Novel ammonium salts of organo-oxyphosphorus acids, organo-thiophosphorus acids and their esters and to the use thereof as additives for lubricants, especially for providing protection against extreme pressure and corrosion, to compositions containing these novel salts, a method for lubricating metal surfaces in frictional contact, and a metal surface treated with the salt or lubricant composition.

The present invention relates to novel ammonium salts of 
organo-oxyphosphorus acids, organo-thiophosphorus acids and their esters 
and to the use thereof as additives for lubricants, especially for 
providing protection against extreme pressure and corrosion, to 
compositions containing these novel salts, a method for lubricating metal 
surfaces in frictional contact, and a metal surface treated with the salt 
or lubricant composition. 
In EP 277,711 there is disclosed a method for protecting metal surfaces 
against corrosion by treating the metal surface with the reaction product 
of a polyester and an amine or salt thereof with an organic acid, chloride 
or sulphate. 
It is also known to improve the wear resistance of metal surfaces by 
incorporating ammonium salts of organophosphorus acid derivatives in 
lubricating oil compositions. Thus, it has been proposed in U.S. Pat. No. 
4,962,227 to use ammonium salts of methyl phosphonic acid as lubricant 
additives and in U.S. Pat. No. 4,514,311 to use specific ammonium salts of 
phosphate esters for a similar purpose. 
None of these compounds are wholly satisfactory under all operating 
conditions, particularly under extreme pressure. It has now been found 
that ammonium salts of organo-oxyphosphorus acids, organo-thiophosphorus 
acids and their esters with the polyesteramine disclosed in EP 277,711 are 
especially effective as lubricant additives and provide a number of 
desirable properties, especially when incorporated in lubricating oils and 
greases. 
According to the present invention there is provided an ammonium salt of an 
organo-oxyphosphorus acid, an organo-thiophosphorus acid or esters thereof 
(hereinafter referred to as the "Polyester ammonium salt") with a 
polyesteramine of Formula I 
EQU Y--CO--[O--A--CO].sub.n --Z--R I 
wherein 
A is a divalent hydrocarbon radical; 
Y is a hydrogen atom or an optionally substituted hydrocarbon group; 
n is an integer from 1 to 100; 
Z is a divalent bridging group; and 
R is an amino group. 
The precise structure of the chain terminating group Y not critical 
provided it is inert to the other components of the composition under the 
normal processing conditions to which it is subjected. It is preferably 
free from ionic and strongly polar groups and preferably has a molecular 
weight of less than 300 and contains only C and H or C, H and O atoms. 
The group Y is preferably alkyl or alkenyl containing up to 35 carbon 
atoms, especially from 7 to 25, and more especially from 7 to 20 carbon 
atoms such as heptyl, octyl, undecyl, lauryl, heptadecyl, heptadecyl, 
heptadecadienyl, stearyl, oleyl, linoleyl or such a group substituted by a 
hydroxy, halo or alkoxy group, especially C.sub.1-4 alkoxy. Particularly 
preferred terminal groups Y--CO-- are 12-hydroxystearyl and 
12-hydroxyoleyl. Other values for Y include, C.sub.4-8 -cycloalkyl, such 
as cyclohexyl; polycycloalkyls, for example, polycyclic terpenyl groups 
which are derivable from naturally occurring acids such as abietic acid; 
aryl, such as phenyl; aralkyl, such as benzyl and polyaryl, such as 
naphthyl, biphenyl, stilbenyl and phenylmethylphenyl. Such groups are 
preferably unsubstituted or substituted by a group selected from hydroxy, 
halogen and C.sub.1-4 alkoxy. 
The divalent hydrocarbon group represented by A may be an aromatic group 
but is preferably an alkylene or alkenylene group, especially one 
containing from 4 to 25 carbon atoms with at least 4 carbon atoms between 
the oxygen atom and carbonyl group. Preferably n has a value of at least 
two. When n is greater than one, the groups represented by A in the 
polyester chain [O--A--CO].sub.n may be the same or different. 
It is generally preferred that n is from 1 to 10, and especially from 1 to 
6, when the group A is an aliphatic chain containing nine or more carbon 
atoms and n is from 1 to 60 when the group A is an aliphatic chain 
containing up to eight carbon atoms. The groups represented by A may carry 
other substituents which do not confer water-solubility on the molecule, 
such as halogen and alkoxy. Preferred examples of the group (--O--A--CO--) 
are 12-oxystearyl, 12-oxyoleyl and 6-oxycaproyl. 
The polyester residue of the formula: 
EQU Y--CO--[O--A--CO].sub.n -- II 
is conveniently derived from a mixture of 
(i) a saturated or unsaturated aliphatic hydroxycarboxylic acid containing 
from 4 to 25 carbon atoms having at least 4 carbon atoms between the 
hydroxy and carboxyl groups or a cyclic precursor thereof, such as a 
lactone and 
(ii) an aliphatic carboxylic acid of the formula Y--COOH, where Y is as 
hereinbefore defined. 
Examples of suitable hydroxycarboxylic acids and precursors are 
12-hydroxystearic acid, 12-hydroxy-9-oleic acid (or ricinoleic acid), 
6-hydroxycaproic acid and E-caprolactone. 
Examples of suitable acids from which the end group --Y--CO-- is derivable, 
by reaction with a terminal hydroxy group on the polyester chain, are 
lauric acid, palmitic acid, stearic acid and 9-oleic acid and mixtures 
containing these acids which are derivable from natural products. 
The divalent bridging group, Z, is preferably of the formula: 
EQU --NQ--L-- or --O--L-- 
wherein 
Q is a hydrogen atom or an alkyl group and L is an alkylene or 
hydroxyalkylene group, or 
N, Q and L, together with the nitrogen atom in the group R to which they 
are attached form a cycloaliphatic bridging group. 
The group Q preferably contains up to 25 carbon atoms. The alkylene group 
which is, or which is present in, the group L preferably contains from 2 
to 6 carbon atoms. 
Examples of the group represented by Q are methyl, ethyl, n-propyl, n-butyl 
and octadecyl and of the group represented by L are --(CH.sub.2).sub.2 --, 
--(CH.sub.2).sub.3 --, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.6 --, and 
--CH.sub.2 --CHOH--CH.sub.2 -- and an example of the cycloaliphatic 
bridging group is piperazin-1,4-ylene. 
The amino group R may be a primary, secondary or tertiary amino group and 
is preferably of the formula: 
##STR1## 
wherein T.sup.1 and T.sup.2 are independently hydrogen, C.sub.1-22 alkyl, 
substituted C.sub.1-22 alkyl, alkaryl or cycloalkyl; or 
T.sup.1 and T.sup.2 may together with the nitrogen atom to which they are 
attached form a 5- or 6-membered ring. 
When T.sup.1 or T.sup.2 is alkyl, it is preferably C.sub.1-6 alkyl, such as 
methyl. When T.sup.1 and T.sup.2 form a ring it is preferably a 
piperidino, morpholino or especially an N-alkyl piperazino ring. When 
T.sup.1 or T.sup.2 is alkaryl, it is preferably benzyl. When the bridging 
group Z is a cycloaliphatic, one of T.sup.1 or T.sup.2 is incorporated 
into the bridging group. Thus, the group --Z--R may be of the formula 
##STR2## 
It is preferred that both T.sup.1 and T.sup.2 are other than hydrogen, so 
that R is tertiary amino. 
The Polyesteramine can be prepared by processes described in UK Patent Nos 
1342746, 1373660 and 2001083 and EP 127325 (with omission of the 
epoxidation). 
The Polyesterammonium salt may be derived from the Polyesteramine alone or 
the latter may be used in admixture with a polyester of general formula 
III (hereinafter referred to as the "Polyester"), 
EQU Y--CO--[O--A--CO].sub.n --OH III 
where A, Y and n are as hereinbefore defined. 
Such a mixture is conveniently obtained by reaction of the Polyester with 
less than the quantity of an amine necessary to completely convert the 
Polyester into the desired Polyesteramine. It is generally more convenient 
to prepare such a mixture than the pure Polyesteramine and it has been 
shown that Polyesterammonium salts prepared from such a mixture are 
effective lubrication additives. 
The acid from which the Polyesterammonium salt may be derived is 
conveniently an organo-oxyphosphorus acid or organo-thiophosphorus acid 
(hereinafter referred to as the Acid) or a partial ester thereof of 
Formula IV 
##STR3## 
wherein R.sup.1 is hydrogen, optionally substituted C.sub.1-30 
hydrocarbyl, a group --X--(A--O--).sub.m R.sup.2 or a group 
--X--P(X)--(XR.sup.2).sub.2 ; 
R.sup.2 is hydrogen or optionally substituted C.sub.1-30 hydrocarbyl; 
A--O-- is C.sub.2-6 alkyleneoxy; m is 0 to 50; and 
X is oxygen or sulphur; 
provided that when m is zero, R.sup.1 and R.sup.2 are not both hydrogen. 
The group R.sup.1 is preferably C.sub.5-20 hydrocarbyl, and more especially 
C.sub.5-14 hydrocarbyl. The group R.sup.1 may be selected from alkyl which 
may be linear or branched, aralkyl, alkaryl, aryl, cycloalkyl, alkenyl and 
alkynyl groups. Examples of suitable alkyl group are methyl, ethyl, 
n-propyl, n-butyl, isobutyl, sec-butyl, amyl, hexyl, octyl, nonyl, 
2-ethylhexyl, octyl, decyl, 2-hexyldecyl and octadecyl. Examples of 
aralkyl are benzyl and 2-phenylethyl. Examples of cycloalkyl are 
cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcycloheptyl, 
3-butyl-cyclohexyl and 3-methylcyclohexyl. Examples of aryl are phenyl and 
naphthyl. Examples of alkenyl are vinyl, amyl but-1-enyl, dodecenyl, 
octadecenyl and octadecadienyl. Examples of alkynyl are ethynyl, propynyl 
and butynyl. Any substituent present in R.sup.1 should not, of course, 
adversely effect the desirable properties of the Polyesterammonium salt or 
a lubricant additive. Preferred substituents are selected from halogen, 
especially chlorine and bromine; alkyl, especially C.sub.1-4 alkyl; 
nitrile; trifluoromethyl; R.sup.1 CO; R.sup.1 O; R.sup.1 OCO and R.sup.1 
COO groups. It is preferred that R.sup.1 is unsubstituted and is 
especially alkyl or cycloalkyl. 
When R.sup.2 is optionally substituted C.sub.1-30 hydrocarbyl, it is as 
defined for R.sup.1. 
A preferred class of the Acid comprises a phosphonic acid of Formula V and 
mono esters thereof 
##STR4## 
wherein R.sup.3 is optionally substituted C.sub.1-30 hydrocarbyl; and 
R.sup.2, A--O-- and m are as hereinbefore defined. 
Examples of phosphonic acids of formula V and monoesters thereof are 
methyl, octyl, in particular n-octyl, 2-ethylhexyl, decyl, dodecyl, 
tetradecyl, phenyl and benzyl phosphonic acids and the monoethyl ester of 
octylphosphonic acid and the mono(2-ethylhexyl) ester of 
2-ethylhexylphosphonic acid. 
A further preferred class of the Acid comprises phosphorous acid esters of 
Formula VI 
##STR5## 
wherein R.sup.2, A--O-- and m are as hereinbefore defined; provided that 
when m is zero R.sup.2 is not hydrogen. 
An example of a phosphorous acid ester is the mono octyl ester. 
A further preferred class of the Acid comprises pyrophosphates of formula 
VII 
##STR6## 
wherein each R.sup.4 is independently a group --O--(A--O--).sub.m R.sup.2 
; and 
R.sup.2, A--O-- and m are as hereinbefore defined; 
provided that when m is zero, at least one R.sup.2 is not hydrogen. 
Examples of suitable pyrophosphates are mono- and di-octyl and dihexyl 
pyrophosphates. 
An especially preferred class of the Acid comprises mono- and di-esters of 
phosphoric acid of Formula VIII, and mixtures thereof 
##STR7## 
wherein each R.sup.5 is independently a group --O--(A--O--).sub.m R.sup.2 
; and 
R.sup.2, A--O-- and m are as hereinbefore defined; 
provided that when m is zero, both R.sup.2 are not hydrogen. 
Examples of phosphoric acid esters include the bis(cyclohexyl), dihexyl, 
bis(2-ethylhexyl), dibenzyl, didodecyl, diisooctyl, dioctadecyl and 
diphenyl esters. 
Examples of phosphoric acid esters also include the monododecyl, mono 
2-ethylhexyl, mono isooctyl, mono decyl, mono hexadecyl, including the 
mono 2-hexyldecyl, and mono octadecyl including the mono iso-octadecyl, 
esters. 
Examples of phosphoric acid esters further include the his and mono-esters 
of alkyleneoxy derivatives of R.sup.2 OH such as the phosphate esters of 
ethoxylated phenols, ethoxylated 2-ethylhexanol, ethoxylated 4-nonylphenol 
and ethoxylated C.sub.6-20 alcohols and ethoxylated C.sub.6-20 amines. 
Phosphoric acid esters of alkoxylated alcohols, amines and phenols of this 
type are commercially available as COPTAL, LENETOL and SUNAPTOL 
surfactants. (COPTAL, LENETOL and SUNAPTOL are trade marks, the property 
of ICI). 
An especially preferred class of the Acid comprises phosphorodithioic acid 
of Formula IX, and partial esters thereof 
##STR8## 
wherein each R.sup.5 is independently the group --O--(A--O--).sub.m 
R.sup.2 ; and 
R.sup.2, A--O-- and m are as hereinbefore defined; 
provided that when m is zero, both R.sup.2 are not hydrogen. 
Examples of phosphorodithioic acid esters are the O,O-diethyl; 
O,O-bis(2-ethylhexyl); O-butyl-O-hexyl; mixed O,O-di-C.sub.1-4 alkyl; 
O,O-di-nonylphenol; O,O-di-isodecyl; O,O-dioctyl and O,O-diisopentyl 
esters. 
A still further preferred class of the Acid comprises phosphorothioic acid 
of Formula X, and partial esters thereof. 
##STR9## 
wherein each R.sup.5 is independently the group --O--(A--O--).sub.m 
R.sup.2 ; and 
R.sup.2, A--O-- and m are as hereinbefore defined; 
provided that when m is zero, both R.sup.2 are not hydrogen. 
Examples of suitable phosphorothioic acid esters are the O,O-dimethyl 
diester, O,O-dioctyl diester and O,O-bis(2-ethylhexyl) diester. 
The hydrocarbyl substituent R.sup.2 in Formulae IV-X is selected so as to 
render the Polyesterammonium salt compatible with, and more especially 
soluble in, the lubricant. The compatibility of the Polyesterammonium salt 
with the lubricant or solubility in the lubricant may be varied by 
altering the length and nature of the group --(A--O--).sub.m. Thus, the 
group --(A--O--).sub.m may be a monomer, a homo- or block oligomer or a 
co-polymer derived from ethylene oxide, propylene oxide and/or butylene 
oxide. 
The Acid of general formula V may be prepared by the reaction of an olefin 
with a phosphite. Thus, for example, tetradecene may be reacted with a 
molar excess of dimethylphosphite in the presence of a radical generator 
such as ditertiarybutyl phenoxide at 130.degree.-150.degree. C. to give 
tetradecylphosphonic acid (Formula V, R.sup.2 is a hydrogen, R.sup.4 is 
C.sub.14 H.sub.29 and m is zero). 
Phosphate mono- and di- esters of general formula VI to X may be made by 
reacting a hydroxy compound R.sup.2 (A--O--).sub.m --OH with phosphorus 
pentoxide at an elevated temperature or pyrophosphoric acid at room 
temperature in appropriate proportions, optionally in the presence of an 
inert organic solvent. 
The diesters are typically prepared by reacting excess hydroxy compound 
with phosphorus pentoxide. Thus, dihexylphosphate (Formula VIII, R.sup.2 
is C.sub.6 H.sub.13, m is zero) may be prepared by reacting 3 moles of 
hexanol with 1 mole of phosphorus pentoxide. The phosphorodithioic acid 
esters are prepared in analogous manner by replacing the phosphorus 
pentoxide with phosphorus pentasulphide. 
The Polyesterammonium salt may be prepared by mixing together the 
Polyesteramine and the Acid or ester thereof in such relative proportions 
necessary to partially or fully neutralise the Acid or ester. This is 
conveniently carried out by determining the `base` value of the 
Polyesteramine and the `acid` value of the Acid or ester and mixing the 
two components together in all appropriate proportions necessary to 
replace some or available hydrogen atoms in the Acid or ester. 
The `base` value of the Polyesteramine derivative is conveniently 
determined by titration with a strong inorganic acid such as perchloric 
acid in an organic solvent such as glacial acetic acid, or hydrochloric 
acid. 
The `acid` value of the Acid or ester is conveniently determined by 
titration with a strong inorganic base such as potassium hydroxide in 
aqueous ethanol solution or tetraethylammonium hydroxide in propan-2-ol, 
in the presence of an appropriate indicator, for example, bromophenol 
blue, phenolphthalein or 1-naphthophthalein. The acid value determined by 
bromophenol blue is used to provide a part neutralised salt and the acid 
value determined by phenolphthalein or 1-naphthophthalein is used to 
provide a fully neutralised salt. 
The `base` value of the Polyesteramine and `acid` value of the Acid or 
esters thereof is conventionally expressed in mg of KOH/g. 
The salts obtained are hereinafter referred to as fully or partially 
neutralised depending on the extent of neutralisation of the Acid or ester 
by the Polyesteramine. 
Formation of the Polyesterammonium salt can be effected at any temperature 
from 20.degree. C. to 200.degree. C., optionally in the presence of a 
material such as tetrabutyl titanate. 
However, the salt is preferably formed at a temperature from 50.degree. to 
150.degree. C. and especially from 70.degree. to 120.degree. C. At 
elevated temperatures the Polyesteramine salt is generally formed within 
about 60 minutes. 
Purification of the Polyesterammonium salt, such as separation from 
unreacted starting materials, is not normally required provided the 
Polyesteramine and Acid or ester are mixed in appropriate proportions. 
The Polyesterammonium salt may be formed from mixtures of different 
Polyesteramines and/or also mixtures of different Acids or esters thereof. 
A particularly useful Polyesterammonium salt is the fully neutralised salt 
formed by heating 
(a) the reaction product of 2 moles of poly(12-hydroxystearic acid) (acid 
value of 35 mg KOH/gm) and 1 mole of dimethylaminopropylamine with 
(b) an equivalent amount of di-n-hexylphosphate. 
The preparation of (a) is described in Comparative Example C of EP 127,325, 
omitting the quaternisation stage with dimethylsulphate. 
The Polyesterammonium salt is useful as an additive for lubricants in which 
it can provide protection against wear of surfaces in contact, protection 
against deposition of sludge, resistance to extreme pressure experienced 
in bearings and resistance to oxidation and corrosion. 
Lubricants in which the Polyesterammonium salt may be used include oils and 
greases for protecting metal surfaces in frictional contact. The 
Polyesterammonium salt may be used at a concentration from 0.01 to 10% by 
weight, based on the total weight of the lubricant. As a further feature 
of the invention there is provided a lubricant composition comprising a 
lubricant containing from 0.01 to 10%, preferably from 0.05 to 5% and 
especially from 0.1 to 2% by weight of the Polyesterammonium salt. 
The lubricant may be an oil or grease. 
The term oil includes oils such as those described in standard texts on 
lubrication such as "Schmiermittel-Taschenbuch" by Schewe-Kobek, (Huethig 
Verlag, Heidelberg 1974), and in "Schmierstoffe and Verwandte Produkte" by 
D. Klamann, (Verlag Chemie, Weinhelm 1982). 
The oil is preferably a mineral oil or a synthetic oil or a mixture 
thereof. 
Examples of such oils include poly(alkyleneglycols); poly(alpha-olefins); 
esters, especially phthalates, such as iso-tridecyl phthalate, 
perfluoroalkylethers and silicones. 
The oil may contain a hydrofluorocarbon, hydrochlorofluorocarbon or 
chlorofluorocarbon or mixtures thereof such as are used in mechanical 
vapour recompression, heat transfer devices. 
Preferred lubricants are those used industrially, especially gear and 
hydraulic oils. 
The oil may contain other additives which are generally incorporated in 
fluid lubricants, such as metal passivators, viscosity-index improvers, 
pour-point depressants, dispersing agents, detergents, and different 
additives providing protection against wear, extreme pressure, corrosion, 
rusting and oxidation. 
Examples of additives are such disclosed in EP 398,843 and U.S. Pat. No. 
4,962,227. More specifically, the oil may contain the anti-corrosion 
composition described in EP 455,451. 
The grease is preferably a mineral or synthetic oil as hereinbefore 
described which has been thickened by the addition of a gelling agent. 
The gelling agent may be a soap, such as a lithium soap, a lithium complex 
soap, a non-soap gelling agent such as a clay, a carbon black, a silica or 
a polyurea which is preferably incorporated into the oil in finely divided 
form. 
Any clay is preferably surface-coated with an organic material such as a 
quaternary ammonium compound. 
Where the grease is based on a silicone oil, the non-soap gelling agent is 
preferably silica, especially fused silica having an average particle 
diameter below one micron. 
Metals which benefit from the protection of the Polyesterammonium salt and 
lubricant compositions containing the Polyesterammonium salt include iron 
and steel and especially copper and brass where the Polyesterammonium salt 
has been found less aggressive than many commercially available lubricant 
additives with this latter group of metals. 
The Polyesterammonium salt has been found particularly effective when the 
metal surfaces in frictional contact are part of a bearing. 
Thus, according to a further feature of the invention there is provided a 
metal surface, particularly a bearing, treated with the Polyesterammonium 
salt or a lubricant composition containing the Polyesterammonium salt. 
As the Polyesterammonium salt also exhibits anti-corrosion and anti-oxidant 
properties it may be applied to metal surfaces in an appropriate carrier 
as described for example in EP 455415. 
The invention is further illustrated in the following examples in which all 
parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 
Antiwear Agent 1 
A) Preparation of Polyesteramine (PED) 
The Polyesteramine was obtained by the reaction of two mole of 
poly(12-hydroxyoctadecanoic acid) of molecular weight about 1600 (as 
determined by titration) with one mole of 
1-amino-3-N,N-dimethylaminopropane as described in Comparative Example C 
of EP 127,325. 
This amine when titrated with 0.1M perchloric acid in glacial acetic acid, 
had an `base` value of 15.69 mg KOH per gram. 
B) Preparation of Hexyl Phosphate (HP) 
A mixture of mono and di-n-hexyl phosphate was prepared by reacting three 
mole of n-hexanol with one mole of phosphorous pentoxide. 
This material when titrated with 0.1M alcoholic potassium hydroxide 
solution using 1-naphthophthalein as indicator had an `acid` value of 
377.9 mg KOH per gram. 
C) Preparation of Antiwear Agent 1 
A mixture of 0.41g of HP and 9.59g PED was heated at 100.degree. C. for 
approximately one hour to ensure reaction. This gave a fully neutralised 
(FN) organophosphorus salt of PED. 
EXAMPLE 2 
Lubricant 1 
A lubricant composition was prepared by adding 1 part of Antiwear Agent 1 
to 99 parts of a solvent neutral base oil (viscosity 24 mm.sup.2 s.sup.-1 
at 40.degree. C.; sulphur content 1.6%). 
EXAMPLE 3 
A sample of Lubricant 1 was subjected to a four ball antiwear test based on 
IP239 (temperature 75.degree. C.; time 1 hour; Load 40 Kg) using the same 
solvent neutral base oil as control. At the end of the test the average 
wear scar diameters (WSD) were measured and these are recorded in Table 1. 
TABLE 1 
______________________________________ 
Example Additive WSD (mm) 
______________________________________ 
3 Antiwear Agent 1 
0.44 
Control Nil 1.16 
______________________________________ 
EXAMPLE 4 
Antiwear Agent 2 
A) Preparation of Mono 2-Hexyldecyl Phosphate (PMH) 
This phosphate was prepared by reacting 2-hexyldecanol (242 g) (Eficay 
Chemicals) with pyrophosphoric acid (213.6 g) (97%, Fluka) at room 
temperature for 4 days. The product was purified via the sodium salt, 
extraction into an inert organic solvent, and acidification. Yield 18%. 
This material had an acid value of 169.9 mg KOH per g from the first 
end-point as determined by auto-titration with M/10 tetraethylammonium 
hydroxide (TEAH) in propan-2-ol, in the presence of bromophenol blue 
indicator. 
B) Preparation of Antiwear Agent 2 
A mixture of 1.0 g of PMH and 10.15 g PED was heated at 100.degree. C. for 
approximately fifteen minutes to ensure reaction. This gave a partly 
neutralised organophosphorus salt of PED. 
EXAMPLE 5 
Antiwear Agent 3 
A mixture of 1.0 g of bis(2-ethylhexyl) phosphate from BDH (having an acid 
value of 169.9 mg KOH per g by auto-titration with M/10 tetraethylammonium 
hydroxide (TEAH)) and 10.43 g PED was heated at 100.degree. C. for 
approximately fifteen minutes to ensure reaction. 
This gave a partly neutralised organophosphorus salt of PED. 
EXAMPLE 6 
Antiwear Agent 4 
A mixture of 1.05 g O,O-bis(2-ethylhexyl) phosphoromonothioate (Hoechst) 
(having an acid value of 138.0 mg KOH per g by auto-titration with M/10 
tetraethylammonium hydroxide (TEAH)) and 10.15 g PED was heated at 
100.degree. C. for approximately fifteen minutes to ensure reaction. This 
gave a fully neutralised organophosphorus salt of PED. 
EXAMPLE 7 
Antiwear Agent 5 
A mixture of 1.0 g of O,O-diethyl phosphorodithioate (Aldrich) (having an 
acid value of 279.0 mg KOH per g by auto-titration with M/10 
tetraethylammonium hydroxide (TEAH)) and 17.3 g PED was heated at 
100.degree. C. for approximately fifteen minutes to ensure reaction. This 
gave a fully neutralised organophosphorus salt of PED. 
EXAMPLE 8 
Antiwear Agent 6 
A mixture of 0.5 g of n-octylphosphonic acid (Johnson Matthey) (having an 
acid value of 320.7 mg KOH per g by auto-titration with M/10 
tetraethylammonium hydroxide (TEAH)) and 5.89 g PED was heated at 
100.degree. C. for approximately fifteen minutes to ensure reaction. This 
gave a 1:1 organophosphorus salt of PED. 
EXAMPLE 9 
Antiwear Agent 7 
A mixture of 1.0 g of 2-ethylhexyl 2-ethylhexylphosphonate from BDH (having 
an acid value of 180.8 mg KOH per g by auto-titration with M/10 alcoholic 
potassium hydroxide solution using 1-naphthophthalein as indicator) and 
11.24 g PED was heated at 100.degree. C. for approximately fifteen minutes 
to ensure reaction. 
This gave a fully neutralised organophosphorus salt of PED. 
EXAMPLE 10 
Antiwear Agent 8 
A) Preparation of Dihexyl Pyrophosphate (DHP) 
This phosphate was prepared as a mixture of symmetrical and non-symmetrical 
esters by reacting two mole of n-hexanol with one mole of phosphorous 
pentoxide in the method of J. H. Cronje, J. S. African Chem. Inst., 1949, 
2, 15-27. 
This material when titrated with M/10 alcoholic potassium hydroxide 
solution using 1-naphthophthalein as indicator had an acid value of 359 mg 
KOH per gram. 
B) Preparation of Antiwear Agent 8 
A mixture of 1.06 g of DHP and 23.5 g PED was heated at 100.degree. C. for 
approximately fifteen minutes to ensure reaction. This gave a fully 
neutralised organophosphorus salt of PED. 
EXAMPLE 11 
Antiwear Agent 9 
A) Preparation of Polyesteramine (PCD) 
The Polyesteramine was obtained by the reaction of 55 g 6-caprolactone with 
10 ml of 1-amino-3-N,N-dimethylaminopropane in the presence of 0.1 ml 
tetrabutyl titanate with stirring for 1.5 hr. at 160.degree. to 
165.degree. C. 
This amine when titrated with 0.1M hydrochloric acid, had an `base` value 
of 15.69 mg KOH per gram. 
B) Preparation of Mono Iso-octadecyl Phosphate (IOP) 
A mixture of mono and di-iso-octadecyl phosphate was prepared by reacting 
three mole of iso-octadecanol with one mole of phosphorous pentoxide. 
This material had an acid value of 169.9 mg KOH per g from the first 
end-point as determined by auto-titration with M/10 tetraethylammonium 
hydroxide (TEAH). 
C) Preparation of Antiwear Agent 9 
A mixture of 7.81 g of IOP and 12.96 g CPD was heated at 50.degree. C. for 
about 20 minutes to ensure reaction. This gave a salt of PCD. 
EXAMPLE 12 
Antiwear Agent 10 
A) Preparation of Polyesteramine (PEP) 
The Polyesteramine was obtained by the reaction of one mole of 
poly(12-hydroxyoctadecanoic acid) of molecular weight about 1600 (as 
determined by titration) with two mole of piperazine dihydrate by heating, 
initially to 110.degree. C. and after removing solvent to 170.degree. C., 
to remove water and excess piperazine. 
This amine when titrated with 0.1M perchloric acid in glacial acetic acid, 
had an `base` value of 33.2 mg KOH per gram. 
B) Preparation of Antiwear Agent 10 
A mixture of 7.81 g of HP and 12.96 g PEP was heated at 50.degree. C. for 
about 20 minutes to ensure reaction. This gave a fully neutralised salt of 
PEP. 
EXAMPLE 13 
Lubricants 2 to 10 
Lubricant compositions 2 to 10 were prepared from each of the Antiwear 
Agents 2 to 10 respectively as described in Example 2. 
EXAMPLE 14 
A sample of each of Lubricants 2 to 8 and 10 was tested as described in 
Example 3 to determine its WSD, and these are recorded in Table 2. 
TABLE 2 
______________________________________ 
Additive WSD (mm) 
______________________________________ 
Antiwear Agent 2 0.37 
Antiwear Agent 3 0.41 
Antiwear Agent 4 0.39 
Antiwear Agent 5 0.37 
Antiwear Agent 6 0.44 
Antiwear Agent 7 0.57 
Antiwear Agent 8 0.46 
Antiwear Agent 10 
0.32 
______________________________________ 
EXAMPLE 15 
Lubricant 11 
A lubricant composition 11 was prepared by adding 1 part of Antiwear Agent 
9 to 99 parts of the synthetic ester di-iso-tridecyl phthalate (ICI C&P). 
EXAMPLE 16 
A sample of Lubricant 11 was tested as described in Example 3 to determine 
its WSD, and this is recorded in Table 3. 
TABLE 3 
______________________________________ 
Additive WSD (mm) 
______________________________________ 
Antiwear Agent 9 
0.52 
Nil 0.92 
______________________________________ 
EXAMPLE 18 
Lubricant 12 
A lubricant composition 12 was prepared by adding 1 part of Antiwear Agent 
5 to 99 parts of a lithium hydroxystearate base grease with a total soap 
content of 9.4%. 
EXAMPLE 16 
A sample of Lubricant 12 was tested as described in Example 3 to determine 
its WSD, and this is recorded in Table 4. 
TABLE 4 
______________________________________ 
Additive WSD (mm) 
______________________________________ 
Antiwear Agent 5 
0.36 
Nil 0.75 
______________________________________