Polymers & Formulation: Methods, Synthesis and Industrial Processes

POLYMERS & FORMULATION
Methodes of polymer synthesis

-
Design & compounding of
thermoplastics
–
Additives
25/10/2021 Lecture STUMBE 1

H H
Ethylene C C C2
Distillation H H
of crude oil H H
Propylene C C
C3
H CH3
petrol C6
Cracking Benzene
Naphta
Toluene CH3
Oils
CH3
Xylenes H3C CH3
Bitumen CH3
H H
Butadiene C C H C4
H C C
H H

Market shares of main polymers

Polyurethanes
Polyethylene O
PE
N O
H Thermosets
*
* n
5% 15%
29% Other
13% thermoplastics
12% 9% 17% PA6, PA6,6
PET
….
PVC
*
* n Polystyrene Polypropylene
Cl
PS PP
*
* n *
* n

Industrial polymers
2 main routes of synthesis
Radical Step polymerization

polymerization - Polycondensation
- Polyaddition
Styrenics
Acrylates Polyesters
Methacrylates Polyamides
Vinylics Polyurethanes

Polymerisable monomers by radical route
Vinylic monomers O CH3

CN
O
styrene Vinyle acetate acrylonitrile
R
R : Functional group CH3 CH3
CH3 CH3
O OH O O O OH O O
Acrylic acid Methyle Methacrylic Methyle
acrylate acid méthacrylate
H H H H H CH3
Olefins C C C C H
C C
Ethylene, H C C
H H H
H2C CH2
H
butadiene, isoprene
Ethylene Isoprene
Butadiene

Industrial processes
Bulk:
 polymerization in monomer
Dispersed medium : emulsion, suspension, dispersion …

 Polymerization in heterogeneous medium
In solution : organic solvant, water (rare, laboratory)

Radical process
« Birth » : Initiation « Life » : Propagation Stop of growth

efficiency Terminaison, transfer
+M +M
Amorceur
initiator A AM AM2 AMn P
Kinetic length l
Dt  1s

Example of chemical initiation
Thermal decomposition thermique

of chemical initiator :
Chemical initiation
Photochemical initiation azoics (AIBN…)
Radiochemical initiation peroxydes (BPO …)
Thermal initiation persulfates
Redox reaction
persulfate - metabisulfite
Ascorbic acid – H2O2

Formation of primary radicals
Thermal decomposition of chemical initiator
Azobisisobutyronitrile (AIBN)
CH3 CH3 CH3

H3C C N N C CH3 2 H3C C + N2
CN CN CN
Benzoyle peroxyde (BPO)

O
O
O O
O 2
O
O
O
+ CO2

Initiation
CH3
CH3
Styrene H3C C
H3C C
CN
CN
Methyle methacrylate
CH3 CH3 CH3
CH3
H3C C O H3C C
CH3
CN O CN O O
CH3
 Efficiency of initiator f < 1

 Generally, radical located on most substituted carbon : addition head - tail

Propagation
CH3 CH3
H3C C H3C C
CN CN
CH3 CH3
H3C C H3C C
CN CN

Bimolecular terminaison
Coupling of 2 macroradicals
CH3 CH3
H3C C C CH3
CN CN
CH3 CH3
m m H3C C C CH3
CN CN
m n
DP = 2 λ
λ λ
λ = number of monomer units in a (macro)radical

DP = degree of polymerization = nbr of monomer units in one polymer chain
Bimolecular terminaison
Dismutation of 2 macroradicals
CH3 Me CH3 Me CH3

H CH2
H3C C CH3
n m
CN O O O O O O O O CN
Me Me Me Me
CH3 Me CH2 CH3 Me CH3

H3C C + H3C C H
m n
CN O O O O CN O O O O
Me Me Me Me
λ λ
DP = λ

Control of molecular weight

 Depends monomer concentration
 Depends ratio monomer / initiator
 Nature of initiator
𝑴𝒏 = 𝑴𝟎 . 𝑫𝑷
M0 = molecular weight of monomer
𝐷𝑃 = 𝐾 . 𝑀 / 𝐼
DP = degree of polymerization = nbr of
monomer units in one polymer chain

Main polymers prepared by radical polymerization

Polystyrene Low density
(PS) Polyethylene
(LDPE)
Polyvinylchloride Polymethylmethacrylate
(PVC) (PMMA)

Polyaddition - polycondensation
 Obtained by reaction of functional monomers (alcohols, acids,
amines, isocyanates …)
 Chemistry of functions: conversion calculated on the basis of
reacted functions
 Polymers named according to name of generated functions
(polyesters …)
Examples
Acid + alcohol → Ester + water (estérification) polyester

Acid + amine → Amide + water (amidification) polyamide
Isocyanate + alcohol → urethane polyurethane
Formation of a polymeric chain requires at least difunctional monomers

(diol + diacid, diamine + diacide, …)
A2 + B2
Monomers systems
A A B B
ρ
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
ρ
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
 Degree of polymerization DP = nbr of monomers in one chain
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒

 𝐷𝑃 = 𝐷𝑃 =
10
=2
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑎𝑐𝑟𝑜𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 5
ρ
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
ρ
A2 + B2
Monomers systems
A A B B
 Degree of polymerization DP = nbr of monomers in one chain

 𝐷𝑃 = 𝐷𝑃 =
10
= 10
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑎𝑐𝑟𝑜𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 1
ρ
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2

𝐷𝑃 =
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑎𝑐𝑟𝑜𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
Unit = monomer
3 groups
Group = macromolecules
5 units /group
Units in 1 group = DP
ρ (15/3 =5)
15 units

A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
NA = number of A groups
NB = number of B groups
NA N B NA + NB
Number of molecules N = + =
2 2 2
ρ Stoichiometric imbalance: 𝑟=
𝑁𝐴
or
𝑁𝐴
NB ≥ NA
𝑁𝐵 =
𝑁𝐵 𝑟
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
NA = number of A groups
NB = number of B groups 𝑁𝐴
𝑁𝐵 =
𝑟
NA NB NA NA NA 1
Number of molecules N = + = + = ( 1+ )
2 2 2 2𝑟 2 𝑟
ρ
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
NA = number of A groups NB = number of B groups
Number of macromolecules
p = extent of réaction = fraction of A groups that reacted
rp = fraction of B groups that reacted
ρ 1-p = fraction of unreacted A groups

1-rp = fraction of unreacted B groups

A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
1-p = fraction of unreacted A groups
1-rp = fraction of unreacted B groups
ρ Number of unreacted A groups: NA.(1-p)

Number of unreacted B groups: NB.(1-rp)

A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
Number of end chains
Number of polymer chains =
2
Number of end chains = unreacted A + unreacted B
ρ = NA.(1-p) + NB.(1-rp)
NA.(1−p) + NB.(1−rp)
Number of polymer chains =
2
A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
Degree of polymerization
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑁𝐴
𝐷𝑃 = 𝑁𝐵 =
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑎𝑐𝑟𝑜𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑟
NA ( 1+ 1 )
ρ 2
𝐷𝑃 = N .(1−p) 𝑟
=
1+ 1/r
=
𝑟+1
+ NB.(1−rp) (1−p) + (1−rp)/r 𝑟 −𝑝𝑟+1 −𝑝𝑟 =
1+𝑟
1+𝑟 − 2𝑝𝑟
A
2

A2 + B2
Monomers systems
A A B B
DP =2 DP =2 DP =2 DP =2 DP =2
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑁𝐴
𝐷𝑃 = 𝑁𝐵 =
𝑁𝑏𝑟 𝑜𝑓 𝑚𝑎𝑐𝑟𝑜𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑟
NA ( 1+ 1 )
ρ 2
𝐷𝑃 = N .(1−p) 𝑟
=
1+ 1/r
=
𝑟+1
+ NB.(1−rp) (1−p) + (1−rp)/r 𝑟 −𝑝𝑟+1 −𝑝𝑟 =
1+𝑟
1+𝑟 − 2𝑝𝑟
A
2

A2 + B2
Monomers systems
𝐍𝐛𝐫 𝐨𝐟 𝐦𝐨𝐧𝐨𝐦𝐞𝐫𝐬 𝐢𝐧𝐢𝐭𝐢𝐚𝐥𝐥𝐲 𝐚𝐯𝐚𝐢𝐥𝐚𝐛𝐥𝐞

𝐃𝐏 =
𝐍𝐛𝐫 𝐨𝐟 𝐦𝐚𝐜𝐫𝐨𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐞𝐬
1+𝑟
𝐷𝑃 =
r=1 1 + 𝑟 − 2𝑝𝑟
p=1
stoichiometry
Full conversion
𝟏 𝟏+𝒓
𝑫𝑷 = 𝑫𝑷 =
𝟏 −𝒑 𝟏 − 𝒓
Control of molecular weight
 Depends on stoechiometry
 Depends on conversion 𝑴𝒏 = 𝑴𝟎 . 𝑫𝑷
M0 = average molecular weight
of average monomer
250
DP
200
150 𝟏
𝑫𝑷 =
100 𝟏−𝒑 p = conversion
DP = degree of polymerization
50
0
0 0,2 0,4 0,6 0,8 1
Conversion p p = 1  100%
Polycondensation : example of polyethylene terephtalate (PET)
HOOC COOH OH
HO Ethylene glycol
Equilibrium
Terephtalic acid OH
O O
+ H2O
HO O
Reaction with toute any alcohol function Reaction with any acid function
Mi + Mj Mi+j + H2O
Polycondensation : elimination of low molecular weight molecules (water, alcohol ..)

Polycondensation : example of a polyamide

COOH NH2
HOOC H2N
PA 6,6 Hexamethylene diamine
Adipic acid
Equilibrium
O
NH2
HOOC N
H
+ H2O
Reaction with any amine function Reaction with any acid function
PA 6,6
Use of a C6 diamine Use of a C6 diacid

How to deal with stoechiometry: the case of PA 6,6
O
OH O
HO O
O O
O
+ Nylon salt
+
NH2 H3N
+ NH3 (conc. 80%)
H2N
• Stable
• Limited oxydation
• Limited yellowing
160°C • Precise stoichiometry
O
H
* N
N *
H
O
n

Polyaddition : example of a polyurethane
NCO OH
OCN HO
Diisocyanate Diol
H Intermediate
N O
OCN OH High reactive
O specie
Reaction with any alcohol function Reaction with any isocyanate function
 Non equilibrated reaction

Features  No possibility to stop / freeze the reaction
 No release of small molecules
Comparison Radical polymerization vs step polymerization
Radical polymerization Step polymerization

Difunctional monomer A2
Vinylic monomer
O O
H
O OH
O
OH
H
O
O OH
O
H H N
CO
OC
N
C C
H H
Difunctional monomer B2
CH3
O CH3 OH
CH3 HO
O O O
N H2
H2N
POLYMERS &
T =FORMULATION
0

Few long
Macromolecules Few dimers
are formed are formed










Comparison Radical polymerization vs step polymerization
Radical polymerization Step polymerization
 Very few active sites (radicals)  All reactive groups can react
generated per time unit  Formation of dimers (50%
 Very fast chain formation ( ̴1s) conv)
 MW depends on monomer  Formation of tri- & tetramers
concentration  Formation of larger oligomers
 MW depends on ratio M/I  High molecular weights
 Formation oh high molecular obtained at very high
weight macromolecules from conversion
beginning  MW depends on stoichiometry
  MW depends on conversion

Polymers & Formulation: Methods, Synthesis and Industrial Processes

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POLYMERS & FORMULATION

Methodes of polymer synthesis

25/10/2021 Lecture STUMBE 1

25/10/2021 Lecture STUMBE 2

Market shares of main polymers

25/10/2021 Lecture STUMBE 3

Radical Step polymerization

25/10/2021 Lecture STUMBE 4

Vinylic monomers O CH3

25/10/2021 Lecture STUMBE 5

Dispersed medium : emulsion, suspension, dispersion …

In solution : organic solvant, water (rare, laboratory)

25/10/2021 Lecture STUMBE 6

« Birth » : Initiation « Life » : Propagation Stop of growth

25/10/2021 Lecture STUMBE 7

Example of chemical initiation

Thermal decomposition thermique

25/10/2021 Lecture STUMBE 8

CH3 CH3 CH3

Benzoyle peroxyde (BPO)

25/10/2021 Lecture STUMBE 9

 Efficiency of initiator f < 1

25/10/2021 Lecture STUMBE 10

25/10/2021 Lecture STUMBE 11

λ = number of monomer units in a (macro)radical

CH3 Me CH3 Me CH3

CH3 Me CH2 CH3 Me CH3

25/10/2021 Lecture STUMBE 13

Control of molecular weight

25/10/2021 Lecture STUMBE 14

Main polymers prepared by radical polymerization

25/10/2021 Lecture STUMBE 15

Acid + alcohol → Ester + water (estérification) polyester

Isocyanate + alcohol → urethane polyurethane

Formation of a polymeric chain requires at least difunctional monomers

 Degree of polymerization DP = nbr of monomers in one chain

𝑁𝑏𝑟 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒

 Degree of polymerization DP = nbr of monomers in one chain

𝑁𝑏𝑟 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒

𝑁𝑏𝑟 𝑜𝑓 𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒

25/10/2021 Lecture STUMBE 22

NA = number of A groups NB = number of B groups

ρ 1-p = fraction of unreacted A groups

25/10/2021 Lecture STUMBE 25

NA = number of A groups NB = number of B groups

ρ Number of unreacted A groups: NA.(1-p)

25/10/2021 Lecture STUMBE 26

NA = number of A groups NB = number of B groups

NA = number of A groups NB = number of B groups

25/10/2021 Lecture STUMBE 28

NA = number of A groups NB = number of B groups

25/10/2021 Lecture STUMBE 29

𝐍𝐛𝐫 𝐨𝐟 𝐦𝐨𝐧𝐨𝐦𝐞𝐫𝐬 𝐢𝐧𝐢𝐭𝐢𝐚𝐥𝐥𝐲 𝐚𝐯𝐚𝐢𝐥𝐚𝐛𝐥𝐞

Control of molecular weight

Polycondensation : example of polyethylene terephtalate (PET)

Polycondensation : elimination of low molecular weight molecules (water, alcohol ..)

25/10/2021 Lecture STUMBE 32

Polycondensation : example of a polyamide

Use of a C6 diamine Use of a C6 diacid

25/10/2021 Lecture STUMBE 33

How to deal with stoechiometry: the case of PA 6,6

25/10/2021 Lecture STUMBE 34