Reversible deactivation radical polymerization: giving a new

life to poly(vinyl chloride)

Jorge F. J. Coelho

http://www.polysyc.pt/ www.uc.pt
OUTLINE

Introduction & Motivation

Our adventure working on RDRP methods for VC

Controlling Agents
New solvents

Industrial perspectives for RDRP of VC

Introduction & Motivation I
MARKET EVOLUTION

Despite all criticisms (e.g the need for halogen free materials)

https://www.grandviewresearch.com/
PVC FEATURES

Limitiations of FRP of VC

▪ Unavoidable occurrence of side reaction CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH
Cl Cl Cl Cl Cl Cl Cl

▪ Structural Defects
CH2
Low Thermal Stability CH2 CH CH CH2 CH2 CH CH CH CH2 CH CH2
Cl Cl Cl
PVC Discovery, Braumman 1872
1st commercialization 1940-1960
allylic chloride tertiary chloride labile

▪ Uncontrolled Molecular Weight => f(T)

▪ Compounding Formulations
heat stabilizers, plasticizers, lubricants, impact
modifiers, processing aids Zipper dehydrochlorination reaction

Termination
Chain Transfer Reactions
 RDRP CLASSES

EQUILIBRIA BETWEEN RADICALS AND DORMANT SPECIES

Reversible deactivation by atom transfer

– Atom transfer radical polymerization (ATRP)
e.g metal complexes (e.g Cu with nitrogen based L)

Reversible deactivation by coupling (RDC)

– Nitroxide-mediated polymerization (SFRP/NMP)
– Co-mediated radical polymerization (OMRP/CMRP)
e.g nitroxides, alkoxyamines, orgametallic metallic complexes (e.g Co, Te,…)

Degenerative transfer (DT)

– Reversible addition-fragmentation chain transfer (RAFT)
– Macromolecular design by interchange of xanthate (MADIX)
– Iodine/Reverse Iodine Transfer Polymerization (ITP/RITP)
e.g dithioesters, dithiocarbamates, trithiocarbonates, xanthates, alkyl
iodides

The dynamics of this equilibrium dictate the rate of polymerization and controlling character of the system
ATRP VARIATIONS

Lower oxidation- Higher oxidation-

state transition-metal complex state transition-metal complex Regeneration of Cu(I)X/L activator via
reduction
ppm levels of Cu (≤ 20 ppm)

“in situ” regeneration of Cu(I)X/L

activator via reduction Development of eco-
friendly ATRP systems
✓ ARGET (sugar, ascorbic acid)
✓ ICAR (conventional radical initiators)
✓ eATRP (applied current)
✓ SARA (zerovalent metals, inorganic sulfites)
✓ Photo-ATRP (photoinitator + light)
RDRP OF VC (2012)

Reversible deactivation by atom transfer

– Atom transfer radical polymerization (ATRP)
Only 6 publications for VC
Metal Catalyzed
Cu(0)/TREN/DMSO&H2O
Reversible deactivation by coupling (RDC)
– Nitroxide-mediated polymerization (SFRP/NMP)
– Co-mediated radical polymerization (OMRP/CMRP)

Degenerative transfer (DT)

– Reversible addition-fragmentation chain transfer (RAFT)
– Macromolecular design by interchange of xanthate (MADIX)
– Iodine/Reverse Iodine Transfer Polymerization (ITP/RITP)
~ 33 publications for VC

Single electron transfer degenerative chain transfer living radical

polymerization (SET-DTLRP)
Our adventure exploring RDRP of VC II
 RAFT OF VC

✓ RAFT agent: Cyanomethyl methyl(phenyl) carbamodithioate (CMPCD)

✓ Conventional Initiator:
Trigonox 187 W40 or AIBN
(t1/2 =1h 39◦C) (t1/2 =1h 82◦C)

✓ Studied conditions: solvents, monomer concentration, polymerization temperature,

degree of polymerization
✓ Solvent: THF(?), cyclohexanone, DCM
✓ Temperature: 30 – 42 ◦C
Optimized geometries of the CMPCD + VC
(dimer) adduct
(Ab-initio Molecular Orbital calculations confirmed its suitability for VC polymerization)

Abreu, C. M. R., et. al., Macromolecules 2012, 45, 2200

© Michelle Coote, Australian National University
 RAFT OF VC

✓ The ln([M]0/[M]) exhibits two linear dependencies on the polymerization time (hybrid behavior: the differences in the initiation and reinitiation
rates by leaving ●CH
2CN in the pre-equilibrium)

✓ Mn,GPC agrees with Mn,th

✓ Mw/Mn is decreasing with monomer conversion (lowest dispersity ever reported for PVC synthesized with RDRP method (∼ 1.4)

Abreu, C. M. R., et. al., Macromolecules 2012, 45, 2200

 RAFT OF VC

PVC-CTA structure determination

1H-NMR

MALDI-TOF-MS

CMPCD

No detectable
structural defect
PVC-CTA

Very similiar isotope

distribution
(no m/z deviation)
Reflecton mode (DP=17, DP=11)
RAFT OF VC

Chain Extension Experiments

Can we replace THF?

 CPME VS THF

1H-NMR

Cyclopentyl methyl ether (CPME)

MALDI-TOF-MS

Abreu, C. M. R., et. al., RSC Advances, 2016, 6, 7495

CPME VS THF

CPME vs THF “One-pot” Chain Extension Experiment

PVAc-CTA

Expand the portfolio of

PVC-based copolymers
using a single solvent?
PVAc-b-PVC
block
copolymer

CPME can be used to replace THF, DMSO, DCM and DMF → ATRP, RAFT and NMP
 SULFOLANE (USING SARA-ATRP)

Dipolar aprotic
industrial solvent
(high dipole moment)

✓ The ln([M]0/[M]) exhibits linear dependence on the polymerization time

✓ Mn,GPC agrees with Mn,th (better than DMSO in the same system)

✓ Mw/Mn is decreasing with monomer conversion (∼ 1.5)

Mendes, J. P., et. al., ACS Macro Letters 2014, 3, 858; RSC Adv., 2016, 6, 9598
 SULFOLANE (USING SARA-ATRP)

Br – PVC – Br structure determination

MALDI-TOF-MS New structures
PS-b-PVC-b-PS and
PMA-b-PVC-b-PMA

Single solvent & catalytic

system (no purifications)

(Na2S2O4)

Mendes, J. P., et. al., ACS Macro Letters 2014, 3, 858; RSC Adv., 2016, 6, 9598
 MADIX OF VC

- Universal/Versatile : polymerization of less

activated and more activated monomers (block
copolymers using “one-pot” process)

- Inexpensive Compounds

- Easier to synthesize

- Xanthates are used in commercial processes (Rayon,

cellulose films and textiles)

a Mnth x 10-3 MnSEC x 10-3

Entry T (° C) Conv. (%) Ð
(g/mol) (g/mol)
1 30 40.5 6.52 6.48 1.30

2 42 56.7 9.06 9.17 1.35

3 60 72.6 11.54 6.24 1.52

a
Reaction conditions: [VC]0/[MEA]0/[Trigonox]0 = 250/1/0.25; [VC]0/[CPME] = 1/1 (v/v).

Abreu CMR et. al. Macromolecules, 2020, 53, 1, 190-202.

 MADIX OF VC

Abreu CMR et. al. Macromolecules, 2020, 53, 1, 190-202.

MADIX OF VC

Careful choice of polymerization conditions (initiator type and its concentration, solvent nature, monomer concentration and temperature) is
required to achieve low dispersities (Đ ∼ 1.2-1.3)
 NMP OF VC

kd (0.34 s-1 120 C)

✓ Monomer: VC

SG1-based
✓ Nitroxide radical (T•) Alkoxyamine BlocBuilder
initiator MAMA-SG1
✓ Conventional Initiator

✓ Studied conditions: solvents, monomer concentration, polymerization temperature, degree of polymerization

✓ Solvents: DMSO and DCM

✓ Temperature: 60C 42C 30C

Abreu, C. M. R., et. al., Macromolecules, 2016, 49, 490

NMP OF VC

✓ The ln([M]0/[M]) exhibits linear dependence on the polymerization time 31P-NMR

✓ Mn,GPC agrees very well with Mn,th 91% chain end

✓ Mw/Mn is decreasing with monomer conversion (∼ 1.5) Diethyl
PVC-SG1 Phosphite
… very robust system
 NMP OF VC

PVC-SG1 structure determination

“One-pot” Chain Extension Experiment BlocBuilder

PVC-SG1

Mechanism???
Ab-initio Molecular Orbital calculations:

C-O bond in PVC-SG1 is too strong to mediate NMP of VC

PVC-b-PMMA and
SG1-mediated dehydrochlorination mechanism involved?
PVC-b-P(MMA-co-S)
but… copolymers
Molar ratio –CH2CHCl- / -CH=CH-CH2Cl (5.8 ppm)
1000/0.82 for PVC-FRP vs 1000/0.42 for PVC-SG1

© Michelle Coote, Australian National University

 ARGET-ATRP OF VC

Activators Regenerated by Electron Transfer ATRP of VC

[VC]0/[CHBr3]0/[CuBr2]0/[TREN]0/[TDO]0 = 222/1/0.5/1/1

AKA “green industrial reductant”

Model experiments showed no activation of dormant
species by Thiourea Dioxide during VC polymerization (formamidine sulfinic acid)

High CEF – preparation of PVC-based block copolymers

Mendonça PV et al., ACS Macro Letters, 2019, 8, 315–319

 EATRP OF VC

eATRP allows reducing the starting CuII species without any by-products
Ratio CuII/CuI is a function of the applied potential or current (Nernst equation)
eATRP can be finely tuned by modulating the electrochemical stimulus

Classical eATRP could not stand with the pressure!!!

Reaction is carried out inside electrochemically glass cells with 3 electrode setup:
Two platinum electrodes serving as cathode (working electrode, WE) and anode
(counter electrode, CE) and a reference electrode (RE).
Potentiostatic electrolysis (fixed potential) or Galvanostatic (current)

SS304 electrochemical reactor

de Bon F, et al., Polymer Chemistry 2020, 11, 6745-6772
 EATRP

SIMPLIFIED GALVANOSTATIC EATRP

Cathode: Pt, Anode: Al.
Excess TREN is requested to complex Al3+ release.
Electrolysis mode: galvanostatic (applied current)

Every 3 activations one

Al Al3+ aluminum ion is released! Pt Cu+

Al3+ + TREN → [AlIIITREN]3+ Cu2+

eATRP

de Bon F, et al., Polymer Chemistry 2020, 11, 6745-6772

 EATRP

SARA ATRP VS EATRP

PVC-Br PVC-b-PMA-Cl
D = 1.80 D = 1.40

PVC-b-PMA-Br
D = 1.50

3 4 5 6
logM
2 3 4 5 6
logM

GPC traces of four-arm star PVC obtained by SARA (▬) or eATRP (▬) after
3h of reaction time in DMSO at 40C.
de Bon F, et al., Polymer Chemistry 2020, 11, 6745-6772
 EATRP

First eATRP of vinyl chloride

First eATRP under pressure
First eATRP in a steel reactor
Simple electrochemical setup
Metal body of the reactor was also
successfully used as a cathode
Scale-up the technology

de Bon F, et al., Polymer Chemistry 2020, 11, 6745-6772

SUMMARY OF OUR ACHIEVEMENTS

Sulfolane & MADIX of

RAFT of VC SARA-ATRP of VC NMP of VC
VC
2012 2014 2016 2020

2015 2019 2021

CPME ARGET- ATRP e-ATRP of
of VC VC
A MYRIAD OF OPPORTUNITIES FOR NEW PVC COPOLYMERS

Method PVC/Copolymer Mn x 10-3 Ð (Mw/Mn)

ARGET ATRP Br-PVC-Br 3 - 10 1.4 - 1.5

Br-PMA-b-PVC-b-PMA-Br 6 - 30 1.4 - 1.4

SARA ATRP Br-PVC-Br 3 - 20 1.4 - 1.6

Br-PMA-b-PVC-b-PMA-Br 6 - 60 1.5 - 1.7

Br-PSty-b-PVC-b-PSty-Br 9 - 65 1.6 – 2.0

eATRP Br-PVC-Br 5 - 30 1.3 - 1.8

Br-PMA-b-PVC-b-PMA-Br 6 - 60 1.3 - 1.4

RAFT PVC-CTA 2 - 20 1.4 - 1.5

PVC-b-PVAc-CTA 9 - 30 1.4 - 1.6

NMP PVC-SG1 4 – 35 1.5 - 1.6

PVC-b-PMMA-SG1 7 – 45 1.6 - 1.9

MADIX PVC-MEA 2 – 25 1.2 - 1.3

PVC-b-PVAc-MEA 4 – 35 1.2 - 1.3

PVC-b-PNVCL-MEA 4 – 25 1.1 – 1.2

 PISA

Polymerization-induced self-assembly (PISA) of block copolymer nanoparticles

PISA involves growing an AB diblock

copolymer chains in a suitable solvent:

✓ an appropriate solvent for the precursor

(A) block

✓ non-solvent for the growing

second (B) block

in situ self-assembly
diblock copolymer
nanoparticles

Derry, M.J., L.A. Fielding, S.P. Armes, Progress in Polymer Science, 2016, 52: p. 1-18.
 PISA

PISA of block copolymer nanoparticles

PISA offers many advantages over traditional self-assembly routes, including:

✓ much higher concentration (up to 50 wt% vs.  1 wt%); very high solid content
✓ simpler and scalable experimental protocols
✓ faster overall processes

Penfold N et. Al. ACS Macro Letters. 2019, 8, 1029−1054

 PISA

20% w/w solids, d ~ 280 nm

Unpublished data
ACKNOWLEDGMENTS
Thank you for your attention !

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