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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!