来自陶氏化学的新型高级合成基础油与添加剂

Oil Soluble Polyalkylene Glycols A New Group V Solution Oil

DOW CHEMICAL COMPANY Dr. Yaokun (Ken) Han

R&D / TS&D

Dow Performance Fluids

Contents

• Traditional PAG & Oil Soluble PAG (OSP)

Difference between PAG and OSP

Product Line and physical properties

• Functional benefits of OSPs

Deposit control

Friction modifier

Corrosion inhibition boosters

Air release property modifier

Ester Hydrolytic stability modifier

• Applications

Compressor fluid/Turbine fluid/Gear/Bearing oil

Grease

Engine/transmission oil

Hydraulic fluid

MWF

• Conclusions

2

Expanding functionality of PAGs using OSPs

Primary base oil in formulations

• Compressor and refrigeration oils

• Hydraulic fluids

• Textile lubricants

• Gear & Bearing oils

Additives

• Viscosity builder in water glycol hydraulic fluids

• Lubricity aid in water miscible MWFs

Traditional uses of PAGs based on

EO and PO derivatives

Use of OSPs

Expansion of formulators options

Primary Base Oil Compressor fluid

Turbine fluid

Hydraulic fluid

Gear/bearing oil

Engine/transmission oil

MWF

Grease

Co-base Oil Update I～III mineral oil

Improve the performance of PAO/POE

Performance Enhancing Additive Deposit control

Friction modifier

Corrosion inhibit booster

Air release property modifier

Hydrolytic stability modifier

3

KV40

cSt

KV100

cSt

Viscosity

Index

CCS

viscosity

at -20oC

mPa.s

Pour Point

oC

Flash

Point, oC

Aniline

Point, oC

ASTM

D445

ASTM

D445

ASTM

D2270

ASTM

D5293 ASTM D97

ASTM

D92

ASTM

D611-01

OSP-18 18 4 123 n/d -41 204 n/d

OSP-32 32 6.5 146 1750 -57 216 <-30

OSP-46 46 8.5 164 2900 -57 210 <-30

OSP-68 68 12 171 5400 -53 218 <-30

OSP-150 150 23 186 17100 -37 228 <-30

OSP-220 220 32 196 29100 -34 226 -22

OSP-320 320 36 163 n/d -37 230 n/d

OSP-460 460 52 177 n/d -35 235 n/d

OSP-680 680 77 196 n/d -30 243 n/d

Polymers derived from downstream derivatives of butylene oxide

New Oil Soluble PAGs – Typical Properties

4

Temperature, oC

Vis

co

sit

y

Starting

Temperature

Operating

Temperature

De

sig

ned

Vis

co

sit

y

Better Fuel

Economy at

low

temperatures

Better

Protection at

High

Temperatures

Impact of Viscosity Index (VI)

5

Comparison of Aniline Points

-40

-20

0

20

40

60

80

100

120

140

GpI GpII GpIII PAO Naphthenic Alk. Napth Ester

An

ilin

e p

oin

t, o

C

OSP

Typical values - Aniline points using ASTM D611-01

Additive technologies

used to boost solvency

in hydrocarbon oils

Oil Soluble PAGs can provide formulators another option for

adding back some solvency power to Group II, III and IV base oils

6

OSPs Vs Esters and Alkylated Naphthalenes Group I Mineral Oil

Deposit

formation

0 14d 50d

0 13d 41d

Group I Mineral Oil + Synthetic Ester (10%)

Deposit

formation

0 13d 41d

Group I Mineral Oil + Alkylated Naphthalene (10%)

Deposit

formation

50d

Group I +

10% OSP46

Deposit

free

50d 50d

Group I +

5% OSP46

Group I +

1% OSP46

Deposit

free Minor

deposit

Modified ASTM D2893B at 120oC 7

OSP Significantly Extend Mineral Oil Life Time

Oxidation Stability－OSP & Mineral Oil & PAO

Modified ASTM D2893, 100C, Air

150N-II 150N+10%PAO8 150N+10%OSP46 150N+20%OSP46

viscosity change, % (KV100), 20d 11.5 5.0 0.0 -2.3

TAN change, mgKOH/g 3.7 2.8 2.3 0.3

viscosity change, % (KV100), 40d 23.1 14.8 4.9 3.9

TAN change, mgKOH/g 6.9 5.2 4.4 0.4

viscosity change, % (KV100), 60d 40.2 22.8 11.9 0.02

TAN change, mgKOH/g 10.1 7.5 7.1 0.6

viscosity change, % (KV100), 80d 60.2 34.1 25.5 2.5

TAN change, mgKOH/g >12.8 9.2 6.6 0.6

8

Friction Performance of OSPs as Additives in PAO

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0 200 400 600 800 1000 1200 1400 1600 1800 2000

Time (s)

Fri

cti

on

Co

eff

icie

nt

PAO

PAO + 10% OSP

PAO + 8% OSP

PAO + 5% OSP

PAO + 8% Polyol ester

Mini-traction machine, steel ball on steel disc, temperature 80oC, speed 15 mm/sec,

Slide roll ratio = 10%, Pressure = 0.9GPa

Polyalphaolefin is a PAO-8 base oil (un-additized)

OSPs may offer another choice to esters and other surface active additives

De-ionised

Water

Synthetic sea

water

De-ionised

Water

Synthetic sea

water

%

PAG (EO/PO random copolymer) 97.0

Additive package 2.75

Sodium dialkylnaphthalene sulphonate* 0.25

%

PAG (EO/PO random copolymer) 92.0

UCON OSP** 5.0

Additive package 2.75

Sodium dialkylnaphthalene sulphonate* 0.25

OSPs as Corrosion Inhibitor Boosters

24 hours ASTM D665 A and B

* Corrosion inhibitor; ** e.g. UCON OSP-46

Traditional corrosion inhibitors are often ineffective in

passing the salt water corrosion test in conventional

EO/PO PAG formulated lubricants

Inclusion of an OSP base oil improves performance

10

Group III + OSP-46

Air Release Property Modifier

Test Method Group III + 10% OSP-46 Group III + 20% OSP-46

Kinematic viscosity at 40oC cSt, ASTM D445 46.6 45.5

Kinematic viscosity at 100oC, cSt ASTM D445 7.7 7.6

Kinematic viscosity at 0oC, cSt ASTM D7042 459 463

Viscosity Index ASTM D2272 132 136

Pour Point, oC ASTM D97 -22 -19

Density at 15oC, g/ml ASTM D7042 0.859 0.859

Total acid number, mgKOH/g ASTM D974 0.15 0.14

Ferrous corrosion, 24 hours, de-ionised water ASTM D665A pass Pass

Ferrous corrosion, 24 hours, synthetic sea water ASTM D665B pass Pass

Copper corrosion, ASTM D130 1a 1a

Four ball anti-wear, mm ASTM D4172 0.38 0.37

Four ball E.P., Kg ASTM D2783 126 126

RPVOT, minutes ASTM D2270 1976 2041

Air release, minutes ASTM D3427 2.6 1.6

Oxidation at 121oC, 13 days, KV100 change, % ASTM D2893B 1 1

Oxidation at 121oC, 70 days, KV100 change, % ASTM D2893B –ext. time 1,6 1.2

TAN change after 70 days, mgKOH/g 0.02 0.04

Thermo-oxidative stability test at 95oC, TAN change after 1000 hours, mgKOH/g

ASTM D943 0 0.05

Stability at 0, 25 and 80oC for 1 month Visual stable stable

Demulsibility, ml ASTMD1401 39/40/1 (10) 39/40/1 (10)

11

Modified ASTM D2619 – Hydrolytic stability

12

OSPs and Hydrolytic Stability Improvements of Esters

Vegetable Oil Vegetable Oil

+

10% OSP-46

Synthetic ester Synthetic ester

+

10% OSP-46

KV40 cSt 32 34.5 22.9 23.9

Viscosity index 225 220 144 151

TAN change mg KOH/g 0.4 0.1 0.07 0.05

Total acidity of

water layer

mg KOH/g

7.3

1.2

3.2

1.2

Copper

appearance

3a

1b

2c

1b

OSP-46 acts as a polymeric sponge for water negating its chemical reactivity and

reducing the rate of hydrolysis

Concepts for OSPs for

Gas and Air Compressors

Compressor types Centrifugal

Rotary screw

Reciprocating

Function of OSPs Deposit control

Long life time and interval for operation

Air release property

Heat removal – higher heat capacity/conductivity

GII Mineral Oil GII + 10% OSP68

Additive concentration, % 100.0 90.9

Four ball anti-wear /mm (147N,RT,1200rpm)

0.53 0.47

PB /kg (392N,RT,1450rpm)

85 90

PD /kg (392N,RT,1450rpm)

140 147

KV40 = 68.7 cst, Viscosity index = 112

Additive effect with commercial available RSAC lube

Customer formulation for RSAC

The additive package was diluted

Synergism between OSP and the additives

Correspond Well to Additive

14

OSP Significantly Extend Mineral Oil Life Time

Modified ASTM D2893, 100C, Air

GII Mineral Oil GII Mineral Oil plus 5% OSP

GII Mineral Oil plus 10% OSP

GII Mineral Oil plus 20% OSP

Additive concentration, % 100.0 95.2 90.9 83.3

KV40, cSt 68.70 68.47 67.39 67.7

TAN, mg/g KOH 0.29 0.16 0.14 0.11

ASTM D2893, Air, 100C, 240Day

KV40, cSt 71.73 70.85 69.99 66.92

TAN, mg/g KOH 0.6 0.57 0.34 0.35

ASTM D2893, Air, 100C, 300Day

KV40, cSt 70.90 70.25 69.63 68.18

TAN, mg/g KOH 0.78 0.36 0.34 0.35

15

Extend Lubricant Life Time

Commercial available RSAC lube

The life time was significantly improved with diluted additives

Deposit

formation

0d 34d

PAO based Air Compressor Lube

Deposit

free

Excellent Deposit control

16

Modified ASTM D2932 - 3 days at 60 C then 3days at 150 C and the cycle repeated

OSP with 2% AO

0d 34d 0d 34d 0d 34d

Formulation A Formulation B Formulation C

Commercially PAO based RSAC lubricant with claimed 8000hrs life time

Deposit Control Case Study – OSPs

The addition of OSP may

provide a solution for deposit

control and system reliability.

Filter membranes sit for 24 hours

in GII base used turbine fluid with

varying levels of VPR

Filter membranes sit for 24 hours

after addition of 10% OSP.

Filter membranes sit for 24 hours

after addition of 20% OSP.

The filter membranes

VPR (varnish potential rating )

17

Four Examples

Example 1 : Using OSPs as primary base oils in fully synthetic hydraulic fluids

Example 2: Using OSPs as primary base oils for biodegradable fluids

Example 3: Using OSPs as an additive in mineral oil hydraulic fluids

Example 4: Using OSPs as an additive in ester based hydraulic fluids

Four Concepts for using OSPs for Hydraulic Fluids

19

Test Method Result

Kinematic viscosity at 40oC, cSt ASTM D445 45.9

Kinematic viscosity at 100oC, cSt ASTM D445 8.2

Kinematic viscosity at 0oC, cSt ASTM D7042 463

Viscosity Index ASTM D2272 157

Pour Point, oC ASTM D97 -54

Density at 15oC, g/ml ASTM D7042 0.968

Ferrous corrosion, 24 hours, de-ionised

water/synthetic sea water

ASTM D665A/B pass/pass

Copper corrosion, ASTM D130 1a

Foam Sequence I, II and III, ml ASTM D892 0/0

Four ball anti-wear, mm ASTM D4172 0.31

Air release at 50oC, minutes ASTM D3427 <1

Oxidation at 121oC, 70days KV40 change, %

Visual appearance after 70d

ASTM D2893B –

ext. time

1.3

Transl. no

deposits

Thermo-oxidative stability test at 95oC, TAN

change after 1000 hours, mg KOH/g (wet

conditions)

ASTM D943 +0.5

Component %

UCON OSP-46 98.15

Additive package 1.85%

Additive package contains anti-oxidants,

anti-wear and corrosion inhibitors

Synthetic OSP Hydraulic Fluid

Typical Performance Properties

Performance of a Synthetic OSP Hydraulic Fluid

All fluids are ISO-VG-46

0.3 0.4 0.6

20

15

10

5

0.5

Water glycol

Mineral oil

PAO

Sat. Synthetic ester

Vegetable oil

OSP synthetic fluid

Phosphate ester

Unsat. synthetic ester

Four ball anti-wear, mm

Air

rele

ase

, m

inu

tes

Commercially available hydraulic fluids Performance

Air release at 50oC using ASTM D3427

Four ball using ASTM D4172 (75oC,

1200 rpm, 40kg for 1 hour)

20

OSP synthetic hydraulic fluid has outstanding air release and

four ball anti-wear performance

• PAO + OSP is also a good

combination as a Hydraulic Oil

being used by customer replacing

20% ester with same amount of

OSP, and giving 5 years warranty to

end user.

Commercial

Hydraulic Product

Weight Loss of

ring and vanes

KV40

change, %

AN Change

mgKOH/g

High oleic canola oil 9.1 2.7 0.2

Polyol oleate 3.4 14.0 0.5

Adipate ester 1.5 0.4 0.1

PAG 3.3 0.5 0.1

OSP 0.4 0.5 0.1

Pump performance and fluid condition

Hydraulic (V104C) Pump Test – ASTM D7043 100 hour duration

2000 psi ,1200 rpm & 65oC

Measure weight loss of ring and vanes

21

Hydraulic Vane Pump Test of Commercially Available Products

All fluids are commercially available from different suppliers

OSP synthetic hydraulic fluid shows excellent low wear values and oxidation stability

22

OSPs & Ester Based Environmental Friendly Hydraulic Fluids

Vegetable based hydraulic fluids (HETG)

- excellent wear performance

- biodegradable and renewable

- high viscosity indices

Synthetic esters (HEES) also used in more

demanding applications

- good oxidation stability

- good low temperature properties

- excellent wear characteristics

- some are biodegradable and renewable

Limitation of Esters

Natural and synthetic esters are prone to hydrolysis

Impact can be a shorter fluid life and higher risk of equipment damage

OSPs can be used as additives in vegetable oils and synthetic

esters to improve hydrolytic stability and deposit control

Concepts for OSPs for Greases

Recent Research Observations

Excellent friction control

High dropping points

Reduced thickener concentration in blend preparations (e.g. Li-complex)

Formulation flexibility (excellent additive solvating power)

Li-Complex Grease (ISO VG 220)

Characteristic Test Method 100%

Mineral Oil

30% OSP

220

%

Improvement

Complexing agent Sebacic Acid Sebacic Acid

% of Soap 17% 14% 18%

Worked Penetration 60X ASTM D217 290 265

4-Ball Weld Load, Kg ASTM D 2596 160 160

4-Ball Wear Scar Dia, mm ASTM D 2266 0.76 0.62 18.4%

Co-efficient of Friction ASTM D 2266 0.1042 0.0950 9%

Roll Stability (2 hrs/rt) ASTM D 1831 5 -2 140%

Wheel Bearing Leakage Test, Gm ASTM D 1263 0.6 0.2 67%

Low Temp Torque, -10oC IP 186 0.448/0.175 0.264/0.146 41%/ 17%

Water Washout, 80oC /1 Hour ASTM D 1264 2.67 0.68 75%

Oil Separation, 100oC/ 30 Hours IS 89 1.15 0.15 87%

24

OSP in Lithium Complex Grease

25

Concepts for OSPs in Engine Oils

Formulation Component of Engine Oil

OSP friction control and film forming behavior (fuel economy benefit)

Deposit control and engine cleanliness (reduced wear)

Heat capacity improvement (improved oxidation stability)

Good correlation with engine oil bench test

OSP shows excellent deposit control

M: Mineral oil

MP20: Mineral oil with 20% PAO

MO20A: Mineral oil with 20% OSP

MO20B=MO20A: duplicate test

Deposit Control Study – OSPs & PAO

Heat tube oxidation 16h @ 255C Heat tube oxidation 16h @ 250C

3.5 9 8.5 4 2.5 9 9 2.5

MP20 MO20A MO20B M MP20 MO20A MO20B M

27

SH/T 0645

OSP Exhibit Excellent Deposit control in Heat Tube Oxidation

SH/T 0623-95

OSP Exhibit Excellent Detergency and Dispersity

SH/T 0300

20% OSP reduce coking ～55%

OSP Dispersity > 60

Detergency & Dispersity

M: Mineral oil

MO-20: Mineral oil with 20% OSP

28

SH/T 0300 (Oil, 150C; Plate, 310C; 6 h)

M MO-20

Coke-forming / mg 11 5

OSP’s in Racing Engine Oil With Oak Racing

29

Concepts for OSPs for Metalworking Fluids

Oxygen rich polymers providing

surface activity and film forming

behaviour

Metal Deformation & Metal Cutting

Lubricity (AW/EP) booster for neat hydrocarbon oils

Metal deformation applications (stamping, drawing,

rolling etc) and metal removal (cutting, drilling)

Detergent additive – to maintain machine cleanliness

and prevent swarf build-up (validated by customers in

machine trials).

30

Product: Semi-Synthetic Metal Working Fluid

Problem: Improve cleanliness of cast iron and Aluminum CNC mill and

lathe unit operations

Solution: Formulate semi-synthetic fluid using Dow UCON™ OSP680 as a

component

Results: Eliminated cast iron residue accumulation

Dow UCON™ OSP’s in Metal Working Fluids

With

OSP

PAO

OSP 32 & 46 are used by

Indian formulators for

making Semi-Synthetic

Cutting Oil with dosage

level of 10% / 20%

31

Mineral Oil

Application : Soluble Cutting Oil for Grinding application

Dosage : 10% of OSP 680

Benefits :

• Oil consumption reduction

• Clean shop flour.

• 15% tool life enhancement.

Dow UCON™ OSP’s in Soluble Cutting Oil

32

Industrial Gear & Transmission Lubricants

Hydrocarbon oils containing OSPs

Improved friction control through excellent film forming behaviour of OSPs

Better energy efficiency

Good deposit control

Extended lubricant and equipment life

Better heat transfer efficiency

Concepts for OSPs in Gear and Transmission Fluids

OSP in Bearing and Industrial Gear Oil

Base Oil Compressor fluid

Turbine fluid

Hydraulic fluid

Gear/bearing oil

Engine/transmission oil

MWF

Grease

Co-base Oil Update I～III mineral oil

Performance Enhancing Additive for Deposit control

Friction modifier

Corrosion inhibit booster

Air release modifier

Hydrolytic stability modifier

OSP Application

Conclusion - OSP Application Expansion

35

Further Information

• Email OSP@Dow.com

• Visit our website at http://www.dow.com/ucon/osp/

• Access our STLE presentations at www.stle2011.com

• Contact our Dow Team directly for samples or further information

36

Thank you