1

Introduction to free-radical polymerization

Polymerization mechanisms - Step-growth polymerization

Polymerization mechanisms - Chain-growth polymerization

Advantages of free-radical polymerization very robust technique wide range of vinyl monomers and functionalities wide range of operating conditions aqueous media: emulsion polymerization Disadvantages of free-radical polymerization - non-selective reaction - non-trivial product control
10

Chain reactions characteristics: each polymer chain grows fast. Once growth stops a chain is no longer reactive. growth of a polymer chain is caused by a kinetic chain of reactions. chain reactions always comprise the addition of monomer to an active center (radical, ion, polymercatalyst bond). the chain reaction is initiated by an external source (energy, reactive compound, or catalyst). examples: radical polymerization ionic polymerization coordination polymerization group transfer polymerization
11

Radical polymerization initiation propagation chain transfer termination (start) (growth) (stop/start) (stop)

During initiation active centers are being formed. During termination active centers disappear. Concentration of active centers is very low (10-9 - 10-7 mol/L). Growth rate of a chain is very high (103 - 104 units/s). Chains with a degree of polymerization of 103 to 104 are being formed in 0.1 to 10 s.

12

Initiation Most common method of initiation: thermal decomposition of a thermally labile compound, the initiator
I kd 2R

These radicals are called primary radicals. Initiation takes place by addition of a monomer unit. ki R + M R1 kd is a first order rate constant. Common values of kd are in the range: 10-4 - 10-6 s1 . The] d[R rate of radical production is then given by:

dt

= 2k d [ I]

13

The actual rate of initiation Ri is expressed in terms of the rate of radical production that leads to actual polymer chains growing!:

R i = 2fk d [ I]

where f is the efficiency factor: the fraction of radicals that really leads to initiation. Therefore, in all cases: f 1 The rate constant ki is not used in the mathematical description of the CN polymerization. Examples of thermal initiators:

CN CH3

H3C

C N N C CH3 CH3

C O O C O O

Ea = 140 160 kJ mol-1

14

propagation This reaction is responsible for the growth of the polymer chain. It is the reaction in which monomer is added at the active center: kp
Mi + M Mi+1

The rate of this reaction Rp can be expressed as:

R p = k p [M][ M ]
Assumption: the reaction rate constant kp is independent on chain length. This appears to be reasonable above chain length i = 5 - 10 Propagation is the most important reaction for monomer consumption. The reaction rate constant kp typically has a value in the
2 4

15

Termination Chain growth stops by bimolecular reaction of two growing radicals: termination Traditionally two different reactions are recognized: termination by combination (ktc ) termination by disproportionation (ktd ) Schematically these reactions can be represented as:

Mi + Mj

ktc

Mi+j

Mi + Mj
R t = 2k t [M]2

ktd

Mi + Mj

The general kinetic equation reads:

The reaction rate constant kt is in the range 106 - 108 L/mol s

16

Termination Every reaction consists of two steps: 1) approach of both reactants 2) chemical reaction The second step in the termination reaction is very fast. This means that the rate of approach (partially) determines the overall termination rate.

17

Termination: which is faster? 1. + or +

2.

+
in a viscous medium

or

+
in a non-viscous medium

3.

+
at 5 % conversion

or

+
at 85 % conversion
18

Rate of polymerization The rate of polymerization in a chain growth polymerization is defined as the rate at which monomer is d[M ] consumed.

dt

= Ri + Rp

Since for the production of high molar mass material Rp Ri this equation can be re-written as:

d[ M] = R p = k p [ M][ M] dt

From the beginning of the polymerization: increasing number of radicals due to decomposition of the initiator increasing termination due to increasing radical concentration (Rt [M]2) eventually a steady state in radical concentration:
19

Ri = R t 2fk d [I] = 2k t [M]2

This steady state assumption leads to:

fk d [I] [M] = kt
From which the differential rate equation is derived:

R p = k p [M]

fk d [I] kt

At low conversion this means: log(Rp) vs log[M] yields a slope = 1 log(Rp) vs log[I] yields a slope = 0.5
20

When the initiator decomposes slowly compared to the entire polymerization process:

R pk [ M ] d[M ] k dt [M] [ M ][ M ]0 e kt
When ln([M]0/[M]) is plotted versus time, then the slope should equal k:

k = kp

fk d [I] kt

21

Kinetic chain length

number of monomer units R p = = initiating species Ri

= Rp Ri = Rp Rt = k p [M ][ M] 2k t [ M]
2

k p [M] 2 fk d [I]k t

Also =kp [M] , with t time of growth of a polymer = chain 2k t [ M ]2 Here we find at low conversion: log(n) vs log[M] yields a straight line; slope = 1 log (n) vs log[I] similar; slope = -0.5 thus: increase in [I] leads to an increase in rate of polymerization and a decrease in chain length.

[ M ]

1 2 fk d [ I ]kt

The special case with a slowly decomposing initiator leads here to: kp kt = 0e wherek =

2 fk d [I]k t

22

The number average degree of polymerization Pn of chains formed at a certain moment is dependent on the termination mechanism: * combination: Pn = 2 * disproportionation: Pn = chemistry: H H
CH2 C +

H CH2 C C H CH2

C CH2

CH3 CH2 C C O OMe +

CH3 C CH2 C O OMe

CH3 CH2 C H + C O OMe

CH2 C CH2 C O OMe

23

Initiatie/terminatie via MALDI-ToF MS Methyl acrylaat met benzoine

O O

A-MA13 (-H) A-MA13 (+H) B-MA12 -A

100 1295.98

+ O A B

CH3 C

B-MA14 (-H)
90 80

B-MA13 -B
1352.03 662.2

16.03 Da

1248.5 1312.01 100 90 80 1313.01 70 60 50 40 30 20 1332.02 1334.04

B-MA14 (+H) ?
16.03 Da
1342.04 1335.04 1343.05 1346.03 1348.03 1350.03 1349.04 1336.05

70

A-MA13 -A
1353.04

1296.99

60

% Intensity

50

100
40

1295.98 1312.01
1297.99

% Intensity

1248.5

30

90 80
1294.02

1314.01

1354.05

1358.07 1359.07 1360.08

20

1382.05

1398.07 1333.02

10

70

1298.99

1315.03

10 0 1329.0 0 1327.0

1296.99
1296.2 1304.4

0 1288.0

1313.01
Mass (m/z)

% Intensity

60 50 40 30 20 10

1312.6

1320.8

1335.4

1343.8 Mass (m/z)

1352.2

1360.6

0 1369.0

1383.05 1352.03 1399.08

1438.09 1353.04 1314.01 1297.99 1334.04 1342.04 1358.07 1359.07 1360.08 1385.08 1401.09 1384.06 1400.08 1420.10 1428.10 1429.10 1435.07 1427.40 0 1449.0 1439.10

1332.02 1294.02 1276.10 1315.03

1343.05 1333.02 1349.04 1336.05 1345.2

1418.10

0 1276.0

1310.6

1379.8 Mass (m/z)

1414.4

24

25

Trommsdorff effect In radical polymerization we speak about: 1) low conversion, i.e. polymer chains are in dilute solution (no contact among chains) 2) intermediate conversion, i.e. the area in between low and high conversion 3) high conversion, i.e. chains are getting highly entangled; kp decreases. Somewhere in the intermediate conversion regime: * polymer chains loose mobility. * Termination rate decreases * Radical concentration increases * Rate of polymerization increases * Molar mass increases This effect is called: gel effect, Trommsdorff effect,or autoacceleration In the polymerization of MMA this occurs at relatively low conversion.

26

Molar mass in the ideal case:

Pn = 2 (termination by combination) Pn = (termination by disproportionation)

However, a growing chain may transfer its activity to a new chain:

Mi

+ T

ktr

Mi

+ T

This reaction is then followed by reinitiation, the start of a new chain:

ki'

M1

27

Chain transfer chain transfer to: monomer initiator solvent or chain transfer agent polymer allylic transfer monomer, initiator and chain transfer agent are mathematically treated identically: d[polymer ] = k tc [M]2 + 2k td [ M]2 + k tr ,X [ M][X] dt k tc [ M] 2k td [ M] k tr ,X [ X ] 1 = + + = As derived before Pn k p [M ] k p [M] k p [M] this leads to: k [ M] 2k td [ M] k tr ,M k tr ,S [S] k tr ,I [ I] = tc + + + + k p [M ] k p [M] kp k p [M] k p [M]
28

d[polymer ] = k tc [M]2 + 2k td [M]2 + k tr [M][T ] dt

d[ M] = k p [ M][ M] dt

The rate of polymer formation is now defined as:

The rate of polymerization as derived before:

From the definition of number average degree of polymerization it follows: d[ M ] d[ polymer ] Pn = dt dt thus: 2 2 1 k [ M] + 2k td [ M] + k tr [M][ T ] = tc = 1 Pn k p [ M ][ M] Pn =

k tc [ M] 2k td [M] k tr [T ] = + + k p [M] k p [M] k p [M]

[T ] + CT Pn , 0 [M]

29

30

Chain transfer to polymer Intermolecular chain transfer Intramolecular chain transfer Traditional approach: intermolecular, strong increase in branching density towards high conversion. Recent results: Hardly conversion dependent
mol% branches
8 7 6 5 4 3 2 1 0 10 20 30 40 50

conversion ca. 25% conversion > 80%

Dilution results in higher degree of grafting

[BA]0 / %(w/w)

31

Ziegler-natta
32

Summary Chain-length Time of chain-growth Rate of polymerization

L = k p [ M ]t 1 t~ [ M ]

R p = k p [ M ][ M ]

Initiator decomposition is the reaction step most strongly influenced by temperature.

33

Chain length distribution Crucial in the derivation of the CLD is the chance on formation of an i-mer chance on propagation:

p=

Rp Rp +R t

thus: chance on chain stop: 1-p During the growth of a single chain p is constant disproportionation mol fraction i-mer: x i = p i 1 (1 p ) mass fraction i-mer:

which yields:

1 1 p 1+ p Pw = w i i = 1 p Pn = x i i =

x ii 2 wi = = ip i 1 (1 p ) x ii

Pw D= =1 + p Pn
34

combination

x i = (1 p) 2 (i 1)p i 2 x ii 1 wi = = i(1 p) 3 (i 1)p i 2 x i i 2

which yields:

2 1 p 2+p Pw = 1 p Pn =

D=

2+p 2

35

Copolymerization
M1 + M1 M1 M1 + M2 M2 M2 + M1 M1 M2 + M2 M2
k22 k21 k12 k11

} }

k11 r1 = k12 k 22 r2 = k 21

36

Copolymerization
fi : fraction of monomer i in reaction mixture f1 = [M1] / ([M1] + [M2]) F i: fraction of monomer i built into polymer F1 = d[M1] / (d[M1] + d[M2])

r1f12 + f1f2 F1 = 2 r1f1 + 2f1f2 + r2f22 Average copolymerisation rate: r1f12 + 2f1f2 + r2f22 k p = r1f1 k11 + r2f2 k 22

Long chain assumption (ki, kd ignored; kp, kt not ~ chain length) Reactivity ratios independent of environmental factors
37

Ideal copolymerisation
1
MMA / BA Ethene / VAc VDC / VC

Composition drift If f1 F1

0.8

0.6 F1 0.4

f1 changes F1 changes What does composition drift mean for the polymer that is formed?

0.2

0 0 0.2 0.4 f1 0.6 0.8 1

38

Polymerization techniques
Sometimes for one monomer several techniques of polymerizing are available. Choice of a specific technique depends on a number of factors:

Kinetic / mechanistic factors related to chain length, chain composition Technological factors e.g. heat removal, reaction rate, viscosity of the reaction mixture, morphology of the product Economic factors; production costs, enviromental aspects, purification steps etc.

39

Polymerization techniques
Homogeneous systems Bulk polymerization Solution polymerization Heterogeneous systems Suspension polymerization Emulsion polymerization Precipitation polymerization Polymerization in solid state Polymerization in the gas phase
40

Bulk polymerization

Polymerization of the undiluted monomer. Viscosity increases dramatically during conversion. Heat removal and hot spots Advantages Disadvantages * Pure products * heat control * Simple equipment * dangerous * No organic solvents * molecular weights very disperse Applications Polymers through step reactions (nylon 6) PMMA-plates

41

Solution polymerization
Monomer dissolved in solvent, formed polymer stays dissolved. Depending on concentration of monomer the solution does not increase in viscosity. Advantages Disadvantages * Product sometimes * Contamination directly usable with solvent * Controlled heat * Chain transfer to release solvent * Recycling solvent Applications Acrylic coating, fibrespinning, film casting
42

Qualitative description of emulsion polymerization kinetics

Suspension polymerization

Water insoluble monomers are dispersed in wate Initiator dissolved in monomer. Stabilization of droplets/polymer particles with non-micelle forming emulsifiers like polyvinylalcohol or Na-carboxymethylcellulose. Equivalent to bulk polymerization, small droplets dispersed in water. Product can easily be separated, particles 0.01-1mm. Pore sizes can be controlled by adding a combination of solvent (swelling agent) and nonsolvent. Viscosity does not change much.
43

Qualitative description of emulsion polymerization kinetics

Suspension Polymerization
Advantages Disadvantages * Heat control simple * Contamination with * Product directly stabilizing agent usable * Coagulation possible * Easy handling

Applications Ion-exchange resins, polystyrene foam, PVC

44

Emulsion Polymerization
A micelle forming emulsifier is used. Initiator is water soluble. The formed latex particles are much smaller than suspension particles (0.05-2 m). Kinetics differ considerable from other techniques. Polymer is formed within the micelles and not in the monomer droplets.

45

Qualitative description of emulsion polymerization kinetics

Antonio de Herrera Tordesillas described an application of natural latex in 1601. A ball game as part of a religious rite.

46

Emulsion Polymerization

Advantages Disadvantages * Low viscosity even * Contamination of at high solid contents products with additives * Independent control * More complicated of rate and in case of water molecular-weight soluble monomers * Direct application of complete reactor contents

47

Applications of latices
Paints-Construction
* Paints / rough casting / heat insulation * Elastomeric coatings / primers * Additives for cement and concrete * Anti corrosives / wood coatings * Industrial coatings * Rheology modifiers * Roof coatings * Fillers and levelling powders * Varnishes

Glues-Adhesives
* Wood glues / adhesives for furniture laminates * Adhesives for floor-, wall- and ceiling materials * Packaging- and lamination glues * Adhesion- and contact glues * Leather fibres * Glues in powder form * Structural Adhesives * Contact Adhesives

Paper
* Binders for rubbed paper * Boxes and wallpaper

Textiles
* Carpet backside coatings * Fleece binder * Spunbond / textile coating * Equipment of technical textiles * Pressure binder /flocculating glue

Other
* Teflon * Elastomers

Source: Clariant 48

Objective

Process

Molecular Microstructure & Morphology

Ho w

to

in f

lu en ce

What is the relation ?

Properties

49

Differential Scanning Calorimetry

50

Glasovergangstemperaturen
Tg [C] Polyvinylacetaat Polyvinylpropionaat Poly(VeoVa 10) Polyvinylidenchloride Polyacrylonitril Polyethyleen Polystyreen Polymethylmethacrylaat Poly 2-ethyl-hexylacrylaat Poly n-butylacrylaat Polyacrylzuur (kristallijn) Poly methacrylzuur Poly acrylamide (kristallijn) + 29 +7 -2 + 80 + 100 (-125) + 100 +105 -85 -54 + 166 + 185 + 153
51

Polyhydroxy-ethyl-methacrylaat + 55

Glasovergangstemperaturen
Monomer: Tg [C]
- Acrylaat - 22 - 54 - 85 +8 Methyl Ethyl - Acrylaat n-Butyl - Acrylaat 2-Ethylhexyl - Acrylaat

Methyl Ethyl n-Butyl 2-Ethylhexyl Decyl n-Butyl iso-Butyl sek.-Butyl tert.-Butyl n-Butyl iso-Butyl sek.-Butyl tert.-Butyl

- Methacrylaat - Methacrylaat - Methacrylaat - Methacrylaat - Methacrylaat - Acrylaat - Acrylaat - Acrylaat - Acrylaat - Methacrylaat - Methacrylaat - Methacrylaat - Methacrylaat

+ 105 + 65 + 20 - 10 - 70 - 54 - 43 - 20 + 41 + 20 + 48 + 60 + 107 52

Monomeer Indeling in groepen

Harde monomeren Styreen Methylmethacrylaat Vinylchloride (Vinylacetaat) (Vinylpropionaat) Acrylonitril

Zachte monomeren
Acrylzuuresters Butadieen Ethyleen Versaticsurevinylester Malein- und Fumaarzuuresters met C > 4

Geladen monomeren
Acrylzuur Methacrylzuur Maleinezuur Fumaarzuur Natrium-Etheensulfonaat Natrium-Etheenphosphaat

Vernettende monomeren
Polyvinyl- und Polyallylverbindingen N-Methylol-verbindingen Aktieve halogeenhoudende verbindingen

53

Spherulieten in de microstructuur van een polymeer.

54

De 3M aspecten van de PE proef. Links de toepassing, een beker (macro), met in het midden de morfologie van dit polymeer (meso). Rechts de atomaire ketens zoals die in het polymeer voorkomen (micro).

55

Copolymeren
Block-Copolymeer

Graft polymeer

Statistisch Copolymeer

Alternerend Copolymeer
56

57

Naast een molmassaverdeling bezit een copolymeer ook een samenstellingsverdeling

w1

Fmnomr1 o e
58

Approach : Raman spectroscopy as on-line sensor

In-situ Raman spectroscopy gives on-line information on concentrations

Properties Monomer Composition

Copolymer Composition Distribution

model
laser

Reactivity Monomer Partitioning Kinetics

59

Mechanical properties
Example: 25% styrene - 75% methyl acrylate

A
1.2
b E

C
200

Elongation at break (%)

Youngs modulus (Gpa)

1.0

0.5 Fsty

150
0.8 0.6 0.4

100

0.5 Fsty

50
0.2 0.0

0.5 Fsty

0.5 Fsty

60

Polymeerveroudering
Plafondtemperatuur Degradatie Stabilisatie

61

Polymeerveroudering
-Ketenbreuk -Depolymerisatie -Crosslinking Bindingsveranderi ng Zijgroepveranderin g
62

Plafondtemperatuur
Temperatuur waarbij in evenwicht
1 mol/l monomeer aanwezig is Of [M]= concentratie zuiver monomeer

Methylmethacrylaat Tc=220 C Alpha-methyl styreen Tc= 61 C

63

64

65

66

67

Degradatie
Thermische degradatie
Willekeurige ketenbreuk Keteneind depolymerisatie (unzipping)

68

Degradatie
Oxidatieve degradatie
Radicaalvorming

door reacties met zuurstof

69

Degradatie
Stralingsdegradatie
Fotolyse (UV) Radiolyse

70

Degradatie
Chemische degradatie
NO2

- SO2

71

Degradatie
Mechanochemische degradatie
Kogelmolen Spuitgieten Vermalen

72

Degradatie
Biologische degradatie
Controlled drug release

73

Composieten

74

75

76

77

78

79

80

81

82

Nanotubes for conductive coatings

Armoured latex particle

Encapsulated pigment Encapsulated clay platelet

83

84