Metal working fluids

Date of inclusion in the List of MAK and BAT Values: 1982

List of Components

The Commission of the Deutsche Forschungsgemeinschaft for the Investigation of Health

Hazards of Chemical Compounds in the Work Area first drew attention to metal working
fluids and their occupational-medical significance in the List of MAK and BAT Values
(Report No. XVIII) in 1982 and put forward a list of components of metal working fluids
which, in collaboration with the Association of German Lubricant Manufacturers (VSI:
Verband der Schmierstoff-Industrie), is continually extended to keep up with technical
and scientific developments. In this fourth revised edition of the list, as in its predeces-
sors, the components are listed where necessary in chemical classes. The names of the
components are, to the best of our knowledge, those in general use; 61 components have
been added to the list. Groups of substances and individual components which have been
deleted from the list are shown in a “historical appendix” and the reasons for their dele-
tion are given. They include, for example, metal working fluid components which are no
longer used for this purpose because of a ban or because the substances are no longer
available. As in the List of MAK and BAT Values, structural formulae and CAS numbers
are given. Components whose use is forbidden by EC law are not included in the list
whereas those which are no longer produced in Germany but which could still be
imported or used are still listed for reasons of occupational safety.
The concentrations given in the list (% w/w) are approximate values and refer to the
metal working fluid concentrate as delivered by the producer. Other compositions and
concentrations intended for specific industrial applications may be encountered. The
water-miscible metal working fluids are mixed with water in various proportions (1:5 to
1:100) before use; therefore the concentrations of the components given here can be
much higher than those in the end product. In revision of the list of metal working fluid
components, every attempt was made to include all the components which are used
today. However, it cannot be claimed that the list is complete because there is no legal
requirement for declaration of metal working fluid components.
The list is intended as a guideline for the toxicological evaluation of metal working fluids
used at the workplace and should facilitate early recognition of any adverse effects on
health so that appropriate protective measures can be taken. Inclusion in the list is not a
suggestion that a substance is toxicologically safe. Before use of a substance as a metal
working fluid component, it should always be checked whether documentation for the
substance is available. Nor is it always permissible to draw conclusions on the basis of
the known effects of homologous substances; every substance should be checked for
toxicity before use, especially with respect to absorption through the skin and sensitizing
effects.
198 Metal working fluids Volume 20

Nitrosamine formation in metal working fluids

Nitrosation of amines can take place not only in acid milieu but also under the alkaline
conditions in metal working fluids. Because nitrogen oxides are effective nitrosating
agents also under alkaline conditions (Challis et al. 1978, IARC Sci Publ (19): 127–42),
when nitrosatable amines are present nitrogen oxides should be excluded. The nitrosation
reaction with nitrite is accelerated in the presence of formaldehyde (Keefer and Roller
1973, Science 181: 1245–1247). Formaldehyde reacts in aqueous systems with the nitro-
gen atom of the amine to form an N-methylol compound. This reduces the basicity of the
nitrogen atom and enables relevant levels of nitrosation to take place even under alkaline
conditions.
Also of significance is the possibility of nitrosamine formation from nitrogen-
containing biocides which can release formaldehyde, e.g. morpholine derivatives with
methylene bridges. After release of formaldehyde from such biocides, molecules of
appropriate structure can yield secondary amines whose nitrosation is favoured by the
presence of the formaldehyde. However, formaldehyde-releasers which do not contain or
release nitrosatable compounds can, as a result of the bacteriostatic effects of the trace
amounts of formaldehyde they release, prevent the bacterial reduction of nitrate to nitrite
and so inhibit nitrosamine formation.
Studies of the nitrosatability of oxazolidines have been carried out by two producers
with two biocides (3,3'-methylenebis(5-methyloxazolidine) and 5-ethyl-3,7-dioxa-1-aza-
bicyclo[3.3.0]octane). The oxazolidines are produced during partial hydrolysis of the
substances or are present as impurities after synthesis. Under conditions corresponding to
intensive use in metal working fluids (concentration as recommended by the producer,
pH 9, nitrite concentration 20 or 50 mg/kg, temperature up to 70°C, incubation for up to
3 weeks), formation of N-nitrosooxazolidines was observed but the amounts produced
were very small (maximum level 0.1 mg/kg which is close to the detection limit of the
GC-TEA detector used). Thus the risk of N-nitrosooxazolidine formation in modern
metal working fluids seems to be rather low (unpublished studies carried out for Dow
Chemical 2000 and Carl Becker Chemie 2000).
Volume 20 Metal working fluids 199

List of Substances

Class of Substance Concentration

in % w/w (approx.)

1. Monohydric alcohols
(solvents/coupling agents)
isopropanol [67-63-0] n. s.
(CH3)2CH–OH
isobutanol [78-83-1] up to 5
(CH3)2CH–CH2–OH
hexanol [111-27-3] up to 5
CH3–(CH2)4–CH2–OH
octanol [111-87-5] up to 5
CH3–(CH2)6–CH2–OH
decanol [112-30-1] up to 5
CH3–(CH2)8–CH2–OH
2-butyl-1-octanol [3913-02-8] n.s.
CH3–(CH2)5–CH(C4H9)–CH2–OH
2-hexyl-1-decanol [2425-77-6] up to 10
CH3–(CH2)7–CH(C6H13)–CH2–OH
isotridecanol [27458-92-0] up to 5
(CH3)2CH–(CH2)9–CH2–OH
fatty alcohols, saturated/unsaturated C12/C18 up to 101
CnH2n+1–OH/CnH2n–1–OH; n = 12–18
isooctadecanol [27458-93-1] n.s.
(CH3)2CH–(CH2)14–CH2–OH

2. Polyhydric alcohols
(solvents/coupling agents/lubricity improvers)
ethylene glycol [107-21-1] up to 20
HO–CH2–CH2–OH
diethylene glycol [111-46-6] up to 10
HO–(CH2–CH2–O)2–H
triethylene glycol [112-27-6] n.s.
HO–(CH2–CH2–O)3–H
polyethylene glycol [25322-68-3] up to 20
HO–(CH2–CH2–O)n–H; n = 4–1000
propylene glycol [57-55-6] up to 10
CH3–CHOH–CH2–OH
2-hydroxy-2-ethyl-1,3-propanediol n.s.
HOCH2–C(OH)(C2H5)–CH2OH
dipropylene glycol [25265-71-8] up to 10
HO–(CH(CH3)–CH2–O)2–H
polypropylene glycol [25322-69-4] up to 10
HO–(CH(CH3)–CH2–O)n–H; n = 3–70
200 Metal working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

2-methyl-2,4-pentanediol [107-41-5] up to 5
(CH3)2–COH–CH2–CHOH–CH3
2-ethyl-1,3-hexandiol [94-96-2] up to 5
HO–CH2–CH(C2H5)–CHOH–CH2–CH2–CH3
glycerol [56-81-5] up to 10
HO–CH2–CHOH–CH2–OH
ethylene glycol/propylene glycol copolymers; e.g.: n.s.
C12–C14 alkylpolyethylene glycol/propylene glycol ethers [68439-51-0]
or polyethylene polypropylene glycol [9003-11-6]

3. Ethers and esters of polyhydric alcohols

(solvents/coupling agents/lubricity improvers)
ethers of polyhydric alcohols
ethylene glycol n-butyl ether [111-76-2] up to 5
C4H9–O–CH2–CH2–OH
diethylene glycol n-butyl ether [112-34-5] up to 5
C4H9–O–(CH2–CH2–O)2–H
triethylene glycol n-butyl ether [143-22-6] up to 10
C4H9–O–(CH2–CH2–O)3–H
2-phenoxyethanol [122-99-6] up to 10
C6H5–O–CH2–CH2–OH
1-phenoxy-2-propanol [4169-04-4] up to 10
C6H5–O–CH2–CHOH–CH3
polyglycol ethers (nonionic surfactants); e.g.:
polypropylene glycol monobutyl ether [9003-13-8] n.s.
HO–(CH2–CH(CH3)–O)n–C4H9
alkyl polyglycol ethers (fatty alcohol ethoxylates)
CnH2n+1–O–(CH2–CH2–O)m–H
– C12/C22 fatty alcohol ethoxylates up to 12 mol ethoxylate/mol fatty alcohol up to 10
n = 12–22, m ≤ 12
acyl polyglycol ethers (fatty acid ethoxylates)
R–CO–O–(CH2–CH2–O)n–H
– tall oil ethoxylate up to 12 mol ethoxylate/mol fatty alcohol up to 10
– ricinus oil ethoxylate up to 40 mol ethoxylate/mol fatty alcohol up to 10
– coconut oil acid ethoxylate up to 12 mol ethoxylate/mol fatty alcohol up to 10
– oleic acid ethoxylate up to 12 mol ethoxylate/mol fatty alcohol up to 10
R = CH3–(CH2)7–CH=CH–(CH2)7; n ≤ 12
alkylphenol polyglycol ethers
R–C6H4–O–(CH2–CH2–O)n–H; e.g.:
– octylphenol polyglycol ethers n.s.
R = C8H17; n ≤ 12
– nonylphenol polyglycol ethers up to 12 mol ethoxylate/mol fatty alcohol up to 10
R = C9H19; n ≤ 12
Volume 20 Metal working fluids 201

Class of Substance Concentration

in % w/w (approx.)

– dodecylphenol polyglycol ethers up to 12 mol ethoxylate/mol fatty alcohol up to 10

R = C12H25; n ≤ 12
alkylaminopolyglycol ethers
R–NH–(CH2–CH2–O)n–H 2
(CH2 CH2 O)m H
R N
(CH2 CH2)n H

– coconut oil amine ethoxylate up to 10

– tall oil amine ethoxylate up to 10

4. Aliphatic amines
(neutralizing agents)
dicyclohexylamine [101-83-7] n.s.
(C6H11)2NH
alkanolamines
2-aminoethanol (monoethanolamine (MEA)) [141-43-5] up to 5
HO–CH2–CH2–NH2
2-((hydroxymethyl)amino)ethanol [34375-28-5] 2 up to 5
HO–(CH2)2–NH–CH2–OH
diethanolamine (DEA) [111-42-2] 2 up to 25
(HO–CH2–CH2)2NH
triethanolamine (TEA) [102-71-6] up to 25
(HO–CH2–CH2)3N
1-amino-2-propanol (monoisopropanolamine (MIPA)) [78-96-6] up to 10
CH3–CHOH–CH2–NH2
2-amino-2-methyl-1-propanol (AMP) [124-68-5] up to 10
CH3–C(CH3)NH2–CH2–OH
2-amino-1-butanol [96-20-8] up to 10
CH3–CH2–CHNH2–CH2–OH
2-(2-aminoethoxy)ethanol (diglycolamine) [929-06-6] up to 10
HO–CH2–CH2–O–CH2–CH2–NH2
methyldiethanolamine (MDEA) [105-59-9] up to 10
(HO–CH2–CH2)2N–CH3
2-amino-2-ethyl-1,3-propanediol (AEPD) [115-70-8] up to 5
HO–CH2–C(C2H5)NH2–CH2–OH
N-(hydroxyethyl)piperidine [3040-44-6] up to 10
N CH2 CH2OH
fatty amines
R–NH2/R2NH 2 / R3N
– C12/C18 fatty amines, saturated/unsaturated up to 5
R = CnH2n+1/CnH2n–1; n = 12–18
– hydrogenated coconut oil amine up to 5
202 Metal working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

5. Aromatic amines
(antioxidants, mainly in non-water-miscible metal working fluids)
diphenylamine [122-39-4] n.s.
(C6H5)2NH
diphenylamine, octylated [68921-45-9] n.s.
2
N-phenyl-1-naphthylamine (PAN) [90-30-2] up to 20
HN C6H5

6. Aminocarboxylic acids and their derivatives

(complexing agents)
N-tosyl-6-aminocaproic acid n.s.
CH3–C6H4–SO2–NH–(CH2)5–COOH
ethylene diamine tetraacetic acid (EDTA) [60-00-4] (in neutralized form) up to 5
(HOOC–CH2)2N–CH2–CH2–N(CH2–COOH)2
polyaspartic acid (sodium salt) [181828-06-8] up to 20

7. Carbamates
(fungicides)
3-iodopropynyl butylcarbamate [55406-53-6] up to 0.5
I–C≡C–CH2–O–CO–NH–C4H9

8. Natural and modified fats

(lubricity improvers)
rape seed oil [8002-13-9] up to 100
jojoba oil [90045-98-0] up to 100
lard oil [8016-28-2] up to 50
palm kernel oil [8002-75-3] up to 50
coconut oil [8001-31-8] up to 20
ricinus oil [8001-79-4] up to 20
soya bean oil [8001-22-7] up to 20
blown (oxidized) oils up to 20
dimerized oils up to 20

9. Aliphatic carboxylic acids and their salts (soaps) 3

(in neutralized form: anionic surfactants, lubricity improvers, corrosion inhibitors;
in not neutralized form: lubricity improvers)
straight chain carboxylic acids
– undecanoic acid [112-37-8] n.s.
CH3–(CH2)9–COOH
Volume 20 Metal working fluids 203

Class of Substance Concentration

in % w/w (approx.)

– lauric (dodecanoic) acid [143-07-7] up to 5

CH3–(CH2)10–COOH
– myristic (tetradecanoic) acid [544-43-8] up to 5
CH3–(CH2)12–COOH
– palmitic (hexadecanoic) acid [57-10-3] up to 5
CH3–(CH2)14–COOH
– stearic (octadecanoic) acid [57-11-4] up to 5
CH3–(CH2)16–COOH
– behenic (docosanoic) acid [112-85-6] up to 5
CH3–(CH2)20–COOH
– 12-hydroxystearic acid [106-14-9] up to 5
CH3–(CH2)5–CHOH–(CH2)10–COOH
– hydrogenated C12/C18 fatty acids up to 5
CnH2n+1–COOH; n = 12–18
branched carboxylic acids (products of the oxo process) up to 5
– isooctanoic acid [25103-52-0]
(CH3)2CH–(CH2)4–COOH
– isononanoic acid [26896-18-4] up to 10
(CH3)2CH–(CH2)5–COOH
– isodecanoic acid [26403-17-8] up to 10
(CH3)2CH–(CH2)6–COOH
– isotridecanoic acid [25448-24-2] up to 10
(CH3)2CH–(CH2)9–COOH
– isostearic acid [30399-84-9] up to 5
(CH3)2CH–(CH2)14–COOH
– neodecanoic acid, mixtures of isomers [26896-20-8]; e.g.: n.s.
2,2-dimethyloctanoic acid
– tert-nonanoic acid (trimethylhexanoic acid) [54868-97-2] n.s.
– tert-decanoic acid (C10-trialkylacetic acid) [52627-73-3] n.s.
alkyl polyglycol ether carboxylic acids up to 5
CnH2n+1–O–(CH2–CH2–O)m–CH2–COOH
n = 12–14, m = 2.5
citric acid [77-92-9] up to 2
(HOOC–CH2)2C(OH)–COOH
– copper(II) citrate [10402-15-0] up to 2
C12H10Cu3O14
polybasic carboxylic acids
– tartaric aid [87-69-4] up to 10
HOOC–CHOH–CHOH–COOH
– succinic (butanedioic) acid [100-15-6] (see also 13.) up to 5
HOOC–CH2–CH2–COOH
– adipic (hexanedioic) acid [124-04-9] up to 10
HOOC–(CH2)4–COOH
204 Metal working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

– azelaic (nonanedioic) acid [123-99-9] up to 10

HOOC–(CH2)7–COOH
– sebacic (decanedioic) acid [111-20-6] up to 10
HOOC–(CH2)8–COOH
– undecanedioic acid [1852-04-6] n.s.
HOOC–(CH2)9–COOH
– dodecanedioic acid [693-23-2] n.s.
HOOC–(CH2)10–COOH
– dimeric acids (dimeric fatty acids) n.s.
(mixtures of acyclic and cyclic dicarboxylic acids, on average C36)
– trimeric acids (trimeric fatty acids) (tricarboxylic acids, about C54, n.s.
with alkyl side chains, double bonds and ring systems)
naphthenic acids [1338-24-5] up to 10
unsaturated carboxylic acids
– oleic acid [112-80-1] up to 20
CH3–(CH2)7–CH=CH–(CH2)7–COOH
– 5(6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid [53980-88-4] n.s.
and its derivatives
CH3 (CH2)5 (CH2)7 COOH

R1 R2
– decyl oleate [3687-46-5] up to 20
CH3–(CH2)7–HC=CH–(CH2)7–COO–(CH2)9–CH3
– isodecyl oleate [59231-34-4] up to 20
CH3–(CH2)7–HC=CH–(CH2)7–COO–(CH2)7–CH(CH3)2
– 2-ethylhexyl oleate [26399-02-0] up to 20
CH3–(CH2)7–HC=CH–(CH2)7–COO–CH2–CH(C2H5)–(CH2)3–CH3
mixtures of fatty acids, e.g.:
– ricinoleic (12-hydroxy-9-octadecenoic) acid [141-22-0] up to 10
CH3–(CH2)5–CHOH–CH2–CH=CH–(CH2)7–COOH
– linoleic acid, dimerized, trimerized up to 10
– rape seed oil fatty acids up to 10
– coconut oil fatty acids up to 10
– soya bean oil fatty acids up to 10
– tallow fatty acid [61790-37-2] up to 10
– distilled tall oil [8002-26-4] up to 10
4
– abietic acid (rosin, colophony, tall oil resin) [514-10-3]
H3C COOH

H3C
CH(CH3)2
Volume 20 Metal working fluids 205

Class of Substance Concentration

in % w/w (approx.)

10. Carboxylic acid amides and related compounds

(corrosion inhibitors)
fatty acid alkanol amides, saturated/unsaturated C12/C18 up to 10
R–CO–NR'–(CH2)n–OH; n ≥ 2, R' = H, (CH2)n–OH
tall oil amides up to 10
oleoyl sarcosine [110-25-8] up to 5
CH3–(CH2)7–CH=CH–(CH2)7–CO–N(CH3)–CH2–COOH

11. Carboxylic esters of monohydric and polyhydric alcohols of the fatty acids and fatty acid
mixtures listed under 9. above
(lubricity improvers)
methyl esters CH3– up to 10 1
butyl esters C4H9– up to 10
isopropyl esters (CH3)2CH– up to 10
isobutyl esters (CH3)2CH–CH2– up to 10
isooctylesters (CH3)2CH–(CH2)4–CH2– up to 10
2-ethylhexyl esters CH3–(CH2)3–CH(C2H5)–CH2– up to 10
2-butyloctyl esters CH3–(CH2)5–CH(C4H9)–CH2– n.s.
pentaerythritol ester (HO–CH2)3C–CH2– up to 10
trimethylolpropane esters (HO–CH2)3C–CH2–CH2– up to 10
glycerol esters HO–CH2–CHOH–CH2– up to 10
neopentylglycol esters (CH3)3C–CH2–CHOH–CH2– up to 10
decyl esters CH3–(CH2)8–CH2– up to 10
isodecyl esters (CH3)2CH–(CH2)6–CH2– up to 10
isotridecyl esters (CH3)2CH–(CH2)9–CH2– up to 10

12. Aldehyde derivatives

(biocides)
1,2-propylene glycol hemiformal n.s.
HO–CH2–O–CH2–CH(CH3)–O–CH2–OH
benzyl alcohol mono(poly)hemiformal [14548-60-8] up to 3
C6H5–CH2–O–(CH2–O)x–H; x = 1.5
1,3-bis(hydroxymethyl)urea [140-95-4] up to 2
OC(NH–CH2–OH)2
hexahydrotriazines, e.g.:
R N N R

N
R
206 Metal working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

N,N',N''-triethylhexahydro-1,3,5-triazine [7779-27-3] up to 4
R = C2H5
N,N',N''-tris(β-hydroxyethyl)hexahydro-1,3,5-triazine [4719-04-4] up to 4
R = CH2–CH2–OH
N,N',N''-tris(β-hydroxypropyl)hexahydro-1,3,5-triazine [25254-50-6] n.s.
R = CH2–CH(OH)–CH3
N,N',N''-tris(methoxypropyl)hexahydro-1,3,5-triazine [3960-05-2] n.s.
R = CH2–CH2–CH2–O–CH3
bisoxazolidines, e.g.:
– 5-ethyl-3,7-dioxa-1-azabicyclo[3.3.0]octane [7747-35-5] up to 2
C2H5
O O
N

– N,N'-methylene-bis(5-methyloxazolidine) [66204-44-2] up to 5
H 3C CH3
N CH2 N
O O
methylene-bistetrahydro-1,3-oxazine [63489-63-4] up to 5

N CH2 N
O O
methylene-bistetrahydro-1,4-oxazine (bismorpholinomethane) [5625-90-1] up to 5

O N CH2 N O

12-hydroxy-5,8,11-trioxadodecane [56289-76-0] up to 5
CH3–(CH2)3–O–(CH2)2–O–(CH2)2–O–CH2–OH
1,6-dihydroxy-2,5-dioxahexane [3586-55-8] up to 5
HO–CH2–O–(CH2)2–O–CH2–OH

13. Succinic acid derivatives

(corrosion inhibitors)
alkenyl succinic acid anhydrides up to 5
R O
R R = H, CnH2n–1
O
R
R O
alkyl succinamides, mostly dodecyl up to 5
O O
H2N C (CR2)2 C NH2 R = H, CnH2n+1

alkyl succinimides, mostly dodecyl up to 5

R O
R R = H, CnH2n+1
NH
R
R O
Volume 20 Metal-working fluids 207

Class of Substance Concentration

in % w/w (approx.)

alkenyl succinic acid half esters

– tetrapropenyl succinic acid isopropyl half ester up to 5
HOOC–(CR2)2–COO–C3H7; R = C3H5

14. Polyalkylacrylate copolymers

(adhesive agents, anti-mist additives)
polyalkylmethacrylates (PMA) up to 5
CH3
C CH2
COOR n

15. Aromatic carboxylic acids 5

(corrosion inhibitors)
benzoic acid [65-85-0] up to 10
C6H5–COOH
m-nitrobenzoic acid [121-92-6] n.s.
O2N COOH

6,6',6''-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid [80584-91-4] up to 20

and its derivatives
R
R = NH–(CH2)5–COOH
N N
R N R
16. Phenols
(biocides, antioxidants)
4-tert-butylphenol [98-54-4] up to 1
(CH3)3C–C6H4–OH
2,6-di-tert-butylphenol [128-39-2] up to 1
((CH3)3C)2C6H3–OH
2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT) [128-37-0] up to 1
((CH3)3C)2C6H2(CH3)–OH
4,4'-methylene bis(2,6-di-tert-butylphenol) (dimeric BHT) [118-82-1] up to 1
(CH3)3C C(CH3)3

HO CH2 OH

(CH3)3C C(CH3)3

o-phenylphenol (OPP) [90-43-7] up to 3

C6H5–C6H4–OH
o-phenylphenol sodium (OPP-Na or SOPP) [132-27-4] up to 3
C6H5–C6H4–ONa
208 Metal working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

tert-butyl-4-hydroxyanisole (BHA) [25013-16-5] up to 0.2

H3CO C(CH3)3

OH
alpha-tocopherol (vitamin E) [59-02-9] n.s.
CH3
HO
CH3
H3C O (CH2 CH2 CH2 CH(CH3))3 CH3
CH3

17. Heterocycles containing N or N and O

(corrosion inhibitors, biocides)
2-benzimidazole carbamic acid methyl ester (carbendazim) [10605-21-7] up to 0.5
O N
H3C O C HN
N
H
1-(2-allyloxy)-2-(2,4-dichlorophenyl)ethyl)-1H-imidazole [35554-44-0] n.s.
CH3
Cl O

Cl N
N
1-hydroxyethyl-2-heptadecenyl imidazoline [21652-27-7] up to 5
CH2 CH2 OH
N
N (CH2)7 CH=CH (CH2)7 CH3
1,3-dimethylol-5,5'-dimethylhydantoin [6440-58-0] n.s.
O CH2OH
H3C N
H3C N O
CH2OH
1,3,4,6-tetra(hydroxymethyl)-[3aH,6aH]-1,3,4,6-tetraazabicyclooctane- n.s.
2,5-dione (tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)imidazo-[4,5-d]-
imidazole-2,5-(1H,3H)-dione) [5395-50-6]
O
HOCH2 N N CH2OH

HOCH2 N N CH2OH
O
Volume 20 Metal-working fluids 209

Class of Substance Concentration

in % w/w (approx.)

1H-benzotriazole [95-14-7] up to 0.5

N
N
N
H
methyl-1H-benzotriazole [29385-43-1] up to 0.5
N
H3C N
N
H
N-alkylbenzotriazoles up to 1
N-hydroxyalkylbenzotriazoles
N
N R = CnH2n+1/CnH2n–OH
N
R
tetrahydrobenzotriazole [6789-99-7] up to 0.1
N
N
N
H
diisooctylaminomethyltolutriazole (N,N'-[bis(2-ethylhexyl)]-1-amino- n.s.
methylene-4-methyl-1H-benzotriazole) [80584-90-3, 80595-74-0]
CH2 N(CH2 CH(C2H5) (CH2)3 CH3)2
N
N
N
CH3
sodium pyrithione (1-hydroxy-2(1H)-pyridinethione sodium salt)
[3811-73-2 and 15922-78-8] up to 0.5

+
N S-Na+ N S
O- O-Na+

18. Heterocycles containing N and S

(corrosion inhibitors, biocides)
1,2-benzisothiazol-3(2H)-one [2634-33-5] up to 0.1
S
NH
O
2-methyl-2,3-dihydroisothiazol-3-one [2682-20-4] and
5-chloro-2-methyl-2,3-dihydroisothiazol-3-one [26172-55-4] up to 0.1
S Cl S
N CH3 N CH3
O O
210 Metal-working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

2-n-octyl-2,3-dihydroisothiazol-3-one [26530-20-1] up to 0.1

S
N C8H17
O
thiabendazole (2-(4-thiazolyl)-1H-benzimidazole) [148-79-8] n.s.
N N
S N
H
dimercaptothiadiazoles, e.g. n.s.
dialkyldimercapto-1,3,4-thiadiazoles,
alkyl = C8, C9, C12, e.g.:
2,5-(nonyldisufide)-1,3,4-thiadiazole
N N
R S S S S R
S

19. Salts of naphthenic acids

Na naphthenate [61790-13-4] up to 10
K naphthenate up to 10
Ca naphthenate [61789-36-4] up to 5

20. Synthetic alkylaryl sulfonates

(anionic surfactants, corrosion inhibitors)
salts of mono or dialkylbenzene sulfonic acids:
Na salts up to 20
K salts SO3H up to 20
R
Ca salts up to 20
Mg salts R = mostly dodecyl up to 20
benzenesulfonyl-N-methyl-6-aminocaproic acid, triethanolamine salt n.s.
C6H5–SO2–N(CH3)–(CH2)5–COO– HN+(CH2–CH2–OH)3

21. Petroleum sulfonates

obtained by sulfonation of lubricating oil fractions
(anionic surfactants, corrosion inhibitors)
Na salts [68608-26-4] up to 20
K salts up to 20
Ca salts up to 20
Mg salts up to 20
fatty alcohol and fatty acid ester sulfates
– Turkey-red oil (sulfated castor oil) up to 10
Volume 20 Metal-working fluids 211

Class of Substance Concentration

in % w/w (approx.)

22. Organic Si compounds

(defoamants)
silicon oils, e.g. polydimethylsiloxane and organomodified polyethersiloxanes up to 0.1

23. Boron compounds

boric acid [10043-35-3] (neutralized) and its salts up to 10
H3BO3
boric acid alkanolamine condensation products
with primary or tertiary alkanolamines, e.g.: up to 40
– B[O–(CH2)n–NH2]3, B[O–CH2–CH2]3N; n = 2, 3, 4
with secondary alkanolamines 2, e.g.: n.s.
– HO-B[O-CH2-CH2]2NH
condensation products of vegetable oil fatty acids, alkanolamines n.s.
and boric acid, e.g.:
product of the reaction between boric acid, octanoic acid and diglycolamine

24. Molybdenum compounds

(lubricity improvers)
molybdenum disulfide [1317-33-5] up to 1
MoS2
ammonium molybdate [11098-84-3] up to 1
(NH4)3MoO4

25. Sulfur compounds

(lubricity improvers)
elemental sulfur [7704-34-9] up to 0.8
(dissolved in base oil)
dialkyl polysulfides up to 0.5
– di-tert-dodecyl polysulfide [31565-23-8]
(C12H25)2Sn; n = 2, 3, ...
dibenzyl disulfide [150-60-7] up to 0.5
(C6H5–CH2)2S2
2,2'-dithiobis(N-methylbenzamide) [2527-58-4] n.s.
H3C HN OC CO NH CH3

SS

dithiocarbamates (neutralized) up to 2
S -
R 2N C S R = CnH2n+1

– sodium diethyldithiocarbamate [148-18-5] up to 2

S
(CH3 CH2)2N C SNa
212 Metal-working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

– zinc diamyldithiocarbamate, also other alkyl groups n.s.

((C5H11)2N–CS–S)2Zn
– molybdenum di(2-ethylhexyl)dithiocarbamate n.s.
((CH3–(CH2)3–CH(C2H5)–CH2)2N–CS–S)2Mo
sulfurized polyisobutene up to 10
sulfurized polypropene up to 5
sulfurized fatty oils
– rape seed oil up to 10
– lard oil up to 10
– cottonseed oil up to 10
– soya bean oil up to 10

26. Organic phosphorus compounds

(lubricity improvers)
neutral alkyl phosphates
– tri-n-butyl phosphate [126-73-8] up to 5
(C4H9–O)3PO
– tri-oleoyl phosphate [3305-68-8] up to 5
(CH3–(CH2)7–CH=CH–(CH2)7–CH2–O)3PO
neutral aryl phosphates
– triphenyl phosphate [115-86-6] up to 5
(C6H5–O)3PO
– diphenyl cresyl phosphate [26444-49-5] up to 5
(C6H5–O)2(CH3–C6H4–O)PO
acid monoalkyl phosphates and their salts up to 5
(HO)2(RO)P=O; R = alkyl, e.g.:
– mono-n-butyl phosphate [1623-15-0]
R = CH3–(CH2)3
acid dialkyl phosphates and their salts up to 5
HO(RO)2P=O; R = alkyl, e.g.:
– dibutyl phosphate [107-66-4]
R = CH3–(CH2)3
acid aryl phosphates and their salts up to 3
(HO)2(RO)P=O; R = aryl
monoesters, diesters and triesters of o-phosphoric acid and
alkylaryl or alkyl phosphoric acids with
– polyethylene glycols up to 5
– polypropylene glycols up to 5
– and their amine or alkanolamine salts n.s.
phospholipid [173010-79-2] n.s.
phosphonic acids, phosphonic acid derivatives and organic phosphites, e.g.:
– diethylenetriamine pentakis(methylenephosphonic acid),
Na salt [22042-96-2] n.s.
Volume 20 Metal-working fluids 213

Class of Substance Concentration

in % w/w (approx.)

– hydroxyethane-1,1-diphosphonic acid, Na salt n.s.

– aminotris(methylenephosphonic acid) n.s.
– hydroxyethylaminodimethylene phosphonic acid n.s.
– di-n-butyl phosphite [1809-19-4] n.s.
H(CH3–(CH2)3–O)2P=O
– trisnonylphenyl phosphite [26523-78-4] n.s.
(CH3–(CH2)8–C6H4–O)3P
– decyldiphenyl phosphite n.s.
CH3–(CH2)9–O–P(O–C6H5)2
– phenyldidecyl phosphite [1254-78-0] n.s.
C6H5O–P(O–(CH2)9CH3)2

27. Sulfur/Phosphorus compounds

(lubricity improvers)
triphenylmonothiophosphate [597-82-0] up to 3
(C6H5–O)3PS
alkyl dithiophosphates n.s.
(R–O)2PS–SH; R = alkyl
molybdenum dialkyldithiophosphates, e.g: n.s.
molybdenum diisobutyldithiophosphate
zinc dialkyldithiophosphate up to 5
((R–O)2PS–S)2Zn; R = Alkyl
aryl dithiophosphates
(R–O)2PS–SH; R = aryl
– triphenyl dithiophosphate [67821-09-4] up to 3
(C6H5–O)2PS–(S–C6H5)

28. Chlorine compounds

(lubricity improvers)
chlorinated paraffins with 40–70 % w/w chlorine up to 100
chlorinated fatty acids up to 5

29. Hydrocarbons
(base oils)
mineral oils
– paraffinic base mineral oils up to 100
– naphthenic base mineral oils up to 100
– mixed base mineral oils up to 100
poly-α-olefins (PAO) up to 100
R
n = 2000
CH2 CH
n
214 Metal-working fluids Volume 20

Class of Substance Concentration

in % w/w (approx.)

polyisobutene (PIB) [9003-27-4] up to 5

CH3
CH2 C n = 2000
CH3 n

30. Other compounds

– quaternary ammonium salts, e.g.:
poly(oxyethylene(dimethylimino)ethylene(dimethylimino)ethylene dichloride) n.s.
– 1,2-dibromo-2,4-dicyanobutane (methyldibromoglutaronitrile) [35691-65-1] n.s.
H2CBr–CBrCN–CH2–CH2–CN

1
in non-water-miscible metal working fluids up to 100 %
2
use in metal working fluids is restricted: see TRGS 611
3
alkali metal and alkaline earth salts and salts of the amines listed under 4.
4
is not an additive but is present in distilled tall oil
5
alkali metal salts and salts of the amines listed under 4.
Volume 20 Metal working fluids 215

Substances which are at present no longer used as components of metal working fluids in
Germany (comments from the Association of German Lubricant Manufacturers (VSI,
Verband der Schmierstoff-Industrie))

Substance Comments

p-tert-butylbenzoic acid [98-73-7] because of suspected prenatal toxicity, the substance was
placed on the draft list of forbidden substances in the
GefStoffV appendix KSS (metal working fluids)
Ba naphthenate
Ba salts of petroleum sulfonates
Ba salts of synthetic alkylaryl sulfonic
acids and amidosulfonic acids
bithionol [97-18-7] no longer used because of its chlorine content; in
addition, the substance is a photosensitizer
2-bromo-2-nitro-1,3-propanediol use totally forbidden since 1993 (see TRGS 611,
[52-51-7] GefStoffV)
p-chloro-m-cresol [59-50-7] no longer used because of its chlorine content
chlorine/sulfur compounds these substances are no longer used because of their
β-chlorosulfides prepared by reaction chlorine content
of sulfur dichloride with olefins,
unsaturated fatty acids, unsaturated
fatty acid esters
4,4'-(2-ethyl-2-nitro-1,3-propanediyl)- use totally forbidden since 1993 (see TRGS 611,
bismorpholine [1854-23-5] GefStoffV)
hexamethylenetetramine [100-97-0] according to the German producers of biocides, this
substance is no longer used in metal working fluids
2-hydroxymethyl-2-nitro- use totally forbidden since 1993 (see TRGS 611,
1,3-propanediol [126-11-4] GefStoffV)
2-mercaptobenzothiazole [149-30-4] no longer used because it is a suspected carcinogen and
has sensitizing effects
chloroacetamide-N-methylol according to the German producers of biocides, this
[2832-19-1] substance is no longer used in metal working fluids
Mg naphthenate
sodium nitrite [7632-00-0] use totally forbidden since 1993 (see TRGS 611,
GefStoffV)
4-(2-nitrobutyl)morpholine [2224-44-4] use totally forbidden since 1993 (see TRGS 611,
GefStoffV)
N-phenyl-2-naphthylamine [135-86-6]
pentachlorophenol [87-86-5] use totally forbidden by law since 1989
piperazine [110-85-0] this secondary amine is not used in metal working fluids
(use restricted according to TRGS 611)
polystyrene, sulfurized
beef tallow [61789-97-7]
sperm oil [8002-24-2]
sperm oil, sulfurized
tallow oil, sulfurized
o-tricresyl phosphate [1330-78-5]
lanolin [8006-54-0]
Zn naphthenate [12001-85-3]