Ethylene-Acrylonitrile Copolymerization with Ni Dii i /EASC/Cl C t l t S tNi-Diimine/EASC/Clay Catalyst System

Sang-Young A. Shin, Joao B. P. Soares, Leonardo C. Simon

Department of Chemical Engineering University of Waterloo

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Contents

Motivation

Experimental Results

- Part 1 : Ethylene/Acrylonitrile Copolymer with α-Dimine-[N,N] Nickel

Dichloride/EASC System

- Part 2 : Ethylene In-Situ Polymerization with a Catalyst Supported onPart 2 : Ethylene In Situ Polymerization with a Catalyst Supported on

Clay Modified with Acrylonitrile

ConclusionsConclusions

Contributions and Acknowledgements

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Motivation

Searching for a new surface modifier of clays

Developing high performance thermoplastic elastomers- Product with properties similar to Therban®oduct t p ope t es s a to e ba ®

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Introduction

C h ld h l h l b h l fi

Polymerization Conditions for Polar Comonomers

- Comonomer should have at least two methylene spacers between the olefin and polar functional groups

- Tolerance to polar groups (approximately 1500 equiv. per metal center)Tolerance to polar groups (approximately 1500 equiv. per metal center)

3° Amines > Halides > Ethers > Ketenes > Esters > Water > Alcohols

Table 1 Amine Monomers Polymerized with Cp* ZrMe /Borate SystemTable 1. Amine Monomers Polymerized with Cp 2ZrMe2 /Borate System

a

Stehling,et al., Macromolecules., 1998, 31,2019

a. Activity = mol of monomer/mol of Zr⋅c[monomer]⋅hIP

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Part 1: Ethylene/Acrylonitrile Copolymer with α-Diimine-[N,N] Nickel Dichloride/EASC System

Nitrile group of acrylonitrile can coordinate metal active

Nickel Dichloride/EASC System

center in Ethylene/Acrylonitrile copolymerization.

L t t iti t l t l t t l t f lLate transition metal catalysts are tolerant for polar comonomer.

Pretreatment acrylonitrile with alkyl aluminum.

EASC as a co-catalyst for ethylene/acrylonitrile copolymerization.

555

p yIP

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Catalysts for Ethylene/Acrylonitrile Copolymer

Purging with N2/Solvent

EASC/CAT

TIBA/A l it il

Ethylene

N NNi

Cl Cl

TIBA/Acrylonitrile

1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine-dichloronickel (II)

Ethylene and acrylate copolymer was reported by Pd-diimine catalyst system by

Brookheart Group.

666

Johnson, L.K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc., 1996, 118, 267.IP

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Copolymerization of Ethylene and Acrylonitrile

N M C [C] Ti Yi ld M PDINo. M C [C](mol/L)

Time(hr.)

Yield(g)

Mw (kg/mol)

PDI

1 C2H4 - - 1 2.1 233 3.22 C2H4 C2H3CN 0.06 1 2.0 247 3.43 C2H4 C2H3CN 0.36 1 0.32 364 2.84 C2H4 C2H3CN 0.48 1 0.30 295 2.45 C2H4 C2H3CN 0.60 1 0.32 249 2.26 C2H4 C2H3CN 0.73 1 0.32 277 2.2

Catalyst :(diimine)NiCl2/EASC systemM: monomer(ethylene); C: comonomer (acrylonitrile with tri-isobutilaluminum) Experimental conditions: solvent: 25 mL;[1] = 4.25μmol/L, [Al]/[1] = 43, temperature = 25oC ;

777

[ ] μ , [ ] [ ] , p ;Pethylene = atmospheric. All samples were dried in the oven at 80 °C for 24 hrs.

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Functional Groups in Ethylene/Acrylonitrile Copolymer,

Xylene Soluble, Xylene Insoluble Fractions

(c) Xylene-soluble fraction- Nitrile groups- Attenuated vinyl groups

(b)

(c)

2214 cm-1

2245 cm-1

(b) Xylene-insoluble fraction- Nitrile groups- vinyl groups- PAN structure an

smitt

ance

(%) ( )

2245 cm-1

2214 cm-1

1250 ~ 1230 cm-1

(a) Ethylene/acrylonitrile copolymer

Tra 2245 cm

1780 ~ 1590 cm-1

copolymer- Nitrile groups

4001000160022002800340040001

(a)2214 cm-1

2245 cm-1

888Figure 1. FT-IR spectra of ethylene/acrylonitrile copolymer sample 3

Wave Number (cm-1)IP

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1H, 13C NMR spectra ; Xylene insoluble part polymer after 24 hours extraction.

(a)CH3-CH(R)−C≡NR2−CH−C≡N R−CH2−C≡NCH CH(C N) )C N

No. Assignmentc Reference(ppm)

Origin sample(ppm)

CH3−CH(C=N)−)R2−CH−C≡N

3 CH3-CH(R)−C≡N 1.23 1.3 (br)

4 CH3−CH(C=N)−) 0.9 0.9

1 R−CH2−C≡N 2.1 2.1 (br)

2 R2−CH−C≡N 3.1 3.05~3.25 (br)

(b)

R2−CH−C≡N116117118119120121122123124

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Transmission and ATR FT-IR spectra of Ethylene/Acrylonitrile Copolymerof Ethylene/Acrylonitrile Copolymer

Transmission ATR

C≡N C≡N?

C=C (CH )

C-Hrocking

C=CC=N

=N-H

(CH2)bending

C-Hstretching

600110016002100260031003600

Wave Number (cm-1)4001200200028003600

Wave Number

stretching

* ATR :Attenuated total reflection infrared IP

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1cm1cm

C

NC

N

CN

CN

CN

CN C

NC

N

N

CN

CNC

N

N

CN

CN

CN

C

CN

CN

CN

CN

NN

CN

CN

CN

CNC

NC

N

NN

CN

CN

CN

CN

CN

CN

CC

CN

C

CNC N

CN

CN

CN

CC

CN

CNC NC N

CN

CN

11

Ethylene Acrylonitrile Copolymer (No. 6 in Table 1)TEM, microtomed section of sample (No.6 in Table 1)(80 nm thickness)

500 nmIP

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Thermal Behavior of Ethylene/Acrylonitrile CopolymerCopolymer

time = 40 min.FT-IR Spectra ;

time = 10 min.

time = 20 min.

time = 30 min. Time increaseethylene/acrylonitrile copolymer(In the heating block at 160 °C)

ansm

ittan

ce (%

)time = 0 min.

Tra

5001000150020002500Wave Number (cm-1)

121212

Wave Number (cm )IP

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Thermal Behavior of Xylene Insoluble Fraction (PAN Rich Part)

STEP 1STEP 1

( )

0

2

4

282.22°C21 9°C

O N NNNOH

Cyclization220~310 °C

STEP 1O N NNNOHO N NNNOHO N NNNOH

Cyclization220~310 °C

STEP 1

-6

-4

-2

eat F

low

(mW

/g) 100.83 °C

91.17 °C0.42 J/g

217.59°C111.2 J/g

OO N N N NHSTEP 2

OO N N N NHOO N N N NHOO N N N NHSTEP 2

PAN, Jung et al., Material Letters,2002, 53, 18012

-10

-8

-6

He

110.99 °C

OO N N N NH

Aromatization330~350 °C

OO N N N NHOO N N N NHOO N N N NH

Aromatization330~350 °C

-12-100 -50 0 50 100 150 200 250 300 350 400

Temperature (°C)

NNOO N NHX1~2STEP 3

NNOO N NHX1~2NNOO N NHX1~2NNOO N NHX1~2STEP 3

Figure 4 16 Proposed mechanism for cyclization and aromatization of nitrile and acid

131313

Figure 4-16. Proposed mechanism for cyclization and aromatization of nitrile and acid

groups during thermal treatment of ethylene/acrylonitrile copolymers.

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Stress-Strain Curves of Ethylene/Acrylonitrile Copolymer

8000Stress-Strain Curves ; T il ti i d

6000 No. 5, [AN] = 0.60

No. 6, [AN] = 0.73

Increase of acrylonitrileconcentration

Tensile properties are increased as the increase of initial loading of acrylonitrile concentrations

4000

Str

ess

(Kpa

) No. 4, [AN] = 0.48

2000 No. 1, [AN]1 = 0

•Sample Dimension : width- 6.5 mm, Height - 0.2 mm, Pressed film[AN] l/L

00 300 600 900 1200

Strain (%)

141414

•[AN] ; mol/L IP

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Conclusion

Successful synthesis of Ethylene/acrylonitrile copolymer.

Presence of PAN structure was confirmed by- FT-IR, 1H-NMR, 13C-NMR

Nano-phase distribution of PAN domains in PE matrix was observed byobserved by- TEM

Improved physical properties were confirmed by- Tensile tests.

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Part 2: Ethylene In-Situ Polymerization with a Catalyst S t d Cl M difi d ith A l it ilSupported on Clay Modified with Acrylonitrile

Intercalation and exfoliation of clay with acrylonitrile.

I i l i i f h l d l i il h lIn-situ copolymerization of ethylene and acrylonitrile on the clay surface.

Strong interfacial interaction between clay surface and PE matrices through introduction of chemical bonds.

Enhanced mechanical properties with PE-acrylonitrile/clay polymercomposite.

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Commercial ApplicationsClay Nanocomposites

Timing belt covers of automotive engines– Standard is glass fiber reinforced nylon or PP

Injection molded nylon 6 nanocomposite– Injection molded nylon 6 nanocomposite used in Toyota’s automotive engine parts

– Exhibited good rigidity and excellent thermal stability with a 25% weight reduction

Step- assists on vans/ trucks– Thermoplastic olefin (TPO) nanocomposite

used on 2002 GM mid- size vansNanocomposites are stiffer lighter less brittle– Nanocomposites are stiffer, lighter, less brittle in cold temperatures and more easily recyclable

– Cost the same as conventional TPOs,with no new tooling required

Nylon-clay nanocomposite bottles

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Morphology of Clays

Clay powder Primary particle Lamella(0.1 ~ 10 μm) (8 ~ 10 nm) (1 nm)

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In-Situ Polymerization of Ethylene and Clay

In-Situ Polymerization

clay

olefin+

organic clay nanocomposites

olefin+

processing(blending) nanocomposites

catalyst

+

catalyst+

(blending)

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Modification of Clay with Acrylonitrile

Small angle X-ray

450MMT

MMT/TIBA/An

3.6

8.86

g ydiffraction patterns for MMT and MMT/TIBA/AN.

150

300

Inte

nsity

, A.u

.

7.248.86

0

150

0 2 4 6 8 10 122 d

TGA and DTG(derivative weight loss) curves of MMT, MMT/TIBA and MMT/TIBA/AN samples

98

100

102

0.14

0.19MMT/TIBA/AN

MMT/TIBA

MMT

MMT

2θ degree

and MMT/TIBA/AN samples.

92

94

96

Wei

ght (

%)

0.04

0.09

Der

iv. W

eigh

t (%

/o C)

20202088

90

0 200 400 600 800

Temperature (oC)

-0.01

0.04IP

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Functional Groups in PE, PE-MMT/TIBA/AN, Clay Residue

Clay Residue(After Soxhlet extraction;

PE-MMT/TIBA/AN )

1742 cm-1(C=O) 1662, 1647 cm-1(C=C)

PE-MMT/TIBA/AN( l 2) sm

ittan

ce (a

.u.)

2244 cm-1(C≡Ν)

Polyethylene

(sample 2)

Tran

Polyethylene(sample 1)

1500180021002400Wavenumber (cm-1)

212121

Figure 5-2. FT-IR spectra for the comparison of functional groups between 1500 cm-1 and 2700 cm-1:IP

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Thermal Behavior of PE-MMT/TIBA/AN

DSC Curves; PE-MMT/TIBA/AN

(sample 6); 1st DSC thermogram

4

2

117.98 °C313 °C

4

2

117.98 °C313 °C

4

6

116.81°C

4

6

116.81°CDSC Curves; PE-MMT/TIBA/AN

(sample 6); 2nd DSC thermogram

0

(W/g

)

250 280 310 340 370

0

(W/g

)

250 280 310 340 370

2

4

W/g

) 5 15 25 35 45 250 280 310 340 370

118.64°C103.6 J/g

2

4

W/g

) 5 15 25 35 45 250 280 310 340 370

118.64°C103.6 J/g

( p ) g

-2

-4Hea

t Flo

w

313.34 °C128.82 °C140.1J/g-2

-4Hea

t Flo

w

313.34 °C128.82 °C140.1J/g

-2

0H

eat F

low

(W

g

124.96°C103.8 J/g-2

0H

eat F

low

(W

g

124.96°C103.8 J/g

-6

136.15 °C5 15 25 35 45

-6

136.15 °C5 15 25 35 45

-4

H

-4

H

-100 0 100 200 300 400-8

Temperature (°C)-100 0 100 200 300 400

-8

Temperature (°C)

-6-100 0 100 200 300 400

Temperature (°C)

-6-100 0 100 200 300 400

Temperature (°C)

222222

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Tensile Properties of PE-MMT/TIBA/AN Composite

Stress-strain curves 3500PE 0% MMT

• Tensile properties are increased as MMT content increase

2500

3000

PE_0% MMT

No.3_5.5 wt% MMT

No.4_16.5 wt% MMT

No.2_6.4 wt% MMT

1500

2000St

ress

(KPa

)Increase of MMT/TIBA/AN

500

1000

S

00 50 100 150 200 250 300 350 400 450 500

Strain (%)

PE-Clay dry blending

23232323

( )IP

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Conclusions

Excellent intercalation and exfoliation of clay particles with acrylonitrileExcellent intercalation and exfoliation of clay particles with acrylonitrilemonomer.

Strong interfacial interaction between polyethylene matrices and clayStrong interfacial interaction between polyethylene matrices and claysurface.

Developed a new synthetic method; in- situ copolymerization of p y p yethylene and acrylonitrile.

Enhanced mechanical properties in polyethylene-acrylonitrile clay composite.

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Contributions

Scientific

• Synthesized ethylene-acrylonitrile copolymer. • Introduced interfacial interaction between polyethylene matrices and clay surface with acrylonitrile modificationclay surface with acrylonitrile modification.

Industry

• Developed a new synthetic method: in-situ copolymerization of ethylene and modified clay with bifunctional molecules.

Society

• Provided new knowledge for PE-Clay hybrid nanocomposites.

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Acknowledgements Thank you!

• Prof. Joao Soares and Prof. Leonardo Simon

• Financial support from – NSERC– NSERC

• Collaborators– Prof. Gunter Scholz (X-Ray and TEM)

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Functional Groups inEthylene/acrylonitrile CopolymerEthylene/acrylonitrile Copolymer

f i i lR−CH2−C N≡

No. Assignmentc Reference

(ppm)Origin sample

(ppm)

1 R−CH2−C≡N 2.0 2.1

2 R−CH2CO−O− 4.1 4.1

3 R−CH2NH− 8.31 8.2

R−CH2NH−

R−CH2CO−O−

012345678910

272727

ppm

1H NMR spectrum of ethylene/acrylonitrile copolymer (No. 6 in Table 1.)

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Shielding effect

of nitrile group

H

H

H

a

bC N≡

HHC

of nitrile group

Hc HbHa

H

Hb

C N HbHaH

H

a

c

C N≡ Hb

HC

a

Shielding effect

H

H

a

bC N—TIBA≡

HaHb

of vinyl group

Hc

HC

Shielding effect

of vinyl group

55.15.25.35.45.55.65.75.85.966.16.26.36.46.56.66.76.86.97

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HbC N TIBA

H

H

a

c

C N—TIBA≡

-0.50.51.52.53.54.55.56.57.58.59.5ppmIP

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