June 2011

Griselda Barrera Galland

Universidade Federal do Rio Grande do Sul – UFRGS

Instituto de Química

Laboratório de Catálise Ziegler-Natta

PROYECTO CYTED

Desarrollo sostenible de la Industria del Polipropileno Controlando sus

Propiedades y Optimizando su Consumo Energético y sus posibilidades de

degradación

PORTO ALEGRE, RIO GRANDE DO SUL, BRAZIL

PORTO ALEGRE, RIO GRANDE DO SUL

UFRGS

UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL

UFRGS

Students• Under-graduated (75%) 24.707• Graduation (25%) 8.415

Master 4.694Ph D 3.290Profissional Master 431

33.122

Professors 2.247

Staff 2.460

INSTITUTO DE QUÍMICA

(CHEMICAL INSTITUTE) -UFRGS

Bacharelado em Química (BS in Chemistry)

Química Industrial (Industrial Chemist)

Licenciatura em Química (Degree in Chemistry)

Tecnólogo em Química (Chemical Technologist)

Under-graduated studies:

Graduated studies:

Master degree

Doctorate degree

Professors: 84

Students: undergraduated (470), graduated (161)

Staff: 44

Elementar Analysis (CHN) Nitrogen Adsorption Analysis

Micrometrics Tristar® II 3020

- Gas Chromatograph with Flame Ionization Detector, Varian 3400- Gas Chromatograph with Electron Capture Detector, Varian 3400- Gas Chromatograph with Flame Ionization, Shimadzu

Chromatographs

- Light Scattering Spectrophotometer Brookhaven Instruments (BI) 9000

Fluorimeter

- Infrared Spectrophotometer (FTIR) Shimadzu Prestige-21

- High Resolution Mass Spectrometer Micromass QTOF Waters 3200

Shimadzu, model UV1601PC

Ultraviolet Spectrophotometer (UV)

Chemistry Institute Facilities

Nuclear Magnetic Resonance Laboratory

Varian Inova e Varian VNMRs operating at 300MHz1H, 13C, 31P, 15N, 17O

-DSCQ2000 + RCS90 – Differential Scanning Calorimeter;- AutoDSCQ20 + RCS40 – Differential Scanning Calorimeter;- TGAQ5000IR – Thermogravimetric Analyzer;- SDTQ600 (TGA-DTA-DSC Simultaneous);- DMAQ800 – Dynamic Mechanic Analyzer;- TGA2050 - Thermogravimetric Analyzer;- DSC2010 + RCS and Gas Chromatograph/mass spectrometer(CG-MS) Shimatzu model QP 2010 with interface for TGA – Thermogravimetric Analyzer.- DSC 4, Perkin Elmer, temperature range: -40 to 400 0C- DSC 2910, DuPont, temperature range: -150 to 400 0C- Melt Index, Ceast Junior

Thermal Analysis Sector

- Scanning Electronic Microcope JEOL JSM 5800

- Scanning Electronic Microcope JEOL JSM 6060- Transmission Electronic Microcope JEOL JEM 1200FxII- Transmission Electronic Microcope JEOL JEM 2010- X Ray Diffraction Phillips – X´Pert MRD- Confocal Fluorescence Microscope OLYMPUS

Electronic Microscopy Center

SYNTHESIS OF NEW

POST-METALLOCENE

CATALYSTS FOR OLEFIN

POLYMERIZATION

PYRONE COMPLEXES (Maltol Derivates)

Sobota, P.; Przybylak, K.; Utko, J.; Jerzykievicz, L.B.; Pombeiro, A.J.L.; Silva, M.F.G.; Szczegot, K. Chem Eur. J. 2001, 7, 951-958.

Carone, C., De Lima, V.; Albuquerque, F.; Nunes, P.; de Lemos, C.; Dos Santos, J.H.Z.; Galland, G.B.; Stedile, F.C.; Einloft, S.; Basso, N.R.S. J. Molecular Catalysis A: Chem. 2004, 208, 285-290.

Fim, F.C.; Machado, T.; De Sá, D.S.; Livotto, P.R.; Da Rocha, Z.N.; Basso, N.R.S.; Galland, G.B. J. Polym. Sci.: Part A: Polym. Chem., 2008, 46, 3830-3841.

O

O

O

R

M

ClCl

O

OR

O

MCl4/THF

M=Ti, ZrO

O

OH

R

R= Me, Et

1 2 3 4

30 C

40 C

60 C

0

100

200

300

400

500

Cata

lyti

c A

cti

vit

ies

(Kg

PE

/nM

.h.a

tm)

1 R=Me; M=Ti

3 R=Me; M=Zr

2 R=Et; M=Ti

4 R=Et; M=Zr

[Zr] = 1 mol Al/Zr = 2500 Cocatalyst=MAO PE = 1.6atm time=1h

O

O

O

R

M

ClCl

O

OR

O

O

O

O

O

OO

Cl

Cl

Ti

[Ti] = 3 10-6 mol; MAO (Al/Ti = 1000); solvent: toluene; T = 40°C.

SUPPORTED

Greco, P.P.; Brambilla, R.; Einloft, S.; Stedile, F.C.; Galland, G.B.; Dos Santos, J.H.Z.; Basso, N.R.S. J. Molecular Catalysis A: Chemical , 2005, 240, 61-66

O

O

O

OO

Cl

Cl

ZrSUPPORTED

16,322,3

45,0

12,5

25,5

45,6

0

10

20

30

40

50

SiO2

MCM

MgO

Al2

O3

SMAO

Hom

o

Suportes

Ati

vid

ad

e C

ata

líti

ca

(Kg

PE

/mo

lZr.h

.atm

)

Zr] = 1x10-6; MAO (Al/Zr= 2500); solvent: toluene;

POLYOLEFIN

NANOCOMPOSITES

BY IN SITU

POLYMERIZATION

GRAPHITE:

CHEMICALLY INERT

HEAT-RESISTANT

ELECTRICAL CONDUCTIVITY

THERMAL CONDUCTIVITY

POLYETHYLENE:

HIGH INSULATING PROPERTIES

HIGH DUCTILITY

GOOD PROCESSABILITY

TO LOAD AN INSULATING POLYMER WITH AN ELECTRICALLY

CONDUCTING FILLER SHOULD INCREASE THE RANGE OF

APPLICATIONS OF PE

APPLICATIONS:

ELECTROMAGNETIC RADIATION SHIELDING

PREVENTION OF CROWN DISCHARGE IN HIGH VOLTAGE CABLES

LOW-TEMPERATURE HEATERS

TRANSDUCERS

PREPARATION OF NANOCOMPOSITES

Melt processing

Solvent processing

In situ polymerization

Potts, J. R., Dreyer, D. R., Bielawski, C. W., Ruoff, R. S., Polymer, 2011, 52, 5.

IN SITU POLYMERIZATION

The nanofillers are mixed with the monomer in the presence of a

solvent and then the polymerization reaction proceeds to make

the nanocomposite.

HDPE – High Density Polyethylene: Fim, F. C., Guterres, J. M., Basso, N. R..

S., Galland, G. B., J. Polymer Science, Part A: Polymer Chemistry, 2010, 48, 692.

PP – Polypropylene: Montagna, L.S., Fim, F. C., Galland, G. B., Basso, N. R.. S.

Macromolecular Symposia, 2011,299, 48.

Monomer of the -

olefin

Exfoliated

nanocompositeNanofiller with

lamelar structure

CRYSTALINE STRUCTURE OF GRAPHITE

basal plane

Covalent bond

Van der Waals forces

- Layer

- Anisotropic

GRAPHENE

PREPARATION OF THE GRAPHENE NANOSHEETS (GNS)

H2SO4/HNO3

1000°C ultrason

(a) Natural graphite flake

(b) Intercalated

graphite flake

(c) Expanded graphite (d) Graphite after the

ultrason treatment

Sample2

(°)d002

(nm)

C

(nm)

Graphite

Flake26.67 0.333 58.38

GNS 26.52 0.336 28.15

Bragg’s Law:

cos

9,0C

dsen2

Scherrer’s Eq.:

STRUCTURE OF GRAPHITE CRYSTAL - XRD

16 24 32

0

400000

Inte

nsi

ty

2

Graphite flake

GNS

(002)

GRAPHENE NANOSHEETS- TEM

10 nm

200 nm

SYNTHESIS OF THE NANOCOMPOSITES BY IN SITUPOLYMERIZATION

do banho

1 10

2

3

45 6

7

8

91 10

2

3

45 6

7

8

9

controller of temperature and

stirring

2.8 bar of ethylene pressure

Cocatalyst MAO - Al/Zr = 1000

Cp2ZrCl2 –

2 mol of Zr

GNS treated

with MAO

PARR Reactor

To prevent the metallocene from being

deactivated by the functional groups at the

graphene surface.

AMOUNT OF GRAPHITE IN THE NANOCOMPOSITES

AND CATALYTIC ACTIVITY

a Graphite percentage calculated from the TGA residue.b (kgPol/molZr.h.bar).

Graphite

mass (g)

Polymer

yield (g)

(2)a

(wt.%)

Catalytic

Activityb

0 4.9 - 1750

0.05 4.1 1.4 1464

0.10 3.6 6.6 1285

0.26 4.6 5.4 1642

0.59 4.1 15.3 1464

NANOCOMPOSITES NANOMETRIC - TEM

6.6

wt.%

GNS

5.4 wt.%

GNS

THERMAL PROPERTIES – DSC and TGA

SAMPLE

(vol.%)

Tm

( C)

Xc

(%)

Tonset

(°C)

Tmax

(°C)

Neat PE 132 74 442±1 480±2

PE/1.4%

GNS132 68 454±1 487±1

PE/5.4%

GNS131 84 471±1 494±2

PE/6.6%

GNS131 71 472±1 495±1

PE/15.3%

GNS131 59 463±1 510±1

0 2 4 6 8 10 12 14 16

480

485

490

495

500

505

510

Deg

rad

ati

on

Tem

pera

ture

(oC

)

Graphite Content (wt.%)

Increase of thermal stability

DYNAMIC MECHANICAL PROPERTIES

Storage Modulus Mechanical Damping

Storage modulus

Stiffness

Sample Tg (°C)

Neat PE -119

PE/1.4% GNS -108

PE/5.4% GNS -108

PE/6.6% GNS -107

-150 -100 -50 0 50 100 150

0

500

1000

1500

2000

2500

3000 Neat PE

PE/1.4% GNS

PE/5.4% GNS

PE/6.6% GNS

E' (

MP

a)

Temperature (oC)

-150 -100 -50 0 50 100 150

0,05

0,10

0,15

0,20

0,25

0,30 Neat PE

PE/1.4% GNS

PE/5.4% GNS

PE/6.6% GNS

Tan

Delt

a

Temperature (oC)

MECHANICAL PROPERTIES

Tensile Strength E = σ/ε

0 1 2 3 4 5 6 7

0

50

100

150

200

250

300

Elo

ng

atio

n a

t b

reak

(%

)

GNS Content (wt.%)

0 1 2 3 4 5 6 7

520

530

540

550

560

570

580

Ela

stic

Mo

du

lus

(MP

a)

GNS Content (wt.%)

0 10 20 30 400

5

10

15

20

25

Neat PE

PE/1.4% GNS

PE/5.4% GNS

PE/6.6% GNS

Str

ess

(M

Pa)

Strain (%)

Increase of stiffness

0 2 4 6 8 10 12 14 160

10x10-13

2x10-12

3x10-12

1x10-8

2x10-8

3x10-8

Ele

ctr

ical

Co

nd

ucti

vit

y

(O

hm

-1.

cm

-1)

Graphite Content (wt.%)

insulating

semiconductor

ELECTRICAL PROPERTIES – IMPEDANCE SPECTROSCOPY

NUCLEAR MAGNETIC RESONANCE

APPLIED TO POLYOLEFINS

Type and amount of branches

Comonomer distribution in the polymer chain (sequences of

comonomers)

Determination of the regio and the stereorregurarity in

poly- -olefins

Monomer reactivity ratios

Mecanism of the polymerization

INTRODUCTION

NUCLEAR MAGNETIC RESONANCE APPLIED TO POLYOLEFINS:

COPOLYMERS

RANDOM AAABAABBBABAABAA

BLOCK AAAAAAAAABBBBBBB

ALTERNATED ABABABABABABABAB

DIADS (XX, XY, YY) CH2 CH CH2 CH

X X

_ _

X

CHCH2CHCH2CH2 CH CH2 CH_

Y Y Y

XX XY YY

YX

_

XY

CHCH2CHCH2 CH2 CH

Y

Y

XX _

XX

CHCH2CHCH2 CH2 CH

Y

Y

X

X

CHCH2CH2 CH CH2CH

X X

_XX

XY

YX

CHCHCH2 CH2 CH

X

X

YY

YY

CHCH2CHCH2 CH2 CH

X

X

Y

Y

CHCH2CH2 CH CH2 CH

Y Y

_YY

_

_CH2

TRIADS

INTRODUCTION

STUDY OF BRANCHED POLYOLEFINS USING

13C NUCLEAR MAGNETIC RESONANCE

SPECTRUM

Chemical Shifts

Integrals

TRIADSEEE PPPEEP PPEPEP EPE

TRIAD: PEP

P PE

= CH2CH2 (ethylene)

= CH2CHCH3

(propylene)

TRIADS COMONOMER AVERAGE SEQUENCE LENGTH

-PEEEEEEP- -EPPPPPE-

nEP = [EEE] + [EEP+PEE] + [PEP] nPE = [PPP] + [EPP+PPE] + [EPE]

[PEP] + ½ [EEP+PEE] [EPE] + ½ [EPP+PPE]

nEP =6 nPE =5

TRIADS

MONOMER REACTIVITY RATIOS

rEP = 2 [EE] rPE = 2 X1 [PP]

X1 [EP] [PE]

being: [EE] = [EEE] + ½ [EEP + PEE] [PP] = [PPP] + ½ [EPP + PPE]

[EP] = [PEP] + ½ [EEP + PEE] [PE] = [EPE] + ½ [EPP + PPE]

X1 = [E] / [P] in the feed

E* + E E*

kEE

E* + P E*kEP

P* + E E*

kPE

P* + P P*kPP

rEP= kEE/kEP rPE= kPP/kPE

13C NMR OF ETHYLENE-PROPYLENE--OLEFINS TERPOLYMERS

OBJETIVE

Determination of all chemical shifts

Quantitative determination of all comonomer sequences

Determination of reaction ratios

Determination of average comonomer sequence lengths

13C NMR OF COPOLYMERS

a) Ethene-propene copolymer, E = 64.7 mol%, P = 35.3 mol %

b) Propene-1-decene copolymer, P = 95.1 mol% D = 4.9 mol%;

c) Ethene-1-decene copolymer, E = 85.6 mol%, D = 14.4 mol %

d) 1-decene homopolymer,

ETHYLENE-PROPYLENE-1-DECENE

13C NMR spectra of Ethene-propene-1-decene terpolymers

E = 86.8 mol%, P = 6.3 mol %, D = 6.9

E = 67.7 mol%, P = 28.9 mol%, D = 3.4 mol%;

E = 12.8 mol%, P = 85.9 mol% D = 1.3 mol %

E = 4.4 mol%, P = 93.3 mol%, D = 2.3 mol%

peak no. chemical shift exp. (ppm)

chemical shift calc. (ppm)

triad assignments

9 24.30 25.08 DED

10 10a 10b 10c 10d

24.35-24-85 24.40 24..57 24.63 24.80

24.58 PEP

PPEPP

EPEPE(m)

PPEPE+EPEPP

EPEPE(r)

DED

E = 28.9 mol%, P = 70.2 mol %, D = 0.9

E = 64.7 mol%, P = 35.3 mol%

E = 86.8 mol%, P = 6.3 mol% D = 6.9 mol %

E = 73.6 mol%, P = 9.0 mol%, D = 17.4 mol%

E = 85.6 mol%,D = 14.4 mol%

PPEPP

EPEPEmPPEPE+EPEPP

EPEPEr

Calculated and observed 13Carbon Chemical Shifts and Assignments for Ethylene-propylene and 1-decene Terpolymers

peak no.

chemical shift exp. (ppm)

chemical shift calc.

(ppm)

triad assignments

1 14.13 13.86 EDE EDD+DDE DDD PDP PDD+DDP

2 19.40-20.3019.58

20.61 PPP (rr)PPP(mrrm)

3 19.87 19.63 EPE

4 20.55 20.12 EPP+PPE

5 20.30-21.00 20.90

20.61 PPP(mr+rm)PPP (mmrr)

6 21.00-21.5021.40

20.61 PPP(mmmr+rmmm + rmmr)PPP(mmmr+rmmm)

7 21.71 20.61 PPP(mmmm) DPD PPD+DPP

8 22.88 22.65 DDP+PDD PDP DDD EDE EDD+DDE

9 24.30 25.08 DED

1010a10b10c10d

24.35-24-8524.4024..5724.6324.80

24.58 PEPPPEPP

EPEPE(m)PPEPE+EPEPP

EPEPE(r)

1111a11b

26.9-27.126.9727.03

27.52 PDP PDD+DDP DDDPDP(mr)PDP(mm)

12 27.15 27.52 EDE EDD+DDE DEE+EED

1313a13b13c

27.18-27.4327.1827.2427.41

27.27 EEP+PEEPPEE+EEPP(r)PPEE+EEPP(m)

EPEE+EEPE

14 28.16 -28.53 28.38 PPP DPD DPP+PPD br

EQUATIONS RELATING TRIADES AND 13C NMR SPECTRUM

INTEGRALS

Equations for the quantitative Analysis of Ethylene–Propylene–1-Decene Terpolymers

Equation of triads centered in E

Equation of triads centered in P

Equation of triads centered in D

[EEE] = (I16+I17-I22)/2

[EEP+PEE] = I13

[PEP] = I10

[EED+DEE] = I12-

I22+I11

[DED] = I9

[EPE] = I23

[EPP+PPE] = I20

[PPP] = I14-I37+I29-I36

[DPP+PPD]+[DPD] = I37-I29+I36

[PDP] = I29-I34-I36

[DDD] = I36

[DDP+PDD] = I34

[EDE] = I33 ou (I25-(I12-

I22+I11)/2)/2

[EDD+DDE] = (2*(I26+I27-I9))/5

Triad sequence distribution of the terpolymers obtained by 13C NMR using the 1-decene concentration in the feed of 0.176 M.

ED 30 EPD 14 EPD 13 EPD 17 EPD 19 EPD 21 EPD 28 EPD 24 PD 33

[EEE] 57.9% 69.7% 64.1% 24.0% 5.7% 3.2% 1.2% 0.3% 0.0%

[EEP+PEE] 0.0% 4.5% 9.3% 27.1% 12.4% 9.7% 4.1% 0.0% 0.0%

[PEP] 0.0% 0.3% 1.0% 8.5% 14.6% 16.6% 9.1% 4.1% 0.0%

[EED+DEE] 23.9% 14.2% 12.0% 6.5% 7.0% 1.7% 0.0% 0.0% 0.0%

[DED] 3.8% 0.6% 0.4% 0.9% 0.8% 0.0% 0.0% 0.0% 0.0%

[EPE] 0.0% 2.3% 5.1% 19.3% 17.5% 11.7% 1.5% 1.5% 0.0%

[EPP+PPE] 0.0% 0.0% 1.2% 5.3% 23.6% 24.8% 16.9% 4.9% 0.0%

[PPP] 0.0% 0.0% 0.0% 2.9% 9.8% 27.0% 64.3% 82.3% 92.3%

[DPP+PPD]+[DPD] 0.0% 0.0% 0.0% 0.0% 1.6% 2.6% 2.1% 4.6% 2.8%

[PDP] 0.0% 0.0% 0.0% 0.0% 0.4% 0.9% 0.8% 2.3% 4.9%

[DDD] 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%

[DDP+PDD] 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%

[EDE] 12.3% 7.7% 6.1% 3.6% 4.7% 1.7% 0.0% 0.0% 0.0%

[EDD+DDE] 2.1% 0.7% 0.8% 1.8% 1.9% 0.0% 0.0% 0.0% 0.0%

[E] 85.6% 89.3% 86.8% 67.1% 40.5% 31.3% 14.5% 4.4% 0.0%

[P] 0.0% 2.3% 6.3% 27.6% 52.5% 66.1% 84.8% 93.3% 95.1%

[D] 14.4% 8.4% 6.9% 5.4% 7.0% 2.6% 0.8% 2.3% 4.9%

Comonomer average sequences lengths (nXY) and reactivity ratios (rXY) calculated by 13C NMR

nEP = [EEE]+[EEP+PEE]+[PEP]

(EP=)[PEP] + ½ [EEP+PEE]

nPE =[PPP]+[EPP+PPE]+[EPE]

(PE=)[EPE]+ ½ [EPP+PPE]

nED = [EEE]+[EED+DEE]+[DED]

(ED=)[DED]+ ½[EED+DEE]

nDE =[DDD]+[EDD+DDE]+[EDE] (DE=)[EDE]+ ½ [EDD+DDE]

nPD =[PPP]+[DPP+PPD]+[DPD]

(PD=)[DPD]+½ [DPP+PPD]

nDE =[DDD]+[PDD+DDP]+[PDP]

(DP=)[PDP] + ½ [DDP+PDD]

rEP = 2 [EE] rED = 2 [EE] rPD = 2 [PP]

X1 [EP] X2 [ED] X3 [PD]

rPE = 2 X1 [PP] rDE = 2 X2 [DD] rDP = 2 X3 [DD]

[PE] [DE] [DP]

X1= [E]/[P] in the feed X2= [E]/[D] in the feed X3= [P]/[D] in the feed

[D] = 0.088 M in the liquid phase

nEP nPE rEP rPE rEPrPE nED nDE rED rDE rEDrDE nPD nDP rPD rDP rPDrDP

ED26 - - - - - 30.5 1.0 24.3 0.1 2.7 - - - - -

EPD16 32.8 1.0 10.3 0.0 0.0 35.7 1.1 30.2 0.1 3.5 - - - - -

EPD15 13.1 1.1 8.3 0.4 3.2 37.7 1.0 33.8 0.1 2.3 - - - - -

EPD18 2.9 1.2 3.8 0.5 1.8 33.6 1.2 36.0 0.3 11.9 - - - - -

EPD20 1.6 1.8 3.9 0.5 1.9 20.3 1.6 31.2 0.7 22.4 - - - - -

EPD23 1.4 3.3 6.6 0.5 3.3 - - - - - 75.8 1.0 55.4 0.0 0.0

EPD27 1.3 6.5 15.1 0.4 6.0 - - - - - 62.8 1.0 38.2 0.0 0.0

EPD25 1.1 10.8 10.8 0.3 3.7 - - - - - 90.5 1.0 52.4 0.0 0.0

PD32 - - - - - - - - - - 90.4 1.1 33.4 0.7 23.6

ZrCl Cl

rac-EtInd2ZrCl2/MAO

Al/Zr=1500

P=1 atm

SILVA. A. A. da; GALLAND. G. B. Study of propylene-1-butene-

ethylene terpolymer and reactor blend by TREF and 13C-NMR. J.

Applied Polymer Science. 2001. 80. 1880.

DA SILVA. M.A.. GALLAND. G.B. Synthesis and Characterization of

Ethylene-Propylene-1-Pentene Terpolymers. J. Polymer Science:Part

A: Polymer Chem.. 2008. 46. 947.

GALLAND. G. B.; ESCHER. F. F. N.. 13Carbon nuclear magnetic

resonance of ethylene-propylene-1-hexene terpolymers. J. Polymer

Science Part A-Polymer Chemistry. 2004. 42. 2474.

GALLAND. G. B.; SANTOS. J. H. Z. dos; DALL´AGNOL. M.; BISATTO.

R.. Study of Ethylene-Propylene-1-Hexene Co- and Terpolymers

obtained with homogeneous and supported metallocene catalysts.

Macromolecular Symposia. 2006. 245-246. 42.

ESCHER. F. F. N.; GALLAND. G. B.; FERREIRA. M.. 13Carbon Nuclear

Magnetic Resonance of Ethylene-propylene-1-decene Terpolymers.

J. Polymer Science Part A-Polymer Chemistry. 2003. 41. 2531.

GALLAND. G. B.; ESCHER. F. F. N.. 13Carbon Nuclear Magnetic

Resonance Characterization of ethylene-propylene-1-octadecene

terpolymers and comparison with ethylene-propylene-1-hexene and

1-decene terpolymers. Polymer. 2006. 47. 2634.

CHARACTERIZATION OF ETHYLENE-PROPYLENE- -OLEFIN TERPOLYMERS

BY 13C NMR

Peak Integrals

Type of branch

Amount of branch

BROOKHART CATALYSTS

Galland, G.B.; de Souza, R.F.; Mauler, R.S.; Nunes, F.F. Macromolecules, 1999, 32 1620-1625.

Galland, G.B.; Da Silva, L.P.S.; Dias, M.L.; Crossetti, G.L.; Ziglio, C.M,; Filgueiras, C.A.. J. Polym. Sci .: Part A:

Polymer Chem., 2004, 42, 2171-2178.

Methyl

Ethyl

Propyl

Butyl

Pentyl

Long

1,4-methyl

1,6-methyl

1,2-ethyl

iso-butyl

2-methyl-hexyl

POLYETHYLENE STRUCTURES OBTAINED WITH DADNi(NCS)2

CATALYST

NN

O

Ni

Br Br

MAO, toluene

R

R = H, CH3, C4H9

poly( -olefin)

Poly(1-hexene) homopolymers obtained using

13C NMR CHARACTERIZATION OF POLY- -OLEFINS OBTAINED

WITH AN -KETO- -DIIMINE NICKEL INITIATOR

1

Azoulay, Jason D., Schneider, Yanika, Galland, Griselda B., Bazan, Guillermo C. Chemical Communications 1996, 6177 - 6179,

2009.

Azoulay, Jason D., Rojas, Rene S., Serrano, Abigail V., Ohtaki, Hisashi, Galland, G. B., Wu, Guang, Bazan, Guillermo C.

Angewandte Chemie (International Edition), 48, 1089 - 1092, 2009.

Entrya Conditionsb TOFc Mnd PDI Tg

e

1/10 25 C, 10 mL 1-hexene 356 120 2.0 -56

2/10 0 C, 10 mL 1-hexene 89 157 1.2 -55

3/12.5f -10 C, 15 mL 1-hexene 300 120 1.05 -62

[a] moL of 1; [b] entries 1-2 carried out in a Schlenk flask in 10 mL toluene at a [1-hexene] = 4 M, In entry 3 [1-hexene] = 0.85 M; [c] hr-1

[d] 10-3 g mol-1 determined by GPC in o-dichlorobenzene at 135 C as determined by GPC versus polystyrene standards; Mn values calculated on the basis of TOF are lower than those shown and indicate that the use of polystyrene standards substantially overestimates the Mn for entries 1- 3. [e] oC; [f] In entry 3, the volatiles were removed from a commercially available MAO solution.

13C NMR spectrum of the poly(1-hexene) obtained in entry 1.

Azoulay, Jason D., Bazan, Guillermo C., Galland, Griselda B. Macromolecules, 43,.2794 - 2800, 2010.

Poly(1-hexene) 13C Nuclear Magnetic Resonance results,

calculated and observed chemical shifts and assignments.

Peak No

Chem. ShiftCalc.(ppm)

Chem. ShiftExp.(ppm)

Assignments Sequences

1 11.36 11.10 1B2[EBE]

2 13.86 14.15 1B4, 1Bn[EHE]+[HHH]+[HHE+EHH]+[PHH]+[PHE]+[ELE]

3 14.35 14.60 1B3[EAE]

4 19.63 19.85 1B1[EPE]

20.21 20.00 2B3[EAE]

5 20.12 20.30 1B1[EPH]

6 22.65 22.86 2Bn[ELE]

7 22.90 23.30-23.45

2B4[EHE]+[HHH]+[HHE+EHH]+[PHH] ]+[PHE]

8 25.08 24.1-24.4

B4[HEH]

9 27.16 26.51 2B2[EBE]

10 27.52 26.9-27.1

B4[EEHH+HHEE]

11 27.52 27.17 B2, B3 B4,

Bn, n-1)Bn,

[EEB+BEE]+[EEA+AEE]+[EEH+HEE]+[EEL+LEE]

[E]= [EEE]+[HEH]+[PEE+EEP]+[EEH+HEE]+[EEB+BEE]+[EEA+AEE]+[EEL+LEE]= I16/2+ I8+ I10+I11+I12

[HEH]=I8

[EEH(H)+(H)HEE]= I10

[EEB+BEE]+[EEA+AEE]+[EEH+HEE]+[EEL+LEE] = I11

[EEP+PEE]= I12

[HEEP*]+[PEEP*]=I13/2

[EEE]=I16/2

[EH*H]=I20/2

[P]= [EPE]+[EPH]= I4-I3+I5

[EPE]= I4-I3

[EPH]= I5

[B]=[EBE]=(I1+ I30)/2

[A]=[EAE]=(I3+ I26)/2

[H]= [EHE]+[HHH]+[HHE+EHH]+[PHH]+[PHE]=(I7+I14)/2 or I23-I1-I26+I22-I4+I3+I25

[EHE]=I23-I1-I26

[HHH]+[PHH]=I22-I4+I3

[HHH]= I22-I4+I3-I35

[(H)HHH]= I33

[(E)HHH]= I22-I4+I3- I35-I33

[HHE+EHH]=(E)HHE + (H)HHE= (I25 -I34)

[PHH]= I35

[PHE]=I34

[L]= [ELE]=(I6+I21)/2

Equations used in the quantitative analysis of the poly(1-hexene)

Methyl branches

Ethyl branches

Propyl branches

Butyl branches

Long branches

13C NMR Spectra of entry 1- 3.

250C

00C

-100C

Sequences 25OC/4M 0OC/4M -10OC/0.85M[E] 48.7% 41.7% 56.5%

[HEH] 0.0% 0.0% 8.6%

[EEHH+HHEE] 10.9% 14.3% 6.5%

[EEB+BEE]+[EEA+AEE]+[EEH+HEE]+[EEL+LEE]+[EEP+PEE] 6.3% 4.8% 15.0%

[EEP+PEE] 12.8% 8.1% 10.4%

[PEEP*]+[HEEP*] 4.8% 2.7% 0.6%

[EEE] 18.6% 14.4% 16.0%

[EEP] 7.0% 4.2% 6.4%

[EEB]+[EEH]+ [EEA] + [EEL] 15.1% 18.2% 13.9%

[EH*H] 1.4% 1.4% 2.0%

[P]= [EPE]+[EPH] 11.7% 6.6% 7.1%

[EPE] 5.4% 3.3% 4.7%

[EPH] 6.2% 3.3% 2.4%

[B]=[EBE] 0.3% 0.8% 0.3%

[A]=[EAE] 0.7% 0.4% 0.9%

[H]= [EHE]+[HHH]+[HHE+EHH]+[PHH]+[PHE] 37.0% 48.6% 33.9%

[EHE] 4.4% 4.2% 14.3%

[HHH]+[PHH] 14.3% 27.2% 6.0%

[HHH]=[(H)HHH+(E)HHH) 10.8% 25.2% 6.0%

[(H)HHH] 8.0% 18.0% 2.1%

[(E)HHH] 2.8% 7.3% 4.0%

[(H)HHE]+EHH 13.5% 12.7% 7.5%

[(E)HHE 2.1% 3.2% 4.8%

[HHE+EHH]=(E)HHE + (H)HHE+EHH 15.6% 16.0% 12.3%

[PHH] 3.5% 2.0% 0.0%

[PHE]= 2.7% 1.2% 1.2%

[L]= [ELE] 1.7% 2.0% 1.2%

[E]+[P]+[B]+[A]+[H]+[L] 100.0% 100.0% 100.0%

Percentage of monomer sequences in mol % of the poly(1-hexene) obtained at different reaction temperatures and concentrations

Butyl branches increase with the decrease of temperature

1,2-insertion becomes less favored at 25oC

Methyl branches increase with the temperature increase

showing acceleration of 2,6-enchainment and chain working

processes

The significant decrease of the

1,2-insertion of 1-hexene is

attributed to the low concentration

of 1-hexene

LNi

P

1 5

4

3

2 61,2-insertionLNi

1 5

4

32

6

P

1,2-insertion2,6-enchainment

LNi P

1

5

4

32

62,1-insertion

LNi P

1

5

4

2

6

5'

4'3'

6'

1'

2'

"chain-walking"

1'2'

3'4'

5'6'

1,2-insertion

LNi P

1

5

4

2

6

5'

4' 3'

6'

1'2'

3

3

LNi

2,6-enchainment

P6'

5'

4'

3'2'

1'

1

5

4

2

6

3

2,6-enchainment

2,1-insertionLNi

5

P

4

2

6

3

1

1,6-enchainmentLNi

15

4

3

26 P

-hydride elimination

LNi

5

P

4

2

3

1H

6

LNi

154

2P3

LNi

54

2

3

1H

6

LNi1

5

4 2

6

3

P

LNi

54

2

3

1H

6

P

1

5

43

2

6

LNiP

1

5

43

2

6

LNiP

Methyl BranchesPHHEPHEEP

Butyl BranchesHHH

HEEP* PEEP*Long Branches

ELE

(EEE)n

6

Propyl BranchesEAE

-hydride elimination

Ethyl BranchesEBE

-hydride elimination

LNi P

Methyl BranchesEPE

1

54 2

6

3

(2)(3)

(4) (5)

(6) (7)

(8)

(9)

(10)

(11)

(12)

(13)

(14)

(15)

(16)

(17)

Proposed mechanism of branch formation

T=-20oC T=-60oC

Structure 1

P PPP

A

BC

D

P P P*E E

PPE

E

Isolated 3,1-enchainment

(1,2)(3,1)(1,2)

Structure 2

P

P

F

G

P EE P*

P E E P*

E

H

I

Alternating 3,1-enchainment

(1,2)(3,1)(1,2)(3,1)

Structure 3

P

PPJK

P E EE P

L

M

N

Successive 3,1 enchainment

(1,2)(3,1)(3,1)

Structure 4

P

P

P

P P* P*

O

PQ

Head to head

(1,2)(1,2)(2,1)(2,1)

Structure 5

P P

P E P

R

S

Isolated 3,1-enchainment after inversion

(2,1)(3,1)(1,2)

Structure 6

PP

P* P* P P

UT

V Tail to tail

(2,1)(2,1)(1,2)(1,2)

Structure 7

P

P

P P* P

W

YX

Z

Head to head +tail to tail

(1,2)(2,1)(1,2)

Structure 8

E

P

P

PP*E E

PE P* (3,1)(2,1)(1,2)(3,1)

ISOTACTIC PROPYLENE OBTAINED WITH AN -KETO- -DIIMINE NICKEL

INITIATOR

13C NMR chemical shifts of regioirregular polypropylene

Peak Chemical shift Exp.(ppm)

Chemical shift Calc.(ppm) Sequence Assignment

1 14.57 16.64 PP*P P

2 15.72 17.13 PP*P*+PPP*(head-to-head) P

3 19.80-20.10 20.61 PPP(rr) 3a 19.82 20.61 PPPPP(mrrm)3b 19.92 19.63 EPE P

19.63 EPP*E+EP*PE P

19.98 19.61 PPPPP(mrrr)3c 20.08-20.30 19.61 PPPPP(rrrr)4 20.69 20.61 PPPPP(mrmr)

P*P*PP+ P*P*PP (tail-to-tail) P

5 20.86 20.61 PPPPP(mmrm+rmrr)20.12 EPP+PPE P

6 21.02 20.61 PPPPP (mmrr)7 21.15-21.50 20.61 PPPPP(rmmr)8 21.59 20.61 PPPPP(mmmr)9 21.82 20.61 PPPPP(mmmm)10 24.58 24.58 PEP S

11 27.16 27.27 EEPP+PPEE S

12 27.32 27.52 PPEE (r) S

13 27.54 27.52 PPEE (m) S

14 27.73 27.52 PEE+EEPE S

15 28.2-28.9 28.38 PPP28.72 PPPPP(mmmm)

16 29.87 29.96 EEE S

17 30.29 30.21 EEEP+PEEE S

18 30.77 30.45 EPP+PPE+ T

19 31.01 30.4531.53

P*P*PP+ P*P*PP (tail-to-tail)PP*P

TS

20 33.13 32.52 EPE T

Quantitative equationsPercentages of sequences

obtained from equationsSequence Calculation from integrals

[PPP] I15

[EPP+PPE] I18

[EPE] I20

[EEE] I16/2

[EEP+PEE] I11+ I12+ I13+ I14

[PEP] I10

[PP*P*+PPP*] (I23 +I26)/2

[P*PP+P*P*PP] I19-I1

[PP*P] I1

[EP*PE+EP*PE] I21

mmmm I9

mmmr I8

rmmr I7

mmrr I6

mmrm+rmrr I5-I18

mrmr I4- (I19-I1)

rrrr I3c

mrrr I3b- I21-I20

mrrm I3a

Sequence -20oC -60oC

[PPP] 70.90% 100.00%

[EPP+PPE] 12.86% 0.00%

[EPE] 0.72% 0.00%

[EEE] 0.49% 0.00%

[EEP+PEE] 9.15% 0.00%

[PEP] 1.50% 0.00%

[PP*P*+PPP*] 1.25% 0.00%

[P*P*PP]+P*P*PP 1.31% 0.00%

[PPP*P] 0.85% 0.00%

[EP*PE+EP*PE] 0.98% 0.00%

[P] 84.48% 100.00%

[E] 11.14% 0.00%

[P*] 4.38% 0.00%

mmmm 62.7% 85.0%

mmmr 19.8% 3.6%

rmmr 2.5% 0.9%

mmrr 5.0% 3.4%

mmrm+rmrr 0.0% 2.1%

mrmr 1.8% 1.4%

rrrr 2.3% 1.3%

mrrr 3.2% 1.2%

mrrm 2.8% 1.0%

mm 84.9% 89.5%

mr+rm 6.8% 6.9%

rr 8.3% 3.5%

m 88.3% 93.0%

r 11.7% 7.0%

Statistical models

Pm Pmm Pmr Prr Pmmmm

EnantiomorphicSite model

0.964 0.896 0.069 0.035 0.833

Chain End model 0.930 0.865 0.130 0.005 0.748

Experimental 0.93 0.895 0.069 0.035 0.850

Structure 1

P PPP

A

BC

D

P P P*E E

PPE

E

Isolated 3,1-enchainment

(1,2)(3,1)(1,2)

Structure 2

P

P

F

G

P EE P*

P E E P*

E

H

I

Alternating 3,1-enchainment

(1,2)(3,1)(1,2)(3,1)

Structure 3

P

PPJK

P E EE P

L

M

N

Successive 3,1 enchainment

(1,2)(3,1)(3,1)

Structure 4

P

P

P

P P* P*

O

PQ

Head to head

(1,2)(1,2)(2,1)(2,1)

Structure 5

P P

P E P

R

S

Isolated 3,1-enchainment after inversion

(2,1)(3,1)(1,2)

Structure 6

PP

P* P* P P

UT

V Tail to tail

(2,1)(2,1)(1,2)(1,2)

Structure 7

P

P

P P* P

W

YX

Z

Head to head +tail to tail

(1,2)(2,1)(1,2)

Structure 8

E

P

P

PP*E E

PE P* (3,1)(2,1)(1,2)(3,1)

Possible structures of isotactic regio- irregular polypropylene

Sequence -20oC -60oC

0 82,9% 100,0%

1 7,9% 0,0%

2 0,8% 0,0%

3 1,5% 0,0%

4 1,5% 0,0%

5 1,7% 0,0%

6 1,5% 0,0%

7 1,0% 0,0%

8 1,1% 0,0%

ACKNOWLEGMENTS

STUDENTS:

Adilson Arli da Silva Filho

Adriane Gomes Simanke

Fernanda Nunes Escher

Marco Antonio da Silva

Fabiana de Carvalho Fim

Marcéo Auler Milani

Grasiela Gheno

ACKNOWLEGMENTS

COLLABORATIONS:

Prof. Dr. Raul Quijada- Universidad de Chile- Chile

Prof. Dr. René Rojas Guerrero- Universidad Católica de Chile- Chile

Prof.a Dra. Maria Lujan Ferreira- Universidad de Bahia Blanca- Argentina

Prof. Dr. Marcelo Villar- Universidad de Bahia Blanca- Argentina

Prof. Dr. Guillermo Bazan- University of California at Santa Barbara- USA

Prof. Dr. Marcos Lopes Dias- Universidade Federal do Rio de Janeiro- Brazil

Prof. Dr. José Carlos Pinto- Universidade Federal do Rio de Janeiro- Brazil

ACKNOWLEGMENTS

ACKNOWLEGMENTS

CNPQ

FAPERGS

Thanks to the following agencies for financial support:

CAPES

THANK YOU FOR YOUR ATENTION!