein
said composition comprises, in combination therewith,
Alk' and Alki are the same or different alkyl groups said oil-soluble sulfonic acid of (iv) being dodecylbenze
having from 1 to 22 carbon atoms, nesulfonic acid, and
Alk is selected from the group consisting of alkyl groups said solvent of (v) being ortho-xylene.
of 1 to 22 carbon atoms and 16. The composition of claim 15, wherein said quaternary
ammonium is dicocodimethyl ammonium nitrite.
17. A composition comprising a major proportion of a
Alk suitable fuel oil and a minor portion of a suitable additive.
18. The composition of claim 17, wherein said suitable
- (CHCHO).H. fuel oil is selected from the group consisting of a petroleum
based fuel, kerosene, jet fuel oil, middle distillate heating
oils, and diesel fuel oil.
where Alki is hydrogen or methyl and n is 1 to 20, 19. The composition of claim 18, wherein said petroleum
based fuel is a gasoline or middle distillate fuel oil.
Alk' is selected from the group consisting of 20. The composition of claim 17, wherein said suitable
(a) an alkyl group having 1 to 22 carbon atoms, additive is an additive defined by claim 1.
(b) an aralkyl group having from 7 to 22 carbon atoms, k k k k k