Note: Descriptions are shown in the official language in which they were submitted.
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TRIAZINE DERIVATIVE AS DISPERSANT FOR LUBRICANTS AND FUELS
The present invention relates to triazine
derivatives, a process for their preparation, lubricating
oil compositions, fuel compositions and additive
concentrates containing them and their use as dispersant
additives.
In accordance with the present invention there is
provided a process for the preparation of a triazine
derivative which comprises:
(i)(a) reacting a compound of the formula
N
R R CI)
R
with a polyamine (II) containing at least two -NH2 and/or
-NH groups and (b) reacting the product of (a) with a
polyalkenyl derivative of an ethylenically unsaturated
carboxylic reagent and/or a chlorinated polyalkenyl
derivative;
or
(ii)(a) reacting a compound of formula (I) with a
lipophilic amine, (b) reacting the product of (a) with a
polyamine (II), and (c) reacting the product of (b) with
a polyalkenyl derivative of an ethylenically unsaturated
carboxylic reagent and/or a chlorinated polyalkenyl
derivative;
or
(iii)(a) reacting a compound of formula (I) with a pre- .~
formed reaction product of a polyalkenyl derivative of an
ethylenically unsaturated carboxylic reagent and a
polyamine (II), and (b) optionally reacting the product
f'.fINFhRAA.ATIO11 fflPY
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of (a) with a polyamine (II) which may be the same as or
different from the polyamine (II) used to form said pre-
formed reaction product, or with a lipophilic amine,
wherein each R, which may be the same or different
from one another, is a chlorine atom, an amino or
hydroxyl group, or a group selected from
-OS02R~, -OS02 / \ and -OCO(CH2)nCR3R4R5,
~ R2
wherein R1 is an alkyl group; R2 is a hydrogen atom or an
alkyl group; R3, R4 and R5, which may be the same as or
different from one another, is each a hydrogen atom or an
alkyl group; and n is 0 or 1;
or
(iv) reacting a compound of formula (I), in which each R,
which may be the same as or different from one another,
is an amino or hydroxyl group, with a polyalkenyl
derivative of an ethylenically unsaturated carboxylic
reagent or with a polyalkenyl derivative of a polyamine
(II).
with the proviso that in reaction (iii)(a) when each R is
a chlorine atom or one R is an amino group and the others
are chlorine atoms, the polyamine (II) used to form said
pre-formed reaction product is not diethylene triamine or
tetraethylene pentamine, unless step (iii)(b) is carried
out.
In the compound of formula (I), each R is preferably
a chlorine atom, an amino or hydroxyl group, or a group
selected from -OS02CH3 and -OS02 / \ CH3~ Said
compounds may be prepared by methods known in the art. ~ -
Especially preferred examples of the compound of formula
(I) are melamine, cyanuric chloride and cyanuric acid.
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The polyamine (II) contains at least two -NH2 and/or
-NH groups, the groups each having at least one active
hydrogen thereon. Examples of polyamines useful in the
present invention are those described in the text from
S page 16, line 21 to page 19, line 53 of EP-B-0287569.
Preferably the polyamine is a compound of the general
formula
H2N-(CHR1)x-CH2-[A-CH2-(CHR1)x]y-NH2 (III)
wherein A is -NH or -O-, each R1 independently represents
a hydrogen atom or a methyl group, x is in the range 1 to
3, and y is in the range 1 to 10 when A is -NH or y is in
the range 1 to 200 when A is -O-. y may also be 0.
In formula (III) above, it is preferred that when A
is -NH, then x is 1, each R1 represents a hydrogen atom,
and y is in the range 1 to 8; or when A is -O-, then x is
1, each R1 represents a methyl group and y is in the
range 1 to 50.
Preferred polyamines are polyethylene polyamines and
polypropylene polyamines, particularly ethylene diamine
(EDA), diethylene'triamine (DETA), triethylene tetramine
(TETA), tetraethylene pentamine (TEPA), pentaethylene
hexamine (PEHA) and hexaethylene heptamine (HEHA).
Especially preferred are EDA and DETA.
The ethylenically unsaturated carboxylic reagent
contains a total of at least 3 carbon atoms, preferably a
total of from 3 to 50, more preferably from 3 to 30,
still more preferably from 9 to 20, and even more
preferably from 4 to 10, carbon atoms.
The ethylenically unsaturated carboxylic reagent may
be an alpha-beta olefinic unsaturated carboxylic reagent
as described at page 6, lines 15 to 48 of EP-B-0285609 or
page 6, lines 11 to 39 of EP-B-0287569, e.g. acrylic acid-
(C3), methacrylic acid (C4), cinnamic acid (Cg), crotonic
acid (C4), 2-phenylpropenoic acid (Cg), malefic acid (C4),
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fumaric acid (C4), glutaconic acid (C5), mesaconic acid
(C5), itaconic acid (methylene succinic acid) (C5),
citraconic acid (methyl malefic acid) (C5) and functional
derivatives thereof such as anhydrides (e. g. malefic
anhydride (C4), glutaconic anhydride (C5), itaconic
anhydride (C5), citraconic anhydride (C5)), esters (e. g.
methyl acrylate (C4)), amides, imides, salts, acyl
halides and nitriles.
Preferably the ethylenically unsaturated carboxylic
reagent is selected from monoethylenically unsaturated
C4-C10 dicarboxylic acids and anhydrides, of which malefic
anhydride is most preferred.
The polyalkenyl derivative of an ethylenically
unsaturated carboxylic reagent may be prepared by methods
known in the art. For example, if the ethylenically
unsaturated carboxylic reagent is malefic anhydride, the
polyalkenyl derivative thereof may conveniently be
prepared by mixing a polyalkene with a specified amount
of malefic anhydride and passing chlorine through the
mixture, e.g. as described in
GB-A-949981. Alternatively, the derivative may be
prepared by reacting thermally, at an appropriate
temperature, the polyalkene with a specified amount of
malefic anhydride, e.g. as described in GB-A-1483729. In
EP-A-0542380 is described a process for preparing such a
derivative, which involves reacting the polyalkene with
malefic anhydride in a mol ratio of malefic anhydride to
polyalkene of greater than 1:1, at a temperature in the
range from 150 to 260°C and in the presence of a
polyaddition-inhibiting amount of a sulphonic acid. The
molar ratio of ethylenically unsaturated carboxylic
moiety to polyalkenyl moiety in the derivative formed is
preferably 1:1 to 5:1, more preferably 1:1 to 3.5:1,
particularly 1.5:1 to 1.2:1.
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The chlorinated polyalkenyl derivative may also be
prepared by methods known in the art, e.g. by passing
chlorine into the polyalkene.
The polyalkene used to prepare the polyalkene
derivative may be a homopolymer or copolymer, for example
of at least one C2_10 monoolefin. Preferably the
polyalkene is a polymer of at least one C2_5 monoolefin,
e.g. an ethylene-propylene copolymer. The monoolefin is
preferably a C3_4 olefin, in particular propylene or
isobutylene, and preferred polyalkenes derived therefrom
include polyisobutylenes and atactic or isotactic or
syndiotactic propylene oligomers. Polyisobutylenes such
as that sold by BASF under the trade mark "GLISSOPAL" and
those sold by the British Petroleum Company under the
IS trade marks "ULTRAVIS (both having high levels (about 80
to 90$) of terminal vinylidene unsaturation), "HYVIS" and
"NAPVIS", e.g. "HYVIS 75", "HYVIS 120", "NAPVIS 10",
"HYVIS 200" and "NAPVIS 120" polyisobutylenes, are
especially preferred for use in the present invention.
The polyalkene has a number average molecular weight
(Mn) preferably in the range from 300 to 7000, more
preferably from 500 to 5000, still more preferably from
700 to 3000.
The lipophilic amines used in the present invention
may be straight chain, branched, saturated or
unsaturated, and include aromatic amines. Especially
preferred are dodecylamine (C12), dioctylamine (C16) and
oleylamine (Clg). A tertiary C18 primary amine sold as
"PRIMENE" JMT (ex. Rohm and Haas) can alternatively be
used.
Reactions (i)(a) and (ii)(b) are preferably carried
out at a temperature in the range 30 to 200°C, more
preferably 40 to 180°C, particularly 50 to I70°C. Said
reactions are carried out in the presence of a solvent.
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Furthermore, in said reactions, preferably a molar excess
of the polyamine (II) over the compound of formula (I) is
used, particularly a molar ratio of 2:1 to 20:1, more
particularly 5:1 to 16:1, especially 9:1 to 16:1.
Reaction (ii)(a) is preferably carried out at a
temperature in the range 0 to 10°C, preferably 0 to 5°C.
Said reaction may be carried out in the presence of a
solvent, and in the presence of a base such as sodium
carbonate or sodium bicarbonate. The product of said
reaction may be subjected to an aqueous wash.
Suitable solvents include hydrocarbon solvents such
as higher alkanes, toluene, xylene, mesitylene, e.g
"SHELLSOL" (trade mark) A solvent available from member
companies of the Royal Dutch/Shell Group of Companies;
also synthetic and mineral oils such as "HVI-60"; ether
solvents such as tetrahydrofuran and 1,4-dioxane;
nitriles such as acetonitrile; alcohols such as 1-
pentanol (amyl alcohol) and 2-methyl-2-propanol (tert-
butyl alcohol); and chlorohydrocarbons such as
1,1,1-trichloroethane. The process may be carried out in
the absence of a solvent but, as indicated above, is
conveniently carried out in the presence of one. Any
water or excess of alcohol may be removed using for
example a Dean and Stark trap.
Reactions (i)(b) and (ii)(c) are preferably carried
out at a temperature in the range 140 to 230°C, more
preferably 150 to 210°C. They are also preferably
carried out in the presence of an inert gas, for example
a nitrogen stream.
The molar ratio of the products of reactions (i)(a)
and (ii)(b):polyalkenyl derivative of an ethylenically
unsaturated carboxylic reagent is preferably in the range ~
1:1 to 10:1, more preferably 1:1 to 5:1, particularly 1:1
to 2.5:1.
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Reaction (iii)(a) is preferably carried out at a
temperature in the range 120 to 280°C, more preferably
140 to 240°C.
Reaction (iii)(b) is preferably carried out at a
temperature in the range 120 to 280°C, more preferably
140 to 240°C.
Reaction (iv) is preferably carried out at a
temperature in the range 25 to 280°C, more preferably 100
to 240°C.
In the process of the present invention, the molar
ratio of lipophilic amine:compound of formula (I) is
preferably 1:1 to 10:1, more preferably 1:1 to 5:1,
particularly 1:1 to 2:1.
The pre-formed reaction product of a polyalkenyl
derivative of an ethylenically unsaturated carboxylic
reagent and a polyamine (II) may be prepared according to
techniques conventional in the art. Thus, for example,
if the ethylenically unsaturated carboxylic reagent is
malefi c anhydride and the polyamine is ethylene polyamine,
they may conveniently be reacted together in a molar
ratio of polyalkenyl derivative to polyamine from 1:1 to
4:1, in a hydrocarbon solvent at a temperature in the
range from 100 to 250°C, e.g. as described in EP-A-
0587250. The molar coupling ratio of polyalkenyl
derivative to amine in the product is preferably in the
range 1:1 to 3:1, more preferably 1:1 to 2.5:1.
The molar ratio (poiyalkenyl derivative of an
ethylenically unsaturated carboxylic reagent):(polyamine)
for the reactants of the present invention is preferably
in the range from 1:1 to 4:1, more preferably from 1:1 to
3:1, most preferably from 1:1 to 2.5:1.
The present invention further provides the reaction -r
product of the above-described process according to the
present invention.
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_ g _
The reaction product of the present invention may be
used as an additive in lubricating oils. Accordingly,
the present invention provides a lubricating oil
composition comprising a major amount (more than 50~w) of
a lubricating base oil and a minor amount (less than
50$w), preferably from 0.1 to 20~w, especially from 0.5
to 10~w (active matter), of a reaction product according
to the present invention, the percentages by weight being
based on the total weight of the composition.
A lubricant formulation may be produced by addition
of an additive package to the lubricating oil. A minor
amount of viscosity modifier may be included if the final
lubricant formulation is to be a multigrade version. The
type and amount of additive package used in the
formulation depends on the final application, which can
include spark-ignition and compression-ignition internal
combustion engines, including automobile and truck
engines, marine and railroad diesel engines, gas engines,
stationary power engines and turbines.
The lubricant formulation is blended to meet a series
of performance specifications as classified in the US by
a tripartite arrangement between the Society of
Automotive Engineers (SAE), American Petroleum Institute
(API) and American Society for Testing and Materials
(ASTM). Also the American Automobile Manufacturers
Association (AAMA) and Japan Automobile Manufacturers
Association Inc. (JAMA), via an organisation called the
International Lubricant Standardisation and Approval
Committee (ILSAC), jointly develop minimum performance
standards for gasoline-fuelled passenger car engine oils.
In Europe, engine oil classifications are set by the
Association des Constructeurs Europeens de 1'Automobile
(ACEA) in consultation with the Technical Committee of
Petroleum Additive Manufacturers (ATC) and Association
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Technique de 1'Industries Europeens des Lubrifiants
(ATIEL). Besides these internationally recognised oil
classification systems, many, if not all, Original
Equipment Manufacturers (OEMs) have their own in-house
performance requirements that must be met by lubricant
formulations used for first (i.e. factory) fill.
Suitable lubricating base oils are natural, mineral
or synthetic lubricating oils.
Natural lubricating oils include animal and vegetable
oils, such as castor oil. Mineral oils comprise the
lubricating oil fractions derived from crude oils, e.g.
of the naphthenic or paraffinic types or mixtures
thereof, coal or shale, which fractions may have been
subjected to certain treatments such as clay-acid,
solvent or hydrogenation treatments. Synthetic
lubricating oils include synthetic polymers of
hydrocarbons, e.g. derived from polyalphaolefins,
isomerised slack wax, modified alkylene oxide polymers
and esters, which are known in the art. These
lubricating oils are preferably crankcase lubricating oil
formulations for spark-ignition and compression-ignition
engines, but include also hydraulic lubricants, metal-
working fluids and automatic transmission fluids.
Preferably the lubricating base oil component of the
compositions according to the present invention is a
mineral lubricating oil or a mixture of mineral
lubricating oils, such as those sold by member companie s
of the Royal Dutch/Shell Group of Companies under the
designations "HVI", or the synthetic hydrocarbon base
oils sold by member companies of the Royal Dutch/Shell
Group of Companies under the designation "XHVI" (trade
mark) . "'~ '
The viscosity of the lubricating base oils present in
the compositions according to the present invention may
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vary within wide ranges, and is generally from 3 to 35
mm2/s at 100°C.
The lubricating oil compositions according to the
present invention may contain various other additives
known in the art, such as:
(a) Viscosity index improvers or modifiers. The
viscosity modifier may be of the solid type or a
concentrate in a natural or synthetic base stock and
can be defined as a substance, usually a polymer,
which substantially improves (e.g. by at least 5
units) the viscosity index (e.g. as determined by
ASTM procedure D2270) by its incorporation. These
can all be incorporated into the final lubricant
formulation to give the desired performance
properties thereof. Examples of such viscosity
modifiers are linear or star-shaped polymers of a
diene such as isoprene or butadiene, or a copolymer
of such a diene with optionally substituted styrene.
These copolymers are suitably block copolymers and
are preferably hydrogenated to such an extent as to
saturate most of the olefinic unsaturation. A number
of other types of viscosity modifier are known in the
art, and many of these are described in Proceedings
of Conference "Viscosity and flow properties of
multigrade engine oils", Esslingen, Germany, December
1977. It is also known in the art that viscosity
modifiers can be functionalised to incorporate
dispersancy (e. g. dispersant viscosity index
improvers based on block copolymers, or
polymethacrylates) and/or antioxidant functionality
as well as viscosity modification and they can also
have pour point depressants mixed in to give
handleable products in cold climates.
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(b) Ashless or ash-containing extreme pressure/anti-wear
additives, such as, for example, those of the metal
containing dithiophosphate or ashless dithiocarbamate
type, and mixtures thereof. The actual composition
of the individual components will vary depending upon
final application and hence can be based on a range
of metal ion types and various alcohols, in which
both alkyl and aryl moieties may be of varying size.
Preferred are zinc dithiophosphates (ZDTPs) or sodium
dithiophosphates.
(c) Dispersants including succinimides and Mannich bases,
both of various molecular weights and amine type,
including borated versions, or esters also of varying
type and molecular weight. Preferred are ashless
dispersants such as polyolefin-substituted
succinimides, e.g. those described in GB-A-2231873.
(d) Anti-oxidants, for example of the aminic type such as
"IRGANOX" (trade mark) L57 (tertiary CQ-C12 alkyl
diphenylamine) or phenolic type such as "IRGANOX"
(trade mark) L135 (2,6-ditertiary-butyl-9-(2-
carboxy(alkyl)ethyl)phenol) (ex. CIBA Speciality
Chemicals) or a soluble copper compound at a copper
concentration of between 50 and 500 ppm.
(e) Anti-rust compounds of, for example, the
ethylene/propylene block copolymer type.
(f] Friction modifiers for fuel economy, either metal
(e. g. molybdenum) containing, or metal free esters
and amines, or synergistic mixtures thereof.
(g) Metal containing detergents such as phenates,
sulphonates, salicylates or naphthenates, or mixtures
thereof, all of which detergents may be either
neutral or overbased, such overbased detergents being
carbonates, hydroxides or mixtures thereof. The
metals are preferably calcium, magnesium or
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manganese, although alkali metals such as sodium or
potassium could also be used.
(h) Copper passivators, preferably of the alkylated or
benzylated triazole type.
The reaction product of the present invention may
also be used as an additive in fuels. Accordingly, the
present invention further provides a fuel composition
comprising a major amount (more than 50$w) of a base fuel
and a minor amount (less than 50gw), preferably from
0.001 to 2$w, more preferably from 0.001 to 0.5$w and
especially from 0.002 to 0.2$w (active matter), of a
reaction product according to the present invention, the
percentages by weight being based on the total weight of
the composition.
Suitable base fuels include gasoline and diesel fuel.
These base fuels may comprise mixtures of saturated,
olefinic and aromatic hydrocarbons, and may contain a
range of sulphur levels, e.g. in the range 0.001 to
O.l~w. They can be derived from straight-run gasoline,
synthetically produced aromatic hydrocarbon mixtures,
thermally catalytically cracked hydrocarbon feedstocks,
hydrocracked petroleum fractions or catalytically
reformed hydrocarbons.
The fuel compositions according to the present
invention may contain various other additives known in
the art, such as:
(a) Anti-knock additives, such as lead compounds, or
other compounds such as methyl cyclopentadienyl-
manganese tricarbonyl or orthoazidophenyl.
(b) Co-antiknock additives, such as benzoylacetone.
(c) Dehazers, such as those commercially available as
"NALCO" (trade mark) EC5462A (ex. Nalco), ~~TOLAD" "~ '
(trade mark) 2683 (ex. Baker Petrolite), EXP177,
EXP159M, EXP175, EP409 or EP435 (ex. RE Speciality
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Chemicals), and T9360-K, T9305, T9308, T9311 or T327
(ex. Baker Petrolite).
(d) Anti-foaming agents, such as those commercially
available as "TEGOPREN" (trade mark) 5851, Q 25907,
MR1027, MR2068 or MR2057 (ex. Dow Corning),
"RHODORSIL" (trade mark) (ex. Rhone Poulenc), and
"WITCO" (trade mark) SAG TP325 or SAG327 (ex. Witco).
(e) Ignition improvers (e. g. 2-ethylhexyl nitrate,
cyclohexyl nitrate, di-tertiary-butyl peroxide and
those disclosed in US-A-4208190 at Column 2, line 27
to Column 3, line 21)
Anti-rust agents (e.g. that commercially sold by
Rhein Chemie, Mannheim, Germany as "RC 4801", or
polyhydric alcohol esters of a succinic acid
derivative, the succinic acid derivative having on at
least one of its alpha carbon atoms an unsubstituted
or substituted aliphatic hydrocarbon group containing
from 20 to 500 carbon atoms (e. g. the pentaerythritol
diester of polyisobutylene-substituted succinic acid)
(g) Reodorants .
(h) Anti-wear additives.
(i) Anti-oxidants (e. g. phenolics such as 2,6-di-tert-
butylphenol, or phenylenediamines such as N,N'-di-
sec-butyl-p-phenylenediamine).
(j) Metal deactivators .
(k) Lubricity agents, such as those commercially
available as EC831, "PARADYNE" (trade mark) 631 or
655 (ex. Paramins) or "VEKTRON" (trade mark) 6010
(ex. Shell Additives International Limited).
(I) Carrier fluids such as a polyether e.g. a C12-Cls
alkyl-substituted propylene glycol ("SAP 949"), "HVI"
or "XHVI" (trade mark) base oil, which are "~ '
commercially available from member companies of the
Royal Dutch/Shell Group of Companies, a polyolefin
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derived from C2-C6 monomers, e.g. polyisobutylene
having from 20 to 175, particularly 35 to 150, carbon
atoms, or a polyalphaolefin having a viscosity at
100°C in the range 2 x 10-6 to 2 x 10'5 m2/s (2 to 20
centistokes), being a hydrogenated oligomer
containing 18 to 80 carbon atoms derived from at
least one alphaolefinic monomer containing from 8 to
I8 carbon atoms.
The lubricating oil and fuel compositions of the
present invention may be prepared by adding the reaction
product of the present invention to a lubricating base
oil or base fuel. Conveniently, an additive concentrate
is blended with the lubricating base oil or base fuel.
Such a concentrate generally comprises an inert carrier
fluid and one or more additives in a concentrated form.
Hence the present invention also provides an additive
concentrate comprising an inert carrier fluid and from 10
to 80~w (active matter) of a reaction product according
to the present invention, the percentages by weight being
based on the total weight of the concentrate.
Examples of inert carrier fluids include hydrocarbons
and mixtures of hydrocarbons with alcohols or ethers,
such as methanol, ethanol, propanol, 2-butoxyethanol or
methyl tert-butyl ether. For example, the carrier fluid
may be an aromatic hydrocarbon solvent such as toluene,
xylene, mixtures thereof or mixtures of toluene or xylene
with an alcohol. Alternatively, the carrier fluid may be
a mineral base oil or mixture of mineral base oils, such
as those sold by member companies of the Royal
Dutch/Shell Group of Companies under the designations
"HVI", e.g. "HVI 60" base oil, or the synthetic
hydrocarbon base oils sold by member companies of the ''
Royal Dutch/Shell Group of Companies under the
designation "XHVI" (trade mark).
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CA 02356282 2001-06-21
WO 00/40678 PCTlEP99/10182
- 16-
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CA 02356282 2001-06-21
WO 00/40678 PCT/EP99/10182
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The present invention still further provides the use
of a reaction product according to the present invention
as a dispersant additive.
The present invention will now be further described
by reference to the following Examples. In these
Examples, the number average molecular weight (Mn)
specified for the polyisobutenyl moiety in the
polyisobutenyl succinic anhydride (PIBSA) was determined
by gel chromatography using polystyrene standards, e.g.
as described in W.W. Yau, J.J. Kirkland and D.D. Bly,
"Modern Size Exclusion Liquid Chromatography", John
Wiley and Sons, New York, 21979.
Examples 1 to 4 describe the steps of reaction (ii).
Example 1
IS (a) Cyanuric chloride (0.01 mol) in toluene was
reacted at 5°C with the lipophilic amine dodecylamine
(0.01 mol) in the presence of aqueous sodium bicarbonate
(0.02 mol). Following an aqueous wash, the mixture was
stripped to give the crude desired 6-dodecylamino-2,4-
dichloro-1,3,5-triazine ("alkylaminocyanuric chloride")
in 99~ isolated yield.
(b) DETA was then reacted with the
alkylaminocyanuric chloride from step (a) (molar ratio
10:1) at a temperature of 60°C. The product was
isolated by toluene/water partition, giving a 82~ yield.
(c) The product from step (b), in toluene, was added
to a low molecular weight PIBSA (PIB Mn about 950).
Toluene was distilled out and heating continued under a
stream of nitrogen for 6 to 7 hours at 160°C.
Example 2
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The steps described in Example 1 were followed
except that in step (c) a high molecular weight PIBSA
(PIB Mn about 2270) was used.
Example 3
The steps described in Example 1 were followed
except that in step (a) dioctylamine was used as the
lipophilic amine.
Example 4
The steps described in Example 2 were followed
except that in step (a) dioctylamine was used as the
lipophilic amine.
Examples 5 to 17
Further compounds were prepared, the characteristics
of all the Examples being set out in Table 1:
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Table 1
Example Lipophilic Polyamine Mn of Coupling Step (c)
amine PIB in ratio reaction
PIBSA PIBSA: temp C
polyamine
1 dodecylamine DETA ~950 2.0 160
2 dodecylamine DETA ~2270 2.0 160
3 dioctylamine DETA ~950 2.0 160
4 dioctylamine DETA ~2270 2.0 160
oleylamine EDA ~950 1.5 200
6 oleylamine EDA ~950 2.0 200
7 oleylamine EDA ~2270 1.5 200
8 oleylamine EDA ~2270 2.0 200
9 oleylamine EDA ~950 2.0 160
oleylamine EDA ~2270 2.0 160
11 oleylamine EDA ~950 1.5 160
12 "PRIMENE" EDA ~950 1.5 200
JMT
13 "PRIMENE" EDA ~2270 1.5 200
JMT
14 oleylamine DETA ~950 1.5 200
oleylamine DETA ~2270 1.5 200
16 oleylamine DETA ~950 2.0 200
17 oleylamine DETA ~2270 2.0 200
Example 18
Carbon Black Dispersancy Test (CBDT)
(British Rail Publication BR 669:1984)
5 Samples of a SAE 15W40 Middle East lubricating oil
containing a commercial package of a zinc
dialkyldithiophosphate, an overbased calcium alkyl
salicylate and VI improver, were modified by
incorporation of the reaction products of Examples 1 to
10 4 to give oils containing said products at a
concentration of 1~w active matter. 3$w of carbon black
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was then added to each oil and (percentage) increase in
kinematic viscosity at 60°C was determined, using an
Ubbelohde viscometer. A low result indicates good
performance. The absolute values obtained are dependent
on the active surface area of the carbon black used, and
therefore comparative series should be tested with
identical samples of carbon black. The tests were
carried out using "Flamruss" (trade mark) carbon black.
The results of this test are given in Table 2:
Table 2
Example ~ viscosity increase*
1 28
2 24
3 35
4 45
* relative to viscosity of dispersant blend
without carbon black
Example 19
Rheology Test
This test used the Haake RV20 Rotary Viscometer and
comprised adding a known concentration (2$w active
matter) of the dispersant under test to a mixture of
other compounds, to produce a fully formulated oil.
Carbon black was then added to result in a content of
9.76~w in the oil and mixed at an elevated temperature
(90°C) for a set period of time (at least 6 hours). The
viscometric characteristics of the oils containing
Examples 5 and 14 were then measured and compared under
the same conditions, together with the commercial
products "SAP 286" and "SAP 230TP" (mono/bis PIB
succinimides, ex Shell Additives International Limited).
The base oil blends used in the Haake rheology test
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consisted of the following components:
Component Concentration ~Sw
Detergents (overbased calcium and
magnesium alkyl salicylates) 3.5
Anti-wear additive
(zinc dithiophosphate(ZDTP)) 1.13
Viscosity index improver
(hydrogenated polyisoprene) 5.88
Pour point depressant
(polymethacrylate) 0.39
Mixture of base oils 89.15
The Haake rheology test apparatus comprises a Haake
RV 20 rheometer with RC 20 rheocontroller and CV 100
measuring system with a ZA 30 cup and rotor.
The samples were prepared by weighing (100/active
matter)g of the dispersant sample, made up to 5.75 g
with HVI-60-AL base oil, and then 50 g total mass with
the base oil blend.
The carbon black (grade XC72) was activated at 140°C
for at least 12 hours prior to use in the rheology test.
An amount, 0.25 to 0.30 g, of the carbon black was
measured, and fully formulated oil was added in an
amount as calculated by the formula:
MFFO - MC x 20
where MFFO is the mass of the fully formulated oil (g),
and MC is the mass of carbon black (g). The mixture was
completely homogenised with the oil. The viscosity
characteristics were measured after at least 6 hours at
90°C over a range of shear rates for 30 minutes, as
shown in Figure 1.
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From Figure l, it can be seen that Examples 5 and 14
exhibit improved dispersancy as compared to "SAP 286"
and "SAP 230TP".
Example 20
Fluoroelastomer Seals Test
Reaction products of the present invention are less
aggressive to fluoroelastomer seals, as demonstrated in
the Mercedes-Benz fluoroelastomer seals test. When seal
fluoroelastomer was subjected to a formulation
containing Example 5 its tensile strength was reduced by
13.3 and the extent to which it could be stretched
before breaking was reduced by only 17.6; the figures
for analogous formulations, at the same dispersant treat
rate (13.5~kw), containing, instead, "SAP 286" and "SAP
230TP", are shown in Table 3:
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TABLE 3
Sample Tensile strength Elongation
change ~ change $
Example 5 -13.3 -17.6
SAP 286 -52.1 -52.5
SAP 230TP -51.9 -57.1
Example 21
Corrosion Test
Reaction products of the present invention display
reduced corrosion, as demonstrated in the L-10 bench
corrosion test without severity adjustment (ref. API CG-
4 test). The results, at the same dispersant treat
rates (13.5~Sw), are shown in Table 4, from which the
improved performance of Example 5 as compared to "SAP
286" and "SAP 230TP" is apparent:
TABLE 4
Sample Metal
content
of the
oil after
test (ppm)
Co per
Lead
Tin
Example 5 3 9 <1
SAP 286 9 86 1
SAP 230TP 12 206 <1
