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Chapter 5

LIVING/CONTROLED POLYMERIZATION
TRÙNG HỢP POLYME SỐNG/CÓ KIỂM SOÁT

What is a controlled polymerization ?

A controlled polymerization is defined here as a synthetic
method for preparing polymers with predetermined
molecular weights (DPn=∆[M]/[I]o), low polydispersity,
controlled functionality, block copolymers, etc. Transfer
and termination is allowed in a controlled polymerization if
their contribution is sufficiently reduced by the proper
choice of the reaction conditions such that polymer
structure is not affected.
Trùng hợp có kiểm soát: là một phương pháp tổng hợp polyme với phân tử lượng được dự đoán trước
(DPn = ∆[M]/[I]o), độ đa phân tán thấp, độ chức được kiểm soát, copolyme khối, v.v.
Quá trình trùng hợp có kiểm soát: chấp nhận quá trình chuyển mạch và tắt mạch phù hợp nào đó để cấu
trúc polyme không bị ảnh hưởng.

INTRODUCTION TO LIVING POLYMERIZATION. LIVING AND/OR

CONTROLLED POYLMERIZATION, Krzysztof Matyjaszewski, J. Phys. Org. 2
Chem., Carnegie Mellon University, 1994.

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▪ A living polymerization is defined as a chain

polymerization without irreversible transfer and
termination.
▪ Living polymerizations will lead to well-defined polymers
only if the following additional prerequisites are fulfilled:
➢ initiation is fast in comparison with propagation,
➢ exchange between species of different reactivities is fast
in comparison with propagation,
➢ rate of de-propagation is low in comparison with
propagation
➢ system is sufficiently homogeneous, in sense of the
availability of active centers and mixing.
INTRODUCTION TO LIVING POLYMERIZATION. LIVING AND/OR
CONTROLLED POYLMERIZATION, Krzysztof Matyjaszewski, J. Phys. Org.
Chem., Carnegie Mellon University, 1994. 3

Living polymerizations are defined as polymerization

reactions where termination or chain transfer is eliminated.

Controlled polymerization reactions are reactions where

termination is suppressed, but not eliminated, through the
introduction of a dormant state of the polymer.

➢ Phản ứng trùng hợp polyme sống: phản ứng trùng hợp trong đó
không có quá trình tắt mạch hoặc chuyển mạch.
➢ Phản ứng trùng hợp có kiểm soát: phản ứng trong đó quá trình tắt
mạch bị triệt tiêu, nhưng không bị loại bỏ, thông qua việc đưa vào
trạng thái không hoạt động của polyme. 4

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Comparison between Living vs Controlled Polymerization 5

Living Polymerization
• No termination or chain-transfer side reaction
during polymerization
– Control of molecular weight
Grams of monomer
• Mn=
Moles of initiator
– Narrow molecular weight distribution.
– Synthesis of block copolymers by sequential monomer
addition.
– Control of polymer chain microstructure.
– End-group functionalization.

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End Group Functionalization

Criteria for Living Polymerizations

1. Polymerization proceeds until all
monomer consumed, further addition of
monomer results in chain extension
2. Number average MW (Mn, Xn) linear
relationship with monomer conversion
3. # of initiator molecules = # of polymer
chains, which is constant throughout
reaction
4. DP = [M]o/[I]o x Conversion
5. Polymers of low polydispersity formed
Mw/Mn= 1 + 1/DPn
6. Block Copolymers formed from sequential
monomer addition to living polymer chain
7. Facile chain end functionalization
8. Linearity of Ln([M]o/[M]) vs. time
(constant # of active centers
8
Ref) Quirk et al., Polym. Int. 1992, 27, 359

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Controlled/Living Polymerizations
Living polymerization: Features: precise DPn(∆[M]/[I]o)
a chain growth process without chain- Low polydispersity
breaking reactions (termination, transfer) Active chain ends-Blocks
Anionic, Insertion (ROMP) Control of architecture
Stringent reaction conditions

Controlled/Living Polymerizations

Controlled/“Living” polymerization: Features: precise

a chain growth process with chain DPn = (∆[M]/[I]o)
breaking reactions Low polydispersity*
Rpropagation>> Rtermination, Rtransfer Active chain ends-Blocks
Control of architecture
Reversible deactivation

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Living Anionic Polymerization

Initiators: ex. organolithium compounds (sec-butyl lithium;
n-butyl lithium) Grignard reagents, alkali bases
Monomers: ex. Styrenes, dienes, (meth)acrylates,
pyridines, epoxides: Functional monomer require protecting
groups; alkyl esters cannot be polym
Features: exquisite control (kiểm soát tinh tế) of MW, block
copolymers, low functional group tolerance

High functional group tolerance, widest scope of

polymerizable monomers

Features: controlled MW, block copolymers, functionality,

bimolecular termination 11

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Controlled Cationic Polymerization

Initiators: ex. Alkyl halides, acetates, inorganic/organic acids,

water

Monomers: ex. Vinyl ethers, alkenes(butylene), styrene,

cyclic ethers Functional monomer require protecting groups;
alkyl esters cannot be polym.

Features: highly reactive cation species susceptible to chain

transfer
Controlled MW, block copolymers
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Controlled/Living Polymerizations: Materials

Block copolymers & Functionalization

Well-defined
initiators: Stars, graft

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Good monomers for anionic polymerization

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Reactivity trend of monomers in anionic polymerization

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Initiators for anionic polymerizations

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Kinetics of Living Polymerizations

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Conversion

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Solvent effect on anionic polymerizations

Solvent and Counter Ion Effect

1,4 trans content increases crystallinity, Tm > 25oC. 1,4 cis content suppress 21
crystallinity, low Tg (-110oC), Tm ~12oC; used for synthetic rubber

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SOLVENT CHARACTERISTICS

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Solvent effect on anionic polymerizations

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Solvent effect on anionic polymerizations

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End functionalization of anionic polymerizations

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End functionalization of anionic polymerizations

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Block copolymers from anionic polymerizations

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Block copolymers from anionic polymerizations

Monomers in increasing electrophilicity

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BLOCK COPOLYMERS FROM ANIONIC POLYMERIZATIONS

Want to make polystyrene-b-poly(methyl methacrylate) PS-b-PMMA

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Living Polymerization (Cationic)

ADDITIONAL DEVELOPMENTS IN THE 1980’S

➢ "Immortal" Polymerization (Cationic)

➢ Mw/Mn ~ 1.05
➢ Blocks, telechelics, stars
➢ (Controlled molecular architecture)
➢ Statistical Compositions and Sequences
Các thành phần và trình tự thống kê
➢ Severe functional group restrictions

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Cationic Polymerization

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Cationic Polymerization

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Monomers for Cationic Polymerization

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KINETIC STEPS IN CATIONIC POLYMERIZATION

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All these reactions kill the chain growth

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Strategy: prolong the life-time of cationic propagating species by reversible formation

of dormant species. (Note: anionic propagating species has a much longer life-time).

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* Szwarc, M., Nature, 1956, 178, 1168. 39

** Flory, P. J., J. Am. Chem. Soc., 1940, 62, 1561.

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State of Art for SFRP

➢ MW > 105, PDI = 1.1-1.2 lower temperature (60-

➢ High reaction temperature ( oC) 80oC), shorter reaction
➢ Long reaction time (24-72 hr) time (several hrs) and
➢ Low to moderate conversion (<70%) higher conversion (> 99%)
➢ Limited scope of monomers: St, MA, are desired
MMA etc.
➢ functionalized alkoxyamine is
required for block or telechelic
polymer synthesis

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Atom Transfer Radical

Polymerization (ATRP)

https://www.cmu.edu/maty/chem/fundamen 47
tals-atrp/atrp.html
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Why ATRP? Control Compositions Topology

Functionality

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* Szwarc, M., Nature, 1956, 178, 1168. 49

** Flory, P. J., J. Am. Chem. Soc., 1940, 62, 1561.

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ATRP types

▪ Normal ATRP
▪ Reverse ATRP
Introduce higher oxidation state metal
Reaction results in lesser concentration of
radicals
More control and better PDI

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Shortcomings of ATRP

➢ Oxygen hinders polymerization forming stable

copper oxides.
- Degassing
- Addition of reducing agent (Cu) provides tolerance
➢ No control over tacticity due to radical nature.
➢ Unwanted catalyst color
➢ Catalyst removal problems

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State of Art for ATRP

➢MW > 105 easily, PDI = 1.1-1.6
reaction temperature (70-130oC)
➢Low to moderate conversion (<80%)
➢Tolerant of functional groups, wide scope of monomers: St,
MA, MMA, acrylamide, vinylpyridine (VP), acrylonitrile
(AN) etc. (acrylic acid, vinyl halide, vinyl ether, a-olefin
cannot be polymerized)
➢Availability of a variety of initiator and catalysts.
➢block polymers and telechelic polymers are readily
prepared.
➢metal contaminant is sometime less desired
A telechelic polymer or oligomer is a prepolymer capable of entering into further polymerization or
other reactions through its reactive end-groups.[1] It can be used for example to synthesize block 61
copolymers.

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REVERSIBLE ADDITION
FRAGMENTATION CHAIN TRANSFER
(RAFT)
TRÙNG HỢP CHUYỂN MẠCH CỘNG-TÁCH,
CHUYỂN MẠCH THUẬN NGHỊCH

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WHAT IS RAFT??
➢ RAFT (Reversible Addition-Fragmentation chain Transfer)
technology is a form of controlled free radical polymerization.
➢ RAFT (Reversible Addition-Fragmentation chain Transfer) is a form
of living radical polymerization involving conventional free radical
polymerization of a substituted monomer in the presence of a
suitable chain transfer (RAFT) reagent.
➢ Operates on the principle of degenerative chain transfer.

❖ RAFT (Reversible Addition-Fragmentation chain Transfer) là một kỹ

thuật trùng hợp gốc tự do có kiểm soát.
❖ RAFT (Quá trình Cộng-Tách,chuyển mạch thuận nghịch) là một dạng
của trùng hợp gốc sống liên quan đến quá trình trùng hợp gốc tự do
thông thường của một monome nhưng tác nhân tạo gốc tự do khi có
mặt của tác nhân chuyển chuỗi thích hợp (RAFT).
❖ Hoạt động theo nguyên tắc chuyển mạch.
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RAFT AGENT
A small organic molecule that is responsible for controlling
growth.
➢ Suitable selection of RAFT agent is needed, because
intermediate radicals may participate in some side
reactions, such as cross-termination.
➢ The key to the RAFT polymerization process is the RAFT
Agent.

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Synthesis of homo poly-styrene via ATRP technique

10 mL of styrene (S), 0.5 g of 3-chloro-1- propanol,

PMDETA, CuCl and DMF (as solvent) were placed in a 100
mL tube. The reaction mixture with nitrogen gas was made
inert. The reaction tube was held in a thermostated oil bath
at 110 ° C for 10 hours with magnetic stirrer. The tube was
poured into excess methanol for precipitation of the homo
poly-styrene. The homo poly-S vacuum conditioned to
room temperature was dried for 72 hours.
The gravimetric follow-up of the product was done.

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Synthesis of a new poly-S based RAFT

macroinitiator
➢ Homo poly-styrene synthesized by ATRP at a
constant amount and 3 g of potassium salt ethyl
xanthate were reacted in THF for 48 hours and 25
°C. The reaction mixture was filtered to remove
unreacted xanthate and the solvent was removed
with a rotary evaporator.
➢ The resulting poly-S based RAFT macroinitiator
was precipitated in cold diethyl ether: petroleum
ether (1:1) solution. It was dried at room
temperature and under vacuum for four days 75

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Living Polymerization

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Living Polymerization
Neutral and Highly Reactive

or

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Living Polymerizations
• Living polymerizations are chain growth polymerizations which
proceed in the absence of irreversible chain transfer and
termination steps.*
• Diagnostic Characteristic of Living Polymerizations
– The reaction proceeds until all monomer is consumed. If more
monomer is introduced then the polymerization will continue
– The number average molecular weight, Mn, is a linear function of
conversion.
– The number of propagating chains (active centers) is constant and
independent of conversion.
– Mn can be controlled by the reaction stoichiometry.
– Sequential monomer addition results in the preparation of block
copolymers.
– Resulting polymers will exhibit a narrow molecular weight distribution
and the polymer must exhibit a Poisson distribution in molecular
weight.**

* Szwarc, M., Nature, 1956, 178, 1168.

** Flory, P. J., J. Am. Chem. Soc., 1940, 62, 1561.

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Initiation
• Nucleophilic Initiation of Vinyl Monomers

CH3

CH3CH2CH Li H2C CH Bu CH2 CH Li

CH Li CH Li CH Li

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Anionic Polymerization of
Styrene

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Anionic Polymerization of
Styrene

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Anionic Polymerization of
Styrene

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Anionic Polymerization of
Styrene

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Initiators: Organolithiums

• Soluble in hydrocarbons
• Direct nucleophilic attack
• No electron transfer

(RLi)N N= 6,4,2

MW= g of monomer
moles of initiator

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The Poisson Distribution in

Molecular Weight
• The constraints imposed on a living polymer require that
the polymer exhibit a Poisson distribution in molecular
weight.*
Conversion & Mw/Mn as a Function of
Time
Conversion

Mw/Mn

Conversion
DPw 1 PDI
=1 +
DPn DPn
Time

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Scale of “Livingness”

• Conversion should be linear with time in semi-logrithmic coordinates

• Deceleration indicates termination or deactivation of catalyst.

• When chain termination cannot

Ln[M]o/[M] vs. Time be completely suppressed
kp/kt = 1.05 (kt > 0):
kp/kt = 10 - deviation from living behavior
ln[M]o/[M]t

kp/kt = 100 becomes more pronounced

Living with time
- The degree to which a
reaction deviates at time, t, is
proportional to the ratio of the
Time
rate of propagation to
termination.

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End Group Functionalization

Carboxylic acid terminated:

Primary alcohol terminated:

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Monomers
• Generally olefin w/ EWG or delocalizing groups

Methyl acrylate (MA)

Methyl methacrylate (MMA)
t-Butyl methacrylate (tBuMA)

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Ion Pair Aggregation

• Need to stabilize propagating anions

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Ion Pair Aggregation

• Need to stabilize propagating anions

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