Transcript Naugalube 810 / MLA

Bench Screening of Novel
Anti-Wear Alternatives
to ZDDP
Victor Bakunin, Trade and Technical representative, CIS
Moscow, Russia
Cyril Migdal, Director, Petrochemical Additives
Middlebury, CT, USA
CHEMTURA – a new brand at the Oils and
Additives market
The chemical
company
of the future
Textile machinery, dyes,
polymer additives,
lubricants, agricultural
chemicals,
urethanes….
(Crompton
Corporation) Specialized chemicals
Our History
Rubber, rubber
components,
industrial rubber
products,
footwear, tires,
synthetic rubber,
agricultural
chemicals
Kaufmann Holdings
was acquired in 2007.
Ester lubricants –
ester polyols + readyto-use synthetic fluids
Crompton
&
Knowles
1830s
Uniroyal
(formerly
Witco
1920s
US Rubber)
Carbon for tires,
plasticizing agents,
stearates, stabilizers,
silicones …
Specialized
chemicals
1890s
Chemtura
2005
Hatco /
Eni
Lowi
Rhone-Poulenc
Anderol
Great Lakes
FMC
Phosphates – noncombustible fluids
(formerly Ciba)
Ordinary and
specialized
phenolic
antioxidants
1930s
Bromine, bromine derivatives,
combustion inhibitors, agricultural
chemicals, polymer additives, pool
chemicals, household chemicals,
fluorine derivatives, optical
monomers
Our Additives Trademarks
Naugalube® and Naugard® antioxidants;
Calcinate™, Hystrene® and Industrene® anti-wear agents;
Lobase®, Hybase® and Petronate® sulfonate detergents;
Synton® high-viscosity polyalphaolefins (PAO);
G-2000™ high-quality lubricants;
Durad® additives based on organic phosphates;
Reolube® non-combustible lubricants and fluids (phosphates);
Reomol® and KP-140® special additives (phosphates);
ANDEROL®, AOSyn®, PQ® special lubricants;
Hatcol® esters and ester lubricants (ready-to-use and basestocks);
Royco® aircraft lubricants.
2016
Евро 5
2014
RUSSIA
EUROPE
2012
Год
Евро 4
2010
Евро 3
2008
2008
Евро 2
2006
2004
Ужесточение экологических требований
Standard
Approval Date
Euro 1
October 1993
Euro 2
October 1996
Euro 3
October 1999
Euro 4
October 2005
Euro 5
Октябрь 2008
October
Zinc dialkyldithiophosphate (ZDDP)
- more than simply anti-wear protection
Экология: SOx
Зола
S
RO
S
P S
-
++
Zn
S P
OR
OR
OR
Зола
Willermet et al, Trib. Inter., 5/95
Яд для катализаторов дожига
•Zinc is the base for the formation of tribolayers (Zinc Polyphosphate)
•ZDDP is an antioxidant
•ZDDP is a synergist for Mo-containing additives
Cumylhydroperoxide (CHP)
CH3
C O OH
CH3
Effect of CHP on anti-wear properties
of engine lubricants (four-ball test machine)
0.0 вес.% КГП
0.5 вес.% КГП
1.0 вес.% КГП
2.0 вес.% КГП
1
0,9
0,8
Ди, мм
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0
ТНДМ
ТНДМ: нет AW
АМ
АМ: нет AW
ASTM D 4172
Effect of CHP on anti-wear properties
of engine lubricants
(Cameron-Plint)
0.0 вес.% КГП
0.5 вес.% КГП
1.0 вес.% КГП
2.0 вес.% КГП
1
0,9
0,8
Ди, мм
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0
ТНДМ
ТНДМ: нет AW
АМ
АМ: нет AW
Ashless P-containing additives
S
S
RO
P
OR
O
S R'
Ñë. ýô èðû äèòèî ô î ñô î ðí î é ê-òû
P
O
O
R
R
R
RO
Òðèàðèëòèî ô î ñô àòû
P
OH
OR
Ôî ñô èòû (í åò S)
O
RO
P
OR
-+
O NR'4
Ôî ñô àòû àì ì î í èÿ (í åò S)
Phosphorus-free additives
(All contain sulfur - SOx, sulfate ash)
S
S
R2N C S S C NR2
N
S
Òèóðàì äèñóëüô èäû
S
R2N C S R'
S
S
R2N C S CH2 S C R2N
Ýô èðû äèòèî êàðáàì èí î âî é ê-òû
N N
HS
S
N N
S
S
S
Òèàäèàçî ëû
S N R
H
Ñóëüô åí àì èäû
S
R2N C S M
Äèòèî êàðáàì àòû
(çî ëüí û å)
Î ñåðí åí í û å î ëåô èí û
SH
Î ñåðí åí í û å ñë. ýô èðû
New anti-wear additives
R1
S
R2
H
N
RN
N
NH
H
R3
R4
Imidazolidine thion
Cyclic thiourea
R1
HO
O
O
O
R3
O
R4
H
N N
O B
O
R5
R
R2
Imidazolidine thion
S
O
Oxamide
R1
R2
NH
NH
O
Hydrazide of succinic acid
Silicon-containing compounds:
Silanes/Siloxanes
O
Si
O
O
O Si
O
O
Octyltriethoxysilane
O
Si
O
O
Bis-(triethoxysilyl) ethane
S
S
O
O
O Si
Si
O
O
O
Bis-(truethoxysilyl) propyl disulfide
Anti-wear properties of engine lubricants containing
silanes (Cameron-Plint)
Zn-ДТФ (0.10% P)
Zn-ДТФ (0.05% P)
нет Zn-ДТФ
1% присадки, без Zn-ДТФ
Бутил дисульфид
Бутил сульфид
Бис(Триэтоксисилил)
пропил
дисульфид
Бис(триэтоксисилил)
этан
Без присадок
0.05 вес. % P
Октил
триэтоксисилан
Silanes & ZDDP synergy!
24
22
20
18
16
14
12
10
8
6
4
2
0
0.10 вес. % P
Max. fin wear depth (uм)
Zn-ДТФ (0.05% P) + 0.5% Присадки
Anti-wear additives based on
esters
• MLA-2837
– Ashless, no S & P
– Synergism with ZDDP
– Free-flowing clear liquid
– Non-corrosive
Sulfur-containing anti-wear
additives
MLA-2877
MLA-2871
• Thiocarbamate derivative
• S-containing heterocycle
• 12 % S
• Synergism with ZDDP
• Free-flowing yellow liquid
• 22 % S
• Non-corrosive
• Free-flowing yellow liquid
• Non-corrosive
Four-ball friction machine
ASTM D 4172
1
0,9
63x
0,8
0,6
73x
14x
0,5
Max. fin wear depth (uм)
0,4
0,3
0,2
0,1
1 additives weight %
(or as stated)
нет присадок
MLA-2877 +
Zn-ДТФ
(0.5/0.05 %P)
MLA-2877
MLA-2871 +
Zn-ДТФ
(0.5/0.05 %P)
MLA-2871
0.05 вес.% P
0
0.10 вес.% P
Ди, мм
0,7
1 additives weight %
(or as stated)
MLA-2877 + ZnДТФ (0.5/0.05
%P)
MLA-2877
MLA-2871 + ZnДТФ (0.5/0.05
%P)
MLA-2871 (2 %)
MLA-2871
нет присадок
0.05 вес.% P
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0.10 вес.% P
Fin wear depth (uм)
Cameron-Plint tribometer
57x
12x
91x
Selection criteria
Use conditions
Compatibility with sealants
• Activation temperature/ pressure
Smell
Price/Quality
Physical condition
Corrosive power
Toxicity
Volatility
Compatibility with packaging
Color
Duration of action
Solubility
Multifunctionality
• AO; AF; contribution to EP
Conclusions
As an anti-wear catalytic agent, CHP reliably
distinguishes among lubricants with respect to antiwear qualities in tests on a four-ball friction machine
and the Cameron-Plint tribometer.
By screening various compounds, it was possible to
identify several quality classes of potential anti-wear
additives for engine lubricants as replacements for
zinc dialkyldithiophosphate:
• Heterocycles with Sulfur/Nitrogen atoms
• Esters with Nitrogen atoms (CHON)
• Silanes/Siloxanes