of 49
S
1
Supporting Information
α
,
ω
-
Diene
Generation
from Ethylene and Butadiene by
Copolymer Upcycling
Meaghan A. Bruening, Shuoyan Xiong, Theodor Agapie*
Division of Chemistry and Chemical Engineering, California Institute of Technology. Pasadena, CA
911
25, United States
*
Corresponding
author:
agapie@caltech.edu
This file includes:
Number of pages:
49
Number of tables:
6
Number of figures:
47
S
2
Contents
1.
General
Considerations
S
3
2.
Experimental
S
3
3. Ethylene/Butadiene Copolymers
S
4
4. Ethenolysis Trials with Polymers A, B, and C
S
4
5
.
Ethenolysis Trials with M202 at Elevated Temperatures
S
5
6
.
GC
-
MS Retention Times for commercial
ly available standards
S
5
7
.
Calibration Curve for GC
-
FID Quantification of 1,9 decadiene
S
6
8
.
Yield calculation for
α
,
ω
-
diene mixture
S
6
9.
Representative GC Chromatograms
S
8
10.
Mass Spectrum Analysis for C
18
Products
S
1
1
1
1
.
1
H
and
13
C
NMR
Spectra
of Copolymers A, B, and C
S
1
5
1
2
.
1
H NMR
Spectra
and selected
13
C NMR
Spectra
of Material after Ethenolysis
S
2
1
1
3
.
Ethylene/Butadiene Copolymerization by Cobalt Catalys
t
and Subsequent Metathesis
S
4
7
References
S
4
9
S
3
1.
General Considerations
Unless otherwise specified, all operations involving air
-
or water
-
sensitive reagents were carried out in an MBraun
drybox under a nitrogen atmosphere or using standard Schlenk and vacuum line
techniques. Solvents for air
-
and
moisture
-
sensitive reactions were dried by the method of Grubbs.
1
Deuterated solvents were purchased from
Cambridge Isotope Laboratories and
C
6
D
6
vacuum transferred from sodium benzophenone ketyl before use. All
solvents, once dried and degassed, were store
d under a nitrogen
atmosphere over 4 Å molecular sieves.
Ligand
precursor 1
2
and Ti OSSO
3
and PDI
-
Co
4
were prepared according to literature procedures. Ligand 2 was prepared
with modification to the published p
rocedure.
1
H
and
13
C{
1
H}
NMR spectra were recorded on Varian 400 MHz
spectrometers at ambient temperatures, unless otherwise denoted.
1
H and
13
C{
1
H} NMR spectra are reported
referenced internally to residual solvent peaks reported relative to tetramethylsi
lane.
Gas chromatography
-
mass
spectrometr
y (GC
-
MS) were performed with on an Agilent 6890A instrument using a HP
-
5MS column (30 m length,
0.25 mm diameter, 0.50 μm film) and an Agilent 5973N mass
-
selective EI detector
.
2.
Experimental
Compound 2 w
as
p
repared with modification to the published procedure.
To a solution of
1
(
1.5
g,
3.1
mmol,
1.0
equiv) in THF was added dropwise a freshly prepared solution of sodium
napthalenide
(
6.9
mmol,
2.2
equiv). The solution was stirred for 1hr at RT, before remova
l of all solvent
in vacuo
.
The material was resuspended in dry MeOH (
30
mL), and 1,2 dibromoethane (
590
m
g,
3.1
mmol,
1.0
equiv) was
added
under a counterflow of N
2
. The reaction was heated to 70
o
C for 1hr. Upon cooling to RT, the product
precipitated a
nd was filtered and washed with DCM. The product was redissolved in Et
2
O and concentrated
in
vacuo
to afford
2
as a white solid. (
1.36
g,
86
%)
1
H
NMR
(C
6
D
6
)
7.49 (d, 2H, J
=
4H), 7.02 (d, 2H, J
=
4H), 2.26
(m, H), 1.65 (s, 9H), 1.17 (s, 9H).
General Polym
erization Conditions
A solution of butadiene (2
0
w
eight
% in toluene, 1000
-
3000 equiv)
and
MAO (1000 equiv)
were transferred to a
Fisher Porter Vessel
, and toluene was added to a final reaction volume of 14mL
.
3
(6.2
mg, 10
mmol, 1 equiv)
was
dissolved
i
n toluene (1
mL) and transferred to a capped luer
-
lock syringe. The N
2
atmosphere was replaced with
ethylene by pressurizing and venting the vessel. The catalyst was injected under 25
psi of ethylene before increasing
the pressure to desired reaction con
ditions. The reaction was quenched by exposure to air, and the polymer was
precipitated with MeOH and dried overnight under vacuum.
General Ethenolysis Conditions
Polymer sample (300 mg) and Grubbs Catalyst 1 (
25
mg, 30
mmol) were dissolved in
10
mL o
f toluene and
transferred to a Fisher Porter Vessel. The N
2
atmosphere was replaced with ethylene by pressurizing and venting the
vessel. The vessel was heated to 60
o
C for desired amount of time (0.25
-
16
hr). Ethyl vinyl ether
(
0.1
mL)
was
inject
ed, and
the vessel was stirred for an additional 30 minutes. The vessel was cooled to room temperature. The
remaining polymer was precipitated with methanol (50
mL) and filtered. The filtrate was analyzed by GC
-
MS to
detect the produced
α
,
ω
dienes. The remaining polymeric material was dried under vacuum overnight, and the
internal and terminal olefins were analyzed via
1
H NMR.
The
filtrate was concentrated under vacuum to remove
solvent and products
C12, and the olefin content was ana
lyzed by
1
H NMR .
S
4
3
.
Ethylene/Butadiene Copolymers
Table S1:
Copolymers A, B, and C Prepared from Copolymerization of Butadiene and Ethylene
Entry
a
[Ti]/
mol
[ethylene]
/psi
[BD]/[Ti]
Temp.
(
°
C)
time
(min)
Yield
(g)
Act.
(kg/(mol
·
h))
b
Mw/10
3
PDI
1,4
-
BD
(mol
%)
c
A
10
100
1000
25
5
3.5
4542
7.1
3.45
4.6
B
10
50
3000
25
5
2.1
2505
7.16
3.76
17.8
C
10
25
3000
25
5
2.0
2345
ND
ND
27.8
a
Polymerization conditions: Ti complex (10
μ
mol), Al/Ti = 1000, total volume = 25
mL
b
Activity = kg/(mol of Ti
h)
c
Determined by
1
H NMR
4
. Ethenolysis Trials with Copolymers A, B, and C
Table S2:
Ethenolysis Trials for Ethylene/Butadiene Copolymers A, B, and C
[a]
Entry
Polymer
Polymer
Mass
(mg)
Ru
(
μ
mol )
C
2
H
4
pressure
(psi)
Time
(hr)
Temp
(
o
C)
Remaining
polymer
mass
(%)
1,4
Butadiene
in
remaining
polymer
(mol %)
Internal
o
lefins in
f
iltrate
(%)
Mw
x10
3
PDI
Before
A
4.7
7.08
3.45
1
A
300
30
0
1
60
97
4.7
NA
ND
ND
2
A
300
30
25
1
60
83
1.2
34
6.95
3.79
3
A
300
30
50
1
60
77
ND
29
6.96
3.97
4
A
300
30
100
1
60
82
0.9
23
ND
ND
6
A
300
30
125
1
60
83
1.2
29
6.55
3.84
7
A
300
0
100
1
60
94
4.7
NA
6.31
3.81
5
A
[b]
150
30
100
1
60
98
0.9
NA
Before
B
17.8
7.16
3.76
8
B
150
15
100
0.25
60
6
1
5.7
40
3.11
2.99
9
B
150
15
100
0.5
60
64
4.6
ND
3.03
2.51
10
B
900
30
100
1
60
55
3.7
49
2.85
2.87
11
B
[c]
450
30
100
1
60
62 (42)
[e]
1.5
23
3.25
2.54
12
B
[d]
150
30
100
1
60
ND
ND
ND
6.87
3.79
13
B
300
30
100
2
60
58
5.3
43
2.86
2.54
14
B
300
30
100
16
60
52
4.5
42
2.89
2.51
Before
C
27
ND
ND
15
C
300
30
100
1
60
39
10.8
49
ND
ND
[a] V = 10 mL, T= 60 °C,
solvent: toluene
.
Following the ethenolysis trial, filtration was performed to remove
remaining polymer. Solvent was concentrated under vacuum, and the olefin content of remaining filtrate (C
1
4
+
)
was
analyzed by 1H NMR
[b] Polymer residue from entry 4 was used as the precursor polymer. [c] Polymer residue from
entry 10 was used as the precursor polymer. [d] Polymer residue from entry 11 was used as the precursor polymer. [e]
Overall yield for two e
thenolysis (entry 11).
S
5
5
. Ethenolysis Trials with M202 at Elevated Temperatures
Table
S3
:
Ethenolysis Trials with M202 at Elevated Temperatures
[a]
Polymer D prepared from copolymerization
of ethylene (100psi) and butadiene (3000equiv)
for 0.08h
with
1000equiv MAO and
10
μ
mol Ti
-
OSSO
6
. GC
-
MS Retention Times for commercially available standards
Table S
4
:
GC
-
MS Retention Times for commer
cially available standards
Compound
Retention Time
(minutes)
1,5
-
hexadiene
2.008
1,7
-
octadiene
4.082
1,9
-
decadiene
6.231
1
-
decene
6.351
1
-
dodecene
8.042
1
-
tetradecene
9.517
1
-
hexadecene
10.780
1
-
octadecene
11.946
Entry
Polymer
Polymer
/
mg
Catalyst
Ru
/
μ
mol
C
2
H
4
/
psi
t/h
Temp
(
o
C)
1,4
butadiene
in
remain
in
g
polymer
(mol %)
Remaining
polymer
mass
(%)
Internal
Olefins in
Filtrate (%)
Before
D
[a]
13.7
1
D
300
M202
30
25
1
100
~5
64
80
2
D
300
M202
30
50
1
100
ND
59
85
3
D
300
M202
30
10
0
1
100
ND
62
94
S
6
7
. Calibration Curve for GC
-
FID Quantification of 1,9 decadiene
Figure S1:
Calibration Curve for GC
-
FID Quantification of 1,9 decadiene
; internal
standard is 1,3,5
trimethoxybenzene
8
.
Yield calculation for
α
,
ω
-
diene
mixture
Due to the formation of a distribution of
α
,
ω
-
dienes, product quantification is somewhat complicated. As an
example, product quantification for Entry 4
, Table 1
was accomplished using a combination of GC
-
FID, GC
-
MS,
and residue mass upo
n removal of volatiles vacuo. This ethenolysis trial provides a simple mixture for
quantification given the formation of a primarily single
α
,
ω
-
diene isomer for each C
n
carbon number product. 1,9
-
decadiene was quantified by GC
-
FID upon calibration against
an authentic commercial sample (8.6 mg produced
upon
ethenolysis). To account only for the mass derived from the degradation of polymer, a correction factor was
applied (see Figure S2), with 6.8 mg of 1,9
-
decadiene produced from polymer degradation. 1,1
1
-
dodecadiene was
quantified based on the GC
-
MS response relative to 1,9
-
decadiene (already quantified
by GC
-
FID
), and a correction
factor was applied to account for product mass derived from the polymer
(
7.7 mg produced, with 6.4 mg
corresponding to the
p
olymer
fragment)
. Due to the more complex distributions observed for higher carbon number
products, products C
14
and
higher
were quantified by mass,
upon
complete removal of smaller dienes and solvent
(C
10
, C
12
) under vacuum. A mass of 28
mg
residue was i
solated
corresponding to products C
14+
. Based on the
decrease in mass of polymer after ethenolysis,
an amount of
54
mg of
α
,
ω
-
diene products is expected. The
quantified amount is 41.2 mg (76%),
indicating that
the degraded polymeric material is primarily being converted to
the desired
α
,
ω
-
dienes
.
S
7
Figure S2
:
α
,
ω
dienes C
10
-
C
30
(left) with e
thylene derived fragment, re
d; butadiene, green; ethylene derived from
ethenolysis; blu
e. Representative molecular weights and polymer
-
derived mass weights for C
10
and C
12
dienes
(center). Correction factors (right) to account for mass derived only from degraded polymer.
110
.
20
138
.
25
=
0
.
797
138
.
25
166
.
31
=
0
.
831
166
.
31
194
.
36
=
0
.
856
194
.
36
222
.
42
=
0
.
874
222
.
42
250
.
47
=
0
.
888
250
.
47
278
.
52
=
0
.
900
278
.
52
306
.
58
=
0
.
908
3
06
.
58
334
.
63
=
0
.
916
334
.
63
362
.
69
=
0
.
923
362
.
69
390
.
74
=
0
.
928
390
.
74
418
.
7
9
=
0
.
933
Molecular weight: 138.25 g/mol
Polymer
-
derived mass: 110.20 g/m
ol
Molecular weight: 166.31 g/mol
Polymer
-
derived mass: 138.25 g/mol
S
8
9
. Repres
entative G
as
Chromatograms
Figure S
3
:
G
as
Chromatogram of liquid products for Table 1, Entry 6
Figure S
4
:
G
as
Chromatogram of liquid products for Table 1, Entry
8
6
7
8
9
10
11
12
13
Retention Time (minutes)
6
7
8
9
10
11
12
13
Retention Time (minutes)
S
9
Figure S
5
:
G
as
Chromatogram of liquid products for Table 1, Entry
9
Figure S
6
:
G
as
Chromatogram of liquid products for Table 1, Entry 10
6
7
8
9
10
11
12
13
Retention Time (minutes)
6
7
8
9
10
11
12
13
Retention Time (minutes)
S
10
Figure S
7
:
G
as
Chromatogram of liquid products for Table 1, Entry
14
Figure S
8
: G
as
Chromatogram of liquid products for Table S1, Entry 3
6
7
8
9
10
11
12
13
Retention Time (minutes)
C
10
C
11
C
12
C
14
C
16
C
18
C
13
C
15
C
17
6
7
8
9
10
11
12
13
14
Retention Time (minutes)
C
20
C
19
C
21
S
11
10.
Mass Spectrum Analysis for C
18
Products
Figure
S
9
: GC Chromatogram of liquid products
from Table 1, Entry 10
after concentration and removal of
solvents, selected region shown only for C
18
products
Figure S10:
Full mass spectrum
corresponding to Figure S9, peak 1. Zoom in for selected region indi
cated with red
box, and shown in Figure S13.
S
12
Figure S11:
Full mass spectrum corresponding to Figure S9, peak 2. Zoom in for selected region indicated with
blue box, and shown in Figure S1
4
Figure S12:
Full mass spectrum corresponding to Figure S9, peak
3. Zoom in for selected region indicated with red
box, and shown in Figure S14
S
13
Figure S13:
Selected region of mass corresponding to Figure S9, peak 1. Molecular ion peak indicated with red
star. Molecular fragments which differ from molecular fra
gments in adjacent peak (Peak 2, Figure S14) by 2 mass
units indicated with blue stars
Figure S14:
Selected region of mass corresponding to Figure S9, peak 2. Molecular ion peak indicated with red
star. Molecular fragments which differ from molecular fr
agments in adjacent peaks (Peak 1, Figure S13 or Peak 3,
Figure S15) by 2 mass units indicated with blue stars
S
14
Figure S15:
Selected region of mass corresponding to Figure S9, peak 3. Molecular ion peak indicated with red
star. Molecular fragments whi
ch differ from molecular fragments in adjacent peak (Peak
2, Figure S14
) by 2 mass
units indicated with blue stars
S
15
1
1
.
1
H and
13
C NMR
Spectra
of Copolymers A, B, and C
Figure S
16
:
1
H NMR analysis at 120
o
C
(80% 1,2 dichlorobenzene, 20% benzene
-
d
6
) of ethylene/butadiene
copolymer A
S
16
Figure S
1
7
:
13
C NMR (APT) analysis at 120
o
C (80% 1,2 dichlorobenzene, 20% benzene
-
d
6
) of ethylene/butadiene
copolymer A