Synthesis and CharacterizationSynthesis and Characterization of Modified Polyisobutyleney y

Succinimide Dispersants

Y li WYulin WangMay 11, 2010y ,

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OutlineOutlineIntroductionIntroduction

DispersantsObjectivesObjectives

Synthesis of modified PIBSICharacteri ation of modified PIBSICharacterization of modified PIBSI

Experimental ResultsModel reactions1H NMR spectra of PIBSI and modified PIBSI

Future WorkAcknowledgementsg

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Two Major ProblemsSludge Formation

E i F il

Particle Emission

H lth P blEngine Failure Health Problem

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C b D itCarbon Deposits

During normal operation, the engine generates a lot of Ultrafine Particles (UFPs) which have alot of Ultrafine Particles (UFPs) which have a diameter smaller than 100 nm.UFPs are mostly carbon richUFPs are mostly carbon-rich.

Without Dispersant Sludge

CRP<100nm CRP~1μm

High degree of aggregation4

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DispersantsDispersants are amphiphilic. They are composed of two long non-polar chains and a polar head.Dispersants are used in engine oils to prevent theDispersants are used in engine oils to prevent the coagulation of carbon deposits which might block oil flow. They help to stabilize small colloidal particles.

With dispersants

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DispersantsDispersants

Sludge

Without Dispersants With Dispersants6

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bis Polyisobutylene Succinimidebis Polyisobutylene Succinimide (b-PIBSI)( )

2 2

o

Polyisobutylene Succinic Anhydride (PIBSA)

b-PIBSI

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Polyamines used to SynthesizePolyamines used to Synthesize PIBSI

DETAH2N-CH2CH2-NH-CH2CH2-NH2

Di th l t i iDETA Diethylenetriamine~99%

TEPAH2N-(CH2CH2-NH)3-CH2CH2-NH2

Tetraethylenepentamine89%~89%

H N-(CH CH -NH) -CH CH -NHPEHA

H2N-(CH2CH2-NH)4-CH2CH2-NH2Pentaethyelenehexamine

~86%

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Modified PIBSI Dispersant

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The modified succinimide possesses improved

2

The modified succinimide possesses improved dispersancy properties when used in lubricating oil.

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ObjectivesSynthesize a series of modified bis-polyisobutylene succinimide (M-b-PIBSI)polyisobutylene succinimide (M b PIBSI) dispersantsCh i h difi d diCharacterize the modified dispersantsObtain the critical micelle concentrationObtain the critical micelle concentration(CMC) of the modified dispersants.M d l th d ti f th difi dModel the adsorption of the modified dispersants onto carbon black particles (CBPs).

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S th i P t lSynthesis Protocols

170oCOH H

H

O HH

H170 C Xylenes

PIBSA b PIBSI

2 Hn

N

O

HH

nN

O

HNH m

PIBSA b-PIBSIO

120oC X l

OO

Xylenes

Modified b-PIBSI11

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Fourier Transform InfraredFourier Transform Infrared Spectrometry (FTIR)p y ( )

CH3

1390 cm-14

O O

H N

O

O

NHn

N

O

OHn

C=O

1705 cm-14

C=O

1785 cm-1

700 900 1100 1300 1500 1700 190012

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1H NMR for Polymers

b-PIBSI-DETA has only one secondary amine in the pol meramine in the polymer.Clean and clear spectrum.p

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PIBSA 1H NMR SpectrumPIBSA 1H NMR Spectrum(1)(2) (1)

(2)+(3)

(3)

H3CO

OH H

H

OH H(2)(1)(P1) (P1)

( ) ( )(1)

3

O

HCH2

CH3

CH3

O

O

On

H H

H (2)+(3)

(2)

(1)(P2)

( )

(3)

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

CH3

(P2)

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

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M d l R ti 1Model Reaction 12 units of MSA were reacted with 1 unit of DETA inxylene at 170oC for 20 hours.Methyl succinimide possess a similar structure as thepolar core of the b-PIBSI-DETA dispersant.

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Model Reaction 1Model Reaction 1PIBSI-DETA Core -CH3

(1)

(3)

(2) (2)+(3) (1)H2O

CDCl3

(5)

(5)

(4)

(2)+(3)+(4)

(1)

7 6 5 4 3 2 1 ppm16

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PIBSA and PIBSIPIBSA and PIBSI(1) (2)

(2)+(3)

(3)

( ) ( )

(1)

H N

OH H

HHN

O HH

H(4)(3)

(1) (2)

(5)(4)

Hn

N

O

Hn

N

ONH(5)

(2)+(3) (1)

7 6 5 4 3 2 1 ppm

5.186

10.730

11.800

91.437

5.187

4.480

29.319

0.616

1.094

0.831

1.000

0.115

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Model Reaction 2:Model Reaction 2:Dibutylamine Reacting with Ethylene Carbonate(1:1 Ratio)

Dibutylamine is reacted with equal amount of

(1:1 Ratio)

Dibutylamine is reacted with equal amount of ethylene carbonate.The reaction is run without any solventThe reaction is run without any solvent.The reaction is run at 120oC.

2 2

3 3

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Model Reaction 2:Model Reaction 2:Dibutylamine Reacting with Ethylene Carbonate

H2 H2 H2 H2(M3)

H3C

2C

CH2

2C

N

2C

CH2

2C

CH3

OO O

H2C

O

CH2

(M1)(M2)

OH

(M1) (M2) (M3)

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm19

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Model Reaction 2:Model Reaction 2:Dibutylamine Reacting with Ethylene Carbonate(1:1 Ratio)

4 Hour Reaction

(1:1 Ratio)

(S3)

H3C

H2C

CH2

H2C

N

H2C

CH2

H2C

CH3

(S1)

( )

H2CCH2

OH

(S1)(S2)

(S1)(S1)

(S2)

(S3)

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm20

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ExtractionThe product mixture wasdissolved in ethyl ether H3C

H2C

CH

H2C

N

H2C

CH

H2C

CH3yand mixed with 1M HClsolution.

H2 H2

O

H2C

O

Both of the ether layerand the water layer wered t t d d th

CH2

OHEther Layer

deprotonated and thendried using MgSO4.At the end the solvents

H2C

H2C

H2C

H2C

HAt the end, the solventswere removed to obtainNMR spectra of each

H3CC

CH2

CN

CCH2

CCH3

H2CCH2p

fraction.2

OHWater Layer21

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Two FractionsTwo FractionsW t F ti

(S3)Water Fraction

(S1)(S2)

Eth F tiH3C

H2C

CH2

H2C

N

H2C

CH2

H2C

CH3

(M3)

Ether FractionO

H2C

O

CH2

OH

(M1)(M2)

OH

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm22

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Ether Layer Separation

Column Chromatography was used toseparate the products in the ether layer.1:1 Ratio of hexane and ethyl acetate wasused as the eluent.Three different compounds were found.

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Column Chromatography toColumn Chromatography to Separate the Ether Layerp y1Ethyl Acetate:1Hexane

(M5)(M3)

(M6)

(M7)

Main Product(M5)

(M7)

(M1)(M2)

M1: 4.2M2: 3.8

(M4)

(M4)

(M3)(M2)(M1)(M5) (M6)

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

6.677

4.557

4.552

1.000

4.557

2.207

2.289

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Ether Layer SeparationEther Layer SeparationSid P d t 1Side Product 1

HBu O

HBu4.31

BuN

CO

CH2

H2C

OC

O

O

H2C

CH2

OC

O

NBu

4.25

4.254.31

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.697

2.313

0.093

0.153

0.078

1.000

0.091

0.953

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Ether Layer SeparationEther Layer Separation

H2C

H2C

H2C

H2C

Side Product 2

H3C CH2

N CH2

CH3

OO4 2

H2CCH2

OH2C

OH

4.2

3.6

3.55CH2

4.2

3.63.63.55

4 5 4 0 3 5 3 0 2 5 2 0 1 5 1 0 0 5 ppm4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.465

0.994

0.995

0.146

0.219

1.000

0.450

0.964

0.556

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Products in the Model ReactionThere are 5 different compounds found in the reaction mixturereaction mixture.H3C

H2C

CH2

H2C

N

H2C

CH2

H2C

CH3

4.25

O

H2C

O

CH24.23 8

4.31

OH 3.8

2.553.5

4.23.6

273.6

3.55

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Dilute Model Reaction 2Dilute Model Reaction 21g Reaction Mixture dissolved in 10 mL Xylenes

Ether Layer

M1M2

M1 M2

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.908

24.176

6.871

189.675

13.807

2.021

0.813

1.000

0.961

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At the region 3.5 to 4.5, there are only peaks at 3.8 and 4.2, which meansthere is only the main product found in the ether layer of the dilutereaction.

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Dilute Model ReactionDilute Model Reaction1g Reaction Mixture dissolved in 10 mL Xylenes

Water Layer

H C

H2C

C

H2C

N

H2C

C

H2C

CH

(2)

(1)

(4)

H3C CH2

N CH2

CH3

H(1) (3)

(4)

(3) (2)

4 5 4 0 3 5 3 0 2 5 2 0 1 5 1 0 0 5 ppm4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.642

2.226

0.126

1.000

0.065

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There is only DBA found in the spectrum of the water layer product, which means no side product is produced in the dilute reaction.

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Predicted NMR SpectraPredicted NMR Spectra(1)+(2)(3)

(5)

(4)

(2)+(3) (1)(5)

(4)

( )

M1M2

M1 M2

M2

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Spectra of the ModificationSpectra of the Modification Reaction

(1)+(2)(3)

(5)

(4)

(2)+(3)(1)

(5)(4)

(5)

M1

M1M2M2

317.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

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Solvents ComparisonSolvents ComparisonSolvents Boiling Point

(oC)Vapour Pressure(mmHg)

ReactionEfficiency( C) (mmHg) Efficiency

Xylenes 147 18(37.7 oC)

Low yield<10%

Triethylamine 88.8 51.75(20 oC)

Low yieldHigh yield

bt i dobtained occasionally

1 1 2 2-Tetrachloroethane 147 8 React with1,1,2,2 Tetrachloroethane 147 8(20 oC)

React with PIBSIs

N,N-Diisopropylethylamine

127 31(37.7 oC)

Low yield

CH3 CH3

32

H3CCH

NCH

CH3

CH2H3C

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Yield of Modification Reaction of bYield of Modification Reaction of b-PIBSI-DETATemperature 

(oC)Triethylamine

( %)Xylenes( %)

Reactant( %)

Time (h )

b‐PIBSI‐DETA:EC R ti

Carbamate Side Ch i Yi ld(oC) (w%) (w%) (w%) (hours) Ratio Chain Yield 

130 0% 50% 50% 4 1:2 5%

125 60% 30% 10% 20 1:2 3%125 60% 30% 10% 20 1:2 3%

120 40% 20% 40% 40 1:2 9%

120 50% 25% 25% 40 1:2 8%

120 80% 10% 10% 20 1:2 3%

120 80% 10% 10% 20 1:10 5%

125 15% 70% 15% 20 1:2 1%

120 0% 0% 100% 20 1:2 5%

The yield of the modification of b-PIBSI-DETA is always lower than 10%.The reactions were run in the sealed reaction vessel.

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M difi ti f b PIBSI DETAModification of b-PIBSI-DETA

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm 34

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Modification of m PIBSI DETAModification of m-PIBSI-DETA

7 5 7 0 6 5 6 0 5 5 5 0 4 5 4 0 3 5 3 0 2 5 2 0 1 5 1 0 ppm7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

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The yield obtained is 13%. It is a big improvement comparing to the yield obtained with b-PIBSI-DETA. The reaction was run with set up 1.

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Polyamines used to SynthesizePolyamines used to Synthesize PIBSI

DETAH2N-CH2CH2-NH-CH2CH2-NH2

Di th l t i iDETA Diethylenetriamine~99%

TEPAH2N-(CH2CH2-NH)3-CH2CH2-NH2

Tetraethylenepentamine89%~89%

H N-(CH CH -NH) -CH CH -NHPEHA

H2N-(CH2CH2-NH)4-CH2CH2-NH2Pentaethyelenehexamine

~86%

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Modification of b-PIBISI-TEPAModification of b PIBISI TEPAOH H

H

O HH

HHn

N

O

HH

nN

O

HNH 2

OH H O HH

Hn

N

O

H

HH

nN

O

H

HN 2

O OH2C

CH2

OH

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

37The yield obtained is17%.

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MicellesfMicelles are aggregates of dispersants in the solvent.

Depending on the different solvents used, the dispersants form micelles or reverse micellesdispersants form micelles or reverse micelles.Two Important parameters: Critical Micelle Concentration (CMC) and Aggregation Number (Nagg).( ) gg g ( agg)

Reverse Micelles Micelles38

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C iti l Mi ll C t tiCritical Micelle ConcentrationTh CMC i d ith th th i lThe CMC is measured with the ruthenium complex (RuNH2) which probes the dispersant micelles at the molecular level by fluorescencethe molecular level by fluorescence.RuNH2 is soluble in polar solvents (e.g. Acetone), but not soluble in apolar solvents (e.g. Hexane).but not soluble in apolar solvents (e.g. Hexane).

ruthenium bisbipyridine

39

py5-aminophenanthroline hexafluorophosphate

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CMC MeasurementCMC Measurement

After stirring RuNH2 is not solubilised.

RuRuRuRu RuRuRuRu

Ru

Ru

After stirring RuNH2 is solubilised..

RuRuRuRu RuRu

Ru

40

Equal amount of RuNH2 is added into each solution. RuNH2 content of the solution increases when the dispersants form micelles.

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Fluorescence Spectrum of RuNHFluorescence Spectrum of RuNH210)

789

H2

(a. u

.)Dispersant with RuNH2

Dispersant

567

of R

uNH

RuNH2

234

o. In

t. o

01

470 570 670 770

Fluo

470 570 670 770Wavelength (nm)

[PIBSI]=0.13 g/L, [RuNH2]= 4 μM

41

[ ] g , [ ] μThe fluorescence spectrum of PIBSI with RuNH2 was subtracted by thePIBSI spectrum to obtain the fluorescence spectrum of RuNH2.

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Time Study of RuNHTime Study of RuNH2Fluorescence Intensityy

6

7

(a.u

.)

6

7

(a.u

.)

3

4

5

of R

uNH

2(

3

4

5

of R

uNH

2(

1

2

3

Fluo

. Int

. o

1

2

3

Fluo

. Int

. o0

0 1 2 3 4 5 6

F

Time (Day)

00 1 2 3 4 5 6

FTime (Day)

[PIBSI]=1.1 g/L, [RuNH2]=4 μM [M-PIBSI]=0.8 g/L, [RuNH2]=4 μM

42The fluorescence intensity of RuNH2 increases as time increases.

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Preliminary Result of PIBSI CMC

6

7a.

u.)

4

5

uNH

2(a

3

4

t. of

Ru

1

2

Fluo

. In

00.001 0.01 0.1 1

F

[Di t] ( /L)43

[Dispersant] (g/L)

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Conclusions

Model reactions enable the assignmentof 1H NMR spectra of the polymers.Low yields are obtained in theLow yields are obtained in themodification of b-PIBSI-DETA.Hi h d f difi tiHigher degrees of modification areobtained with m-PIBSI-DETA, b-PIBSI-TEPA, and m-PIBSI-TEPA.

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Future Work

Determine the CMC of the modifiedDetermine the CMC of the modifiedPIBSI.

Model the adsorption of the modifiedpPIBSI onto the surface of carbon blackparticles.p

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Acknowledgements

Dr. Jean DuhamelDr. ChongDr Gauthier and Dr TzoganakisDr. Gauthier and Dr. TzoganakisImperial Oil and NSERCEverybody in the Duhamel and Gauthier LabLab.

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Questions?Questions?

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