Supporting Information

Facile synthesis of polyhydroperoxides from ethylene and carbon

monoxide

Hyuk-Joon Jung, Hootan Roshandel, Yin-Pok Wong, Paula L. Diaconescu*

Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095
(USA)

Table of Contents

A. Experimental section ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S2

B. NMR spectra and DOSY plots ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S5

C. IR spectra ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S23

D. SEC traces ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S25

E. DSC traces ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S34

F. TGA traces ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S37

G. PXRD patterns ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S38

H. References ꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏꞏ S39

S1
A. Experimental section
General considerations. Unless otherwise indicated, all air and/or water-sensitive reactions were
performed under a dry nitrogen atmosphere using either an MBraun glovebox or standard Schlenk
techniques. NMR spectra were recorded on a Bruker AV-300, Bruker AV-400, Bruker AV-500, or
Bruker DRX-500 spectrometers at room temperature. 1H NMR chemical shifts are reported in ppm
versus residual protons in deuterated solvents as follows: δ 7.27 CDCl3, δ 7.16 C6D6, δ 2.50
(CD3)2SO, and δ 8.03, 2.92, and 2.75 (CH3)2NCOD. 13C{1H} NMR chemical shifts are reported in
ppm versus residual 13C in the solvent: δ 77.2 CDCl3, and δ 128.39 C6D6. Diffusion ordered
spectroscopy (DOSY) experiments were conducted on a NEO600 NMR instrument with a sample
concentration of 3-5 mg/mL. All DOSY experiments were conducted with gradient pulse lengths
(δ) ranging from 0.700 ms to 1.25 ms, and with diffusion times (Δ) ranging from 40 ms to 300 ms,
depending on the sample, and the linear gradient split to 64 steps from 2% to 95% strength. Nuclear
overhauser spectroscopy (NOESY) was performed on polyhydroperoxide in d1-
dimethylformamide, which was dried over 3Å molecular sieves with a mixing time of 300 ms.
Molar masses of polyketones were determined by size exclusion chromatography using an Agilent
1100 Series HPLC system at the University of Florida. The instrument is equipped with a PL-HFIP
gel column and a refractive index detector. Polymers were separated by the column at a flow rate
of 0.3 mL/min at a column temperature of 0 oC in HFIP with trifluoroacetic acid (10-20 mM), and
the column was calibrated using a standard poly(methyl methacrylate). Molar masses of
polyhydroperoxides were determined by size exclusion chromatography using an Infinity 1260 II
HPLC system at UCLA. The Infinity 1260 II HPLC system from Agilent is equipped with a diode
array detector DAD from Wyatt technology, a multiangle light scattering detector MALS, and a
differential refractive index detector dRI from Wyatt technology. Polymers were separated on two
Plgel Mixed-D gel columns PL1110-6504 (300 × 7.5 mm) at a flow rate of 0.60 mL/min. Column
temperature was set at 40 oC in DMF with LiBr (0.1 M). The number average molar mass and
molecular weight distribution values were determined using the dn/dc values of the polymers.
Molar masses of graft copolymers were determined by size exclusion chromatography using an
SEC-MALS instrument at UCLA. SEC-MALS uses a Shimazu Prominence-i LC 2030C 3D
equipped with an autosampler, two MZ Analysentechnik MZ-Gel SDplus LS 5 μm, 300 × 8 mm
linear columns, a Wyatt DAWN HELEOS-II, and a Wyatt Optilab T-rEX. The column temperature
was set at 40 oC. A flow rate of 0.70 mL/min was used, and samples were dissolved in THF. The
number average molar mass and molecular weight distribution values were determined using the
dn/dc values, which were calculated by the 100% mass recovery method from the RI signal.
Thermal gravimetric analysis (TGA) was performed using a PerkinElmer Pyris Diamond TG/DTA
Instruments under nitrogen. Samples were placed in an alumina crucible and heated under nitrogen
at a rate of 10 °C/min from 30 to 800 °C. Differential scanning calorimetry (DSC) was obtained
using a PerkinElmer DSC model 8500 heat flow system with Intracooler II. Experiments were
carried out under a nitrogen atmosphere with Ca. 5 mg of the polymer samples sealed in an
aluminum pan with a punctured lid. The samples were heated from -50 to 200 ℃ with a 10 ℃ /min
heating rate. Powder X-ray diffraction data were collected using a PANanalytical Xpert Pro
diffractometer with Cu Kα radiation (Cu Kα1 = 1.5406 Å, Cu Kα2 = 1.5444 Å; Kα2/ Kα1 = 0.5)
with step side of 0.02°, an accelerating voltage of 45 kV, and a current of 40 mA. Diffraction
patterns were collected from 6° to 50° 2θ. Attenuated total reflection Fourier transform infrared
(ATR-FTIR) spectroscopy was performed on an Agilent Cary 600 series FTIR microscope
equipped with a universal ATR assembly. Ca. 5 mg of each polymer sample was placed onto the

S2
ATR crystal for FTIR measurements. The spectra were acquired from 4000 to 700 cm-1 with a
resolution of 4 cm-1 and 32 scans at room temperature.

Materials. Solvents were purified with a two-state solid-state purification system by the method
of Grubbs1 and transferred into a glovebox without exposure to air. Deuterated NMR solvents
(CDCl3, C6D6, and (CH3)2NCOD) were purchased from Cambridge Isotope Laboratories, dried
over CaH2, collected by vacuum distillation, degassed through a series of freeze-pump-thaw
cycles, and stored over activated molecular sieves prior to use. Aqueous hydrogen peroxide (30%
w/w) and 1,1,1,3,3,3-hexafluoro-2-propanol were purchased from Fisher Scientific and Oakwood
Chemical, respectively, and used as received. The cationic palladium methyl complex
[(dppp)Pd(Me)(MeCN)][BArF4] (dppp = 1,2-bis(diphenylphosphino)propane, ArF = 3,5-
bis(trifluoromethyl)phenyl) was synthesized following a published procedure.2

General procedure for the synthesis of alternating polyketone. In a nitrogen-filled glovebox,

5 mM stock solutions of Pd complex were prepared in toluene. A 20 mL scintillation vial was
charged with 5 mL of the stock solution and a stir bar. The vials (three vials in total) were placed
in a 300 mL high-pressure reactor. The reactor was sealed and brought outside the glovebox to be
charged with a gas mixture of CO (100 psi) and C2H4 (100 psi) at room temperature. After the
solutions were saturated with gases, the reactor was placed on a stirring plate. The gases were
vented to atmospheric pressure after 2 h at room temperature. 10 mL of MeOH and 0.6 mL of 35%
HCl were added to the vials retrieved from the reactor, and the mixture was vigorously stirred for
16 h. The insoluble polymer products were collected by a centrifuge, washed with additional
MeOH, and dried under vacuum overnight. Isolated polymer samples were dissolved in a mixture
of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and C6D6 (1:4, v/v) and analyzed by 1H NMR
spectroscopy at 25 °C. The assignment of peaks in the 1H NMR spectra was made based on reports
in the literature.2

General procedure for the synthesis of polyhydroperoxide 1. A 20 mL scintillation vial was

charged with polyketone (200 mg) in HFIP (2 mL) and a stir bar. An aqueous solution of hydrogen
peroxide (H2O2, 30% w/w, 121 mg, 1 equiv.) was added to the stirring mixture dropwise. The
reaction mixture was stirred for a designated period of time at room temperature. Cold methanol
(0 °C, 15 mL) was added to the reaction mixture. The polymer products were collected by a
centrifuge, washed with additional MeOH (3 x 10 mL), and dried under vacuum overnight. Isolated
polymer samples were dissolved in CDCl3 and analyzed by 1H and 13C{1H} NMR spectroscopies
at 25 °C. 1H NMR (400 MHz, 298 K, CDCl3): δ 9.75 − 9.43 (2H, m, OOH) δ 2.40 − 1.65 (4H, m,
CH2). 13C NMR (125 MHz, 298 K, CDCl3): δ 111.0 (C), 34.8 − 28.6 (CH2).

Synthesis of polyketone derivatives. Polyketones bearing alkyl or aryl groups were synthesized
via copolymerization of CO, ethylene, and a third olefin monomer, either 1-hexene (42 mg, 20
equiv.) or 4-methyl styrene (59 mg, 20 equiv.), following the same procedure described above for
alternating polyketone.

S3
Synthesis of polyhydroperoxide from a mixture of polyketone derivatives. In a scintillation
vial, polyketone bearing an alkyl group (25 mg) and polyketone bearing an aryl group (25 mg)
were dissolved in 4 mL of HFIP. After the addition of aqueous hydrogen peroxide (H2O2, 30%
w/w, 121 mg, 4 equiv.), the reaction mixture was stirred overnight. The polymer was precipitated
out using cold methanol (0 °C, 15 mL) and collected by a centrifuge. The polymer products were
washed with additional methanol (3 x 10 mL) and dried overnight to give the product as an off-
white powder.

General procedure for oxidation of sulfide with 1. In a glovebox, a 25 mL Schlenk tube was
charged with tetrahydrothiophene (8.3 mg, 1 equiv.) followed by 1 (10 mg, 1 equiv.) in DMF (0.5
mL). The Schlenk tube was sealed and taken out of the glovebox. The reaction mixture was stirred
in an oil bath with a preset temperature of 100 °C for 16 hours. The reaction mixture was cooled
down to room temperature. The crude mixture was dissolved in CDCl3 to be analyzed by 1H NMR
spectroscopy to determine the conversion of tetrahydrothiophene to tetramethylene sulfoxide.

General procedure for graft copolymerization of vinyl monomers initiated by 1. In a glovebox,

a 25 mL Schlenk tube was charged with 4-methylstyrene (205 mg, 50 equiv.) followed by 1 (5 mg,
1 equiv.) in DMF (2 mL). The Schlenk tube was sealed and taken out of the glovebox. The reaction
mixture was stirred in an oil bath with a preset temperature of 80 °C for 16 hours. The reaction
mixture was cooled down to room temperature. Aliquot of the crude mixture was dissolved in
CDCl3 to be analyzed by 1H NMR spectroscopy to determine the conversion of monomer. Cold
methanol (0 °C, 15 mL) was added to the remaining reaction mixture. The precipitated polymer
products were collected by a centrifuge, washed with additional MeOH (3 x 10 mL), and dried
under vacuum overnight prior to analysis.

General procedure for degradation of graft copolymers. A 50 mL round bottom flask was
charged with polyethylene-g-poly(methyl methacrylate) (50 mg) in 1,2-dichloroethane (5 mL). An
aqueous solution of sulfuric acid (0.5 mL, 50%, v/v) was added to the solution of graft copolymer
dropwise at room temperature. The reaction mixture was stirred with a condenser in an oil bath at
80 °C. After 48 hours, the reaction mixture was cooled down to room temperature, and cold
methanol (0 °C, 20 mL) was added to the reaction mixture. The viscous degradation products were
washed with additional MeOH (3 x 10 mL), and dried under vacuum overnight prior to analysis.

S4
B. NMR Spectra

Figure S1. 1H NMR spectrum (1:4 HFIP/C6D6, 400 MHz, 25 °C) of alt-polyketone.

Figure S2. 13C{1H} NMR spectrum (1:4 HFIP/C6D6, 125 MHz, 25 °C) of alt-polyketone.

S5
Figure S3. 1H NMR spectrum (CDCl3, 400 MHz, 25 °C) of polyhydroperoxide 1.

Figure S4. 13C{1H} NMR spectrum (CDCl3, 125 MHz, 25 °C) of polyhydroperoxide 1.

S6
Figure S5. DEPT-135 spectrum (CDCl3, 125 MHz, 25 °C) of polyhydroperoxide 1.

Figure S6. 1H NMR spectrum (1:4 HFIP/C6D6, 400 MHz, 25 °C) of poly(ketone-co-peroxide) 2.

S7
Figure S7. 13C{1H} NMR spectrum (1:4 HFIP/C6D6, 125 MHz, 25 °C) of poly(ketone-co-
hydroperoxide) 2.

Figure S8. 1H NMR spectrum (1:4 HFIP/C6D6, 500 MHz, 25 °C) of polyketone bearing an alkyl
substituent.

S8
Figure S9. 13C{1H} NMR spectrum (1:4 HFIP/C6D6, 125 MHz, 25 °C) of polyketone bearing an
alkyl substituent.

1
Figure S10. H NMR spectrum (1:4 HFIP/C6D6, 500 MHz, 25 °C) of polyketone bearing an aryl
substituent.

S9
Figure S11. 13C{1H} NMR spectrum (1:4 HFIP/C6D6, 125 MHz, 25 °C) of polyketone bearing
an aryl substituent.

Figure S12. 1H NMR spectrum (1:4 HFIP/C6D6, 500 MHz, 25 °C) of polyhydroperoxide derived
from a mixture of polyketone derivatives.

S10
Figure S13. 13C{1H} NMR spectrum (1:4 HFIP/C6D6, 125 MHz, 25 °C) of polyhydroperoxides
derived from a mixture of polyketone derivatives.

Figure S14. 1H NMR spectrum (CDCl3, 400 MHz, 25 °C) of polyethylene-g-poly(4-methyl

styrene) (Table 2, entry 1).

S11
Figure S15. 13C{1H} NMR spectrum (CDCl3, 125 MHz, 25 °C) of polyethylene-g-poly(4-methyl
styrene) (Table 2, entry 1).

Figure S16. 1H NMR spectrum (CDCl3, 400 MHz, 25 °C) of polyethylene-g-poly(methyl

methacrylate) (Table 2, entry 6).

S12
Figure S17. 13C{1H} NMR spectrum (CDCl3, 125 MHz, 25 °C) of polyethylene-g-poly(methyl
methacrylate) (Table 2, entry 6).

Figure S18. 1H NMR spectrum (CDCl3, 400 MHz, 25 °C) of polyethylene-g-poly(4-methyl

styrene) (Table 2, entry 3).

S13
Figure S19. 13C{1H} NMR spectrum (CDCl3, 125 MHz, 25 °C) of polyethylene-g-poly(methyl
methacrylate) (Table 2, entry 3).

Figure S20. 1H NMR spectrum (CDCl3, 400 MHz, 25 °C) of polyethylene-g-poly(methyl

methacrylate) (Table 2, entry 8).

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Figure S21. 13C{1H} NMR spectrum (CDCl3, 125 MHz, 25 °C) of polyethylene-g-poly(methyl
methacrylate) (Table 2, entry 8).

Figure S22. DOSY (CDCl3, 600 MHz, 25 °C) plot of polyhydroperoxide 1 with gradient pulse
duration (δ) of 0.700 ms, and diffusion time (Δ) of 40 ms.

S15
Figure S23. DOSY (1:4 HFIP/C6D6, 600 MHz, 25 °C) plot of poly(ketone-co-hydroperoxide) 2
with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 300 ms.

Figure S24. DOSY (1:4 HFIP/C6D6, 600 MHz, 25 °C) plot of polyketone bearing an alkyl group
with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 300 ms.

S16
Figure S25. DOSY (1:4 HFIP/C6D6, 600 MHz, 25 °C) plot of polyketone bearing an aryl group
with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 250 ms.

Figure S26. DOSY (1:4 HFIP/C6D6, 600 MHz, 25 °C) plot of polyhydroperoxide derived from
a mixture of polyketone derivatives with gradient pulse duration (δ) of 0.800 ms, and diffusion
time (Δ) of 40 ms.

S17
Figure S27. DOSY (CDCl3, 500 MHz, 25 °C) plot of polyethylene-g-poly(4-methyl styrene)
(Table 2, entry 1) with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 95 ms.

Figure S28. DOSY (CDCl3, 500 MHz, 25 °C) plot of polyethylene-g-poly(methyl methacrylate)
(Table 2, entry 6) with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 95 ms.

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Figure S29. DOSY (CDCl3, 500 MHz, 25 °C) plot of polyethylene-g-poly(4-methyl styrene)
(Table 2, entry 3) with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 120 ms.

Figure S30. DOSY (CDCl3, 500 MHz, 25 °C) plot of polyethylene-g-poly(methyl methacrylate)
(Table 2, entry 8) with gradient pulse duration (δ) of 1.250 ms, and diffusion time (Δ) of 90 ms.

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Figure S31. 1H NMR spectrum ((CH3)2NCOD, 500 MHz, 25 °C) of 1 after addition of D2O (top)
and before addition of D2O (bottom).

Figure S32. 1H NOESY ((CH3)2NCOD, 600 MHz, 25 °C) plot of 1 (blue signal = exchange peak,
red signal = NOE peak) with mixing time of 300 ms.

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Figure S33. 1H NMR spectrum (CDCl3, 400 MHz, 25 °C) of the crude products from the
oxidation of tetrahydrothiophene using 1.

Figure S34. 13C{1H} NMR spectrum (CDCl3, 125 MHz, 25 °C) of products obtained from the
reaction of 1 with p-toluenesulfonic acid.

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Figure S35. 1H NMR spectrum ((CD3)2SO, 400 MHz, 25 °C) of degradation products. The
degradation reaction was performed in 1,2-dichloroethane at 80 °C for 48 hours.

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C. IR Spectra

Figure S36. ATR-FTIR spectrum of alt-polyketone.

Figure S37. ATR-FTIR spectrum of polyhydroperoxide 1.

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Figure S38. ATR-FTIR spectrum of poly(ketone-co-hydroperoxide) 2.

Figure S39. ATR-FTIR spectra of polyethylene-g-poly(4-methyl styrene) (top, Table 2, entry 1)

and polyethylene-g-poly(methyl methacrylate) (bottom, Table 2, entry 6).

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D. SEC traces

Figure S40. SEC trace of alt-polyketone.

Figure S41. SEC trace of alt-polyketone with a bimodal molecular weight distribution.

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Figure S42. SEC trace of polyhydroperoxide 1 (Table 1, entry 1).

Figure S43. SEC trace of polyhydroperoxide 1 (Table 1, entry 2).

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Figure S44. SEC trace of polyhydroperoxide 1 (Table 1, entry 4).

Figure S45. SEC trace of polyhydroperoxide 1 (Table 1, entry 8).

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Figure S46. SEC trace of polyethylene-g-poly(4-methyl styrene) (Table 2, entry 1).

Figure S47. SEC trace of polyethylene-g-poly(4-methyl styrene) (Table 2, entry 2).

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Figure S48. SEC trace of polyethylene-g-poly(4-methyl styrene) (Table 2, entry 3).

Figure S49. SEC trace of poly(4-methyl styrene) (Table 2, entry 4).

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Figure S50. SEC trace of poly(4-methyl styrene) (Table 2, entry 5).

Figure S51. SEC trace of polyethylene-g-poly(methyl methacrylate) (Table 2, entry 6).

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Figure S52. SEC trace of polyethylene-g-poly(methyl methacrylate) (Table 2, entry 7).

Figure S53. SEC trace of polyethylene-g-poly(methyl methacrylate) (Table 2, entry 8).

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Figure S54. SEC trace of poly(methyl methacrylate) (Table 2, entry 9).

Figure S55. SEC trace of poly(methyl methacrylate) (Table 2, entry 10).

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Figure S56. SEC trace of degradation products. The degradation reaction was performed in
chloroform at room temperature for 24 hours.

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E. DSC traces

Figure S57. DSC thermograms of alt-polyketone.

Figure S58. DSC thermograms of polyhydroperoxide 1.

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Figure S59. DSC thermograms of poly(ketone-co-hydroperoxide) 2.

Figure S60. DSC thermograms of polyethylene.

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Figure S61. DSC thermograms of polyethylene-g-poly(4-methyl styrene) (Table 2, entry 1) and
polyethylene-g-poly(methyl methacrylate) (Table 2, entry 6).

Figure S62. DSC thermograms of polyethylene-g-poly(4-methyl styrene) (Table 2, entry 3) and

polyethylene-g-poly(methyl methacrylate) (Table 2, entry 8).

S36
F. TGA traces

Figure S63. TGA curves of alt-polyketone, polyhydroperoxide 1, and poly(ketone-co-

hydroperoxide) 2.

Figure S64. TGA curve of polyethylene.

S37
G. PXRD patterns

Figure S65. PXRD patterns of alt-polyketone (top, blue) and polyhydroperoxide 1 (bottom, red).

S38
H. References

1. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J., Safe and
Convenient Procedure for Solvent Purification. Organometallics 1996, 15 (5), 1518-1520.
2. Dodge, H. M.; Natinsky, B. S.; Jolly, B. J.; Zhang, H. C.; Mu, Y.; Chapp, S. M.; Tran, T. V.;
Diaconescu, P. L.; Do, L. H.; Wang, D. W.; Liu, C.; Miller, A. J. M., Polyketones from carbon
dioxide and ethylene by integrating electrochemical and organometallic catalysis. ACS Catal. 2023,
13 (7), 4053-4059.

S39