I.

Polymer Analogous Reactions

II. Grafting and Block-Copolymerization
III. Cross-linking Reactions
IV. Polymer Degradation
I. Polymer Analogous Reactions
Polymer analogous reaction - chemical modification
of a polymer that changes the chemical structure of
the substituents (pendant groups) without affecting
the polymerization degree or the molecular weight
distribution of the macromolecular compound.

X X X Y Y Y

2
I. Polymer Analogous Reactions
Applications
 Synthesis of polymers that do not have a corresponding
monomer, or for which the monomer is not stable. Examples:
poly-vinyl alcohol, polyacetals.
 Obtaining copolymers by partial modification of the chemical
nature of the substituents. Depending on the mechanism of the
transformation reaction, the corresponding copolymers can be
random or block-type.
 Improving the properties of a natural macromolecular
products, by total or partial transformation of its substituent
groups . Example: chemical modification of cellulose.
 Changing the properties of pre-formed polymers by
modifying the nature of the pending groups in order to improve
properties (solubility, compatibility to other polymers or
additives, coloured products, etc.)
3
I.1.Reactivity of Substituents
in Polymer Analogous Reactions
 Mechanism, catalysts and reaction conditions similar
to the corresponding reactions for low-molecular
compounds.
 Differences in reactivity of the modified groups due to
the coil structure of macromolecules
 General rule: in order to disentangle the
macromolecular coil, reactions on polymers have
to be performed in solution
 Exception – surface modification of polymers

4
I.1.Reactivity of Substituents
in Polymer Analogous Reactions
Transformation degree of polymers in polymer
analogous reaction is always less that 100%.
Reasons:
1. Biphasic structure of polymers – in the crystalline phase molecules are
tightly packed – differences of mobility = reactivity between the amorphous
and crystalline phase (applies for the surface modification but not for the
reactions performed in solution)
2. Changes in solubility during the reaction – the initial polymer and the
product may not be soluble in the same solvent -> phase separation before
the reaction is completed
3. Isolated groups on the macromolecular chain – for reactions that involve
two pending groups

X X X X X X X X X X X
Y Y Y Y
4. Effect of the neighbour group – may inhibit or increase reactivity
5. Coil conformation of the chain – penetration of the reagent inside the
coil may be hindered 5
I.2. Examples –
Polymer Analogous Reactions
a. Chemical modification of cellulose
b. Synthesis of poly(vinyl alcohol)
c. Synthesis of polyacetals
d. Chlorination processes
e. Surface modification of polymers

6
I.2.a. Chemical modification of cellulose
H OH CH2OH
O
H H O
O OH
OH H
O
O
CH2OH H
OH
n

 High number of intra- and intermolecular hydrogen bonds ->

insoluble in water -> difficulty of purification, spinning
 Method:
1. Solubilisation by chemical modification (reducing the number
of hydrogen bonds)
2. Purification
3. Regenerating the initial groups (insolubilisation)
7
I.2.a. Chemical modification of cellulose
1. Solubilisation of cellulose
a. Obtaining alkali-cellulose (room temperature, water solution)
Cell OH + NaOH Cell ONa + H O
2
Alkali-cellulose retains the fibrous structure but it is swollen. The
product (after purification and re-precipitation) is the mercerised
cotton.
b. Obtaining cellulose xantogenate
Cell ONa + CS2 Cell O C SNa
S
Cellulose xantogenate is water-soluble.
2. Purification (filtration) and spinning of the cellulose xantogenate
(from aqueous solution)
3. Regeneration of the insoluble polymer
Cell O C SNa + H2SO4 Cell OH + CS2 + NaHSO4
S
8
Product: viscose (artificial satin). Highly toxic process, EU-banned.
I.2.a. Chemical modification of cellulose
Other industrial cellulose derivatives
 Cellulose nitrate - varnishes (10% nitrogen),
explosives (12-13% nitrogen)
Cell-OH + HNO3 Cell-ONO2 + H2O
 Carboxymethyl cellulose – thickening agent (food),
additive for paper industry, textile sizing, etc.
Cell-ONa + Cl-CH2COONa Cell-O-CH2COONa + NaCl
 Cellulose acetate - transparent films (cellophane),
“acetate” artificial silk, varnishes
-H2O
Cell OH + RCOOH Cell OCOR
H2SO 4 / HClO 4

-RCOOH
Cell OH + (RCO)2O Cell OCOR 9
I.2.b. Synthesis of poly(vinyl alcohol)
 Transesterification with methanol, basic catalysis
NaOH
CH2 CH + CH3OH CH2 CH + CH3OCOCH3
n
OCOCH3 OH

 Zip mechanism: the newly formed OH groups “fix” the catalyst

(by physical attraction forces) and the presence of the “adsorbed”
catalyst favours the transformation of the neighbouring group on
the chain. Consequence: the resulting product is a block
copolymer (hydroxyl and non-reacted acetate pending groups)
 Change of solubility during the reaction (poly vinyl acetate
soluble in methanol, polyvinyl alcohol soluble in water)
 Applications of polyvinyl alcohol: fibres (insolubilisation after
spinning, by acetalization), adhesives, paper industry
10
I.2.c. Synthesis of polyacetals

 Poly(vinyl-formal) - varnish for the electronic industry, adhesive for

metals.
 Poly(vinyl-acetaldehyde) - varnishes resistant to abrasion and
atmospheric agents.
 Poly(vinyl-butyral) - varnishes, moulding material, in mixture with
phenol-formaldehyde or urea-formaldehyde resins.
 Surface/bulk acetalization of PVA with formaldehyde, acetaldehyde
or propyon-aldehyde for insolulubilisaion of the spun fibres – intra-
and intermolecular acetalization (partial cross-linking)
CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2
CH CH CH CH CH CH
OH OH OH CH2 O O O O
CH2 CH2
OH OH OH O CH2 O O
CH CH CH CH CH CH
CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2

11
I.2.d. Chlorination processes
 PVC chlorination – substitution, random distribution of
chlorine atoms => perchlorvinyl (adhesive)
 Polyethylene chlorination – substitution, 24-43%
chlorine => rubber
 Natural rubber chlorination – addition + substitution,
65% chlorine => chloro-rubber, anticorrosive coating
 Polyethylene sulfo-chlorination (Cl2 + SO2) => Hypalon
rubber (chemical inertia, heat resistant 120°C)
Cl
( CH2 CH2 CH2 C ) ( CH2 CH2 CH2 CH )
x y
H SO2Cl n

12
I.2.e. Surface modification of polymers
 Superficial oxidation of polyolefins -> producing
polar groups (-OH; -C=O; -COOH) on the surface
(increased dyeability, improved antistatic properties).
 Ion exchangers (either cations or anions) are
usually prepared starting from partially cross-linked
polystyrene (with several per-cents of p-divinyl-
benzene). Example:
CH2 CH CH2 CH

+ H2SO4

CH2 CH SO3H

13
II. Grafting and Block-Copolymerization
 Copolymerization leads usually to random copolymers =>
need for special methods to obtain block and grafted
copolymers.
 Special properties of block and grafted copolymers:
presence of properties of the two blocks (random
copolymer -> intermediate properties between the two
copolymers, except for crystallization, that may not occur)
 Simple mixing of polymers leads to microscopic phase
separation => need for chemical bonding of different
chains => block and grafted copolymers
 Applications of block and grafted copolymers:
 Thermoplastic elastomers (SBS, polyester/polyamide)
 Impact resistant polystyrene
 Spandex (Lycra, elastane) fibres and other polyurethane-
ethylene-oxyde products
 Nanomaterials (self-assembling structures)
14
II. Grafting and Block-Copolymerization
Synthesis methods
1. Block and graft copolymers obtained in monomer-
polymer systems
a. Grafting and block-copolymerization by chain transfer
b. Grafting and block copolymerization via chemically generated
active centres
c. Grafting and block copolymerization via active centres obtained y
physical methods
2. Ionic grafting and block-copolymerization
3. Grafting and block-copolymerization by condensation
polymerization
4. Grafting and block-copolymerization using high
functionality initiators
Note: all the synthesis methods will lead to a mixture of
copolymer and homopolymers
15
II.1. Block and graft copolymers obtained in
monomer-polymer systems
 Principle: chain or step polymerization of a monomer
in presence of a preformed polymer (support polymer)
that has on its chain active centres.
 Active centres distributed on the preformed chain =>
grafted copolymer
 Active centres located at the end of the preformed chain =>
block copolymers
 Active centres:
 pre-existent on the chain of the support polymer (groups
that react through condensation polymerization)
 created during the reaction (methods: functionalization of
the support chain, chain transfer, activating the polymer
through irradiation, etc.)

16
II. 1. a. Grafting and block-
copolymerization by chain transfer
 Principle: a vinyl monomer (A) is polymerized by chain
mechanism (free-radical or ionic polymerization) in
presence of a preformed polymer (B)
 Grafting by chain transfer towards the preformed polymer
chain
 Most cases – free-radical mechanism
 To increase the number of branches
C  has
 the vinyl monomer (A) ktrP /to
k phave a high chain transfer
constant

 The preformed polymer must have labile atoms, susceptible

to react via chain transfer
 The reaction product is a mixture of:
 Grafted copolymer
 Homopolymers (preformed polymer not grafted and homopolymer
of the vinyl monomer) 17
II. 1. a. Grafting and block-
copolymerization by chain transfer
Example: Butadiene (B) – Styrene (A) To obtain block copolymers, the
grafted copolymer (preformed chain: preformed polymer should have labile
polybutadiene) atoms at the chain ends. Result:
mixture of di- and tri-block copolymer
+ homopolymers.
CH2 CH
+n CH2 CH
CH CH + CH2 CH2
+ CH CH2
CH CH t / h Cl3 C ( CH2 CH )n Br
CCl3 Br CCl3 + Br
CH2 CH2

h
Cl3 C ( CH2 CH )n Br Cl3C ( CH2 CH )n-1CH2 CH + Br

CH CH CH CH2
CH CH CH3
+ n CH CH2
CH CH m CH2 C
CH3
CH2 CH2 CO OCH3
Cl3 C ( CH2 CH )n ( CH2 C )mBr
COO CH3
18
II.1.b. Grafting and block copolymerization
via chemically generated active centres
 Principle: pre-formed polymers that contain in their
structure labile groups (peroxide, hydroperoxide, perester
or azo-type) may act as macromolecular initiators for a
monomer. Advantage: lower content of homopolymers in
the final reaction mass.
 Synthesis of a polymer with labile groups in the chain:
 Polymerization of vinyl monomers in presence of oxygen

(by homolytic scission in presence of a vinyl monomer block

copolymers are obtained)
 Polymer analogous reactions – see example
19
II.1.b. Grafting and block copolymerization
via chemically generated active centres
Example: Friedel-Crafts reaction on the aromatic pending groups
of polystyrene followed by oxidation and obtaining the active
centers via Redox initiation (peroxides + ferrous ions)
(CH3)2CHCl O2
CH2 CH CH2 CH
AlCl3

H3C CH CH3
+Fe+2
CH2 CH CH2 CH
-Fe+3, -HO-

H3C C CH3 H3C C CH3

O O H O

In presence of a vinyl monomer a graft copolymer will be obtained

20
II.1.c. Grafting and block copolymerization via
active centres obtained y physical methods
 Principle
 The energy transmitted a physical method is used to break
covalent bonds in the main chain or for the homolytic
scission of the bonds between the carbon atoms and the
substituents
 The radicals/ions thus obtained initiate the polymerization of
another monomer => block and grafted copolymers
 Low selectivity => mixture of block copolymer, grafted
copolymer and homopolymers.
 Physical methods
 Radiochemical grafting (lowest selectivity, mostly used for
surface modification)
 UV grafting (only for polymers with chromophore groups)
 Mechanical grafting (internal mixers, two-roll mills,
calenders, extruders, etc)
21
 II.2. Ionic grafting and block-copolymerization
“Living” anionic polymerization
Applications: poly(isoprene-b-styrene), poly(isoprene-b-α-methyl-styrene),
poly(butadiene-b-styrene), poly(butadiene-b-isoprene), poly(butadiene-b-α-
methyl-styrene), poly(styrene-b-methylmethacrylate), etc.

 Initiation of the ionic polymerization of the first

monomer:
-
BuLi + CH2 CH Bu CH2 CH Li+

 Propagation of the first monomer:

- - +
Bu CH2 CH Li+ + x CH2 CH Bu ( CH2 CH ) CH2 CH Li
x

22
 Initiation of the anionic polymerization of the second monomer by
the living chains of the polymer present in the reaction system:
- +
Bu ( CH2 CH ) CH2 CH Li + CH2 CH CH CH2
x

-
Bu ( CH2 CH ) CH2 CH CH CH2 Li+
x+1

Chain growth by propagation until the complete consumption of the

second monomer:
-
Bu ( CH2 CH ) CH2 CH CH CH2 Li+ + y CH2 CH CH CH2
x+1

-
CH CH2) CH2 CH +
Bu ( CH2 CH ) ( CH CH CH CH2 Li
x+1 2 y

Notes:
1. Advanced purity of the reaction system required
3. The process may be continued for obtaining tri-block-copolymers, etc.
2. General method for block-copolymerization, less for grafting

23
II.3. Grafting and block-copolymerization by
condensation polymerization
a. Successive step-growth polymerization reactions => block
copolymers
n H2C CH2 HO ( CH2 CH2 O ) H
n

HO ( CH CH O )n H + ( x+ y) H2C CH CH
3
2 2

HO ( CH2 CH O ) ( CH CH O )n ( CH CH O) H
x 2 2 2 y
CH CH
3 3

24
II.3. Grafting and block-copolymerization by
condensation polymerization
b. Step-growth polymerization of a monomer in presence of a polymer chain
that possesses functional pending groups => grafted copolymers

CH2 CH + n HN C=O CH2 CH

COOH (CH2)5 CO

NH (CH2)5 CO OH
n

c. Transcondensation (interchange) reactions between two preformed

polymers => block copolymers

R Z R R Z R
+ +
R' Z R' R' Z R'

25
II.4. Grafting and block-copolymerization
using high functionality initiators
t
R O O C R N N R C O O R R O
1 O C R
2 2 1 -N2 1 2
O O O
M1 R O O C R (M1)n R C O O R
1 2 2 1
termination
by combnination O O
M1 n
termination
R O O C R (M1)n
by dis proportionation 1 2
O
t M2
R (M1)n R + R O (M2)x R (M1)n R (M2)y + RO (M )
-CO2 2 2 1 2 2 1 2 z

t M2
R (M1)n + R O (M2)x R (M1)n + RO (M )
-CO2 2 1 2 z
2 1

26
III. Cross-linking reactions
 Obtaining network polymers
 No melting or dissolution of networks => cross-linking has to be ulterior to the
application/shaping of the polymer
 Networks may swell in solvents
 Depending on the cross-linking density, elasticity can be preserved (vulcanized
rubber, 3% sulfur) or is lost (ebonite=vulcanized rubber with 30% sulfur)
 For monomers with f > 2 cross-linking is ensured by the supplementary
functions (ex: mixtures of vinyl monomers and divinyl monomers, such as
styrene + divinyl-benzene)
 For monomers with f=2 cross-linking agents (hardeners) have to be added to
the reaction mixture
 Formulations:
 One component mixtures – contain the polymer + hardener, cross-linking
occurs at high temperature (most common) or in presence of an environmental
agent (moisture, oxygen) -> sealed packages
 Two component mixtures– the hardener /initiator/catalyst is provided in a
separate package, mixing before use (a diluent may be use to ensure a
convenient mixing ratio, such as 1:4, etc)
 Mechanisms:
 Chain polymerization
 Step-growth polymerization

27
III.a. Cross-linking by chain polymerization
Rubber vulcanization
i. Vulcanization with sulfur
 Homolytic scission of the cyclic sulphur molecule (the slowest reaction):
·S
S8 Sx S ·
; x6
 Free-radical generation on the rubber chain:
· · · ·
CH2 C CH CH2 + S Sx S HSx+2 + CH C CH CH2

CH3 CH3
 Cross-linking:
Sx·
·
CH C CH CH2 + S8 CH C CH CH2

CH3 CH3
Sx· CH C CH CH2
CH C CH CH2 + CH2 C CH CH2 Sx CH3
CH3 CH3 ·
CH 2 C CH CH2

CH3 28
i. Vulcanization with sulfur
Accelerators-compounds with labile sulphur-sulphur bonds or
other labile bonds that are decomposed easier and provide
the initial radicals that start the chain reaction. Commercial
name of the group: Vulkacit (ex. thiourea, guanidine,
thiurams, etc.)
Activators –metallic oxides (CaO, MgO, PbO, ZnO)
Vulcanization group: sulfur + accelerator(s) + activator
ii. Vulcanization with metallic oxides
For rubbers that posses halide atoms in the molecule
(polychloroprene, chlorinated PE, etc)

Cl
+ ZnO O + ZnCl2
Cl

29
iii. Vulcanization with peroxides
 For saturated rubbers
 Peroxides decomposition, by homolytic scission of the O-O bond
·
R O O R 2 R O

 Initiation, by extraction of a labile hydrogen atom from the rubber chain:

·
CH2 CH CH2 CH2 + R O· CH CH CH CH + R OH
2 2
CH3 CH3

 Cross-linking through combination of two radicals situated on different

macromolecular chains:
CH3

· · CH CH
CH CH CH2 CH2 + CH CH CH2 CH2
CH CH
CH3 CH3
CH3

 The process is more difficult to control as compared with vulcanization with sulfur
=> usually in saturated rubbers double bonds are added (during synthesis) by
copolymerization in presence of a small amount of long-chain diene (ex. 1,5
hexadiene)

30
III.a. Cross-linking by chain polymerization
Unsaturated polyesters
i. Synthesis of the linear polyester with double bonds in the main
chain, via step-growth polymerization

ii. Dissolution in styrene (or another vinyl monomer)

iii. Free-radical copolymerization of styrene with the double bonds in
the polyester chain (cross-linking) -peroxide initiator or redox
initiation system -> hardening
31
III.a. Cross-linking by chain polymerization
Alkyd resins
i. Synthesis of the main chains (linear/branched): complex
mixtures of aliphatic diols & polyols (glycerol),
aromatic/aliphatic acids/anhydrides, monocarboxilic (fatty)
acids. Usually glycerol & monocarboxilic acids are replaced by
oils.

i. Cross-linking (hardening) - cross-linked free-radical

polymerisation ( in presence of atmospheric oxygen), of the
double bonds in the lateral chains – oxydopolymerisation,
siccativation.
32
III.b. Cross-linking by step-growth polymerization
(condensation polymerization)

Phenolic Resins – polycondensation of phenol (f=3)

and formaldehyde (f=2)
 Novolac resins – fenol excess

OH
OH
CH2 CH2 CH2 CH2

HO OH
HO CH2
OH

Cross-linking in presence of a formaldehyde donor

(HMTA or paraformaldehyde)
33
III.b. Cross-linking by step-growth polymerization
(condensation polymerization)

Phenolic Resins – polycondensation of phenol

(f=3) and formaldehyde (f=2)
 Resols– formaldehyde excess – mixtures of methylol-
phenoles and lower oligomers

OH OH OH
CH2OH HOH2C CH2OH
OH
CH2OH
CH2OH CH2OH CH2OH

Cross-linking by heating (no hardener needed)

34
Aminic resins
Urea-formaldehyde

Melamine-formaldehyde

Hardening: acidic medium (catalyst), sometimes with addition of

ammonium derivatives
X-H + HOCH2-X  X-CH2-X + H2O 35
III.b. Cross-linking by step-growth polymerization
(condensation polymerization)
Epoxy Resins
CH3 CH3

CH2 O C O CH2 CH CH2 O C O CH2

O O
CH3 OH CH3
n

Cross-linking: in presence of hardeners with active

hydrogen atoms, such as polyamines:

H NH CH2 CH2 NH2

x

Y H + H2C CH Y CH2 CH

O OH
36
Polyurethanes
Raw materials: Diisocyanates + diols
1. Urethanisation – main reaction, chain growth
N C O + HO NH COO
2. Cross-linking:
 Allophanate formation => cross-linking
N C O+ NH COO NH C N COO
O
 Hydrolysis in presence of the environmental moisture
N C O + H2O NH COOH NH2 + CO2
unstable
 Formation of urea functions:
N C O + H2N NH C NH
O
 Formation of allophanamide (biuret) => cross-linking
N C O + NH C NH NH C N C NH
O O O 37
IV. Polymer degradation
 Polymer degradation (destruction) - series of reactions that
result in the breaking of the chemical bonds, with reduction of
the molecular weight of the polymer and loss of the physical and
mechanical properties of the macromolecular compound.
 End products - oligomers, monomer or other types of low-
molecular compounds, sometimes accompanied by a certain
amount of cross-linked product, resulted from the side reactions.
 Factors that produce degradation:
 Physical: thermal, photochemical, mechanical or radiation
 Chemical: water, moisture, alcohols, acids, oxygen, ozone, etc
 Preferential destruction mechanism – depending on the
polymer structure:
 Polymers with carbon chains are sensitive mainly to degradation
by physical agents through homolytic scission of the carbon-carbon
or carbon-hydrogen bonds.
 Polymers containing heteroatoms in the main chain are
sensitive to chemical agents that attack mainly the carbon-
heteroatom bonds.
38
IV. Polymer degradation
1. Polymer destruction by physical factors
a. Thermal destruction
b. Radiation destruction
c. Photochemical degradation (photolysis)
d. Mechanical destruction
2. Chemical degradation of polymers
a. Degradation by proteolytic substances
b. Oxidative degradation

39
IV.1.a. Thermal destruction of polymers
 Thermal destruction temperature (Td)- the temperature at which
the destruction rate reaches 1%/min.
 Thermostabiliy - capacity of a polymer to preserve its properties and
not undergo chemical transformation at high temperature. Polymers
usually considered thermo-stable have Td>200 °C.
 Examples: poly(tetrafluoroethylene) - 510°C, polyethylene- 400°C,
polystyrene - 360°C, poly(methyl methacrylate) - 330°C.
 Thermoresistant polymers (Td up to 800°C) - ladder-type, usually
consisting in condensed aromatic cycles.
 Depolymerization – Tc = ceiling temperature - temperature at which
propagation becomes reversible => the polymer transforms
quantitatively into monomer. Consequences:
 If Tc is too low, the monomer cannot be used for obtaining
homopolymer (ex. -methyl-styrene, Tc60°C
 Usually Tc is higher than the temperature at which other degradation
processes occur
 If Tc is convenient, depolymerization is a method for recycling (waste
processing): ex: poly--caprolactam, PMMA

40
Hydrocarbon chains-mechanism of thermal destruction
 Scission of the macromolecular chain
CH2 CH CH2 CH CH2 CH + CH CH
2
R R R R
 Depolymerization
CH2 CH CH2 CH CH2 CH + CH2 CH
R R R R
 Inter-molecular chain transfer
CH2 CH CH2 CH + CH2 CH CH2 CH
R R R R
CH2 CH2 + CH CH + CH2 CH
R R R
 Intra-molecular chain transfer
CH2 CH2 CH2 CH2 CH2 CH2 CH2+ CH2 CH CH2 CH2 CH3

 Termination, mostly by disproportionation

CH2 CH CH2 CH + CH2 CH CH2 CH

R R R R

CH2 CH CH CH + CH2 CH CH2 CH2

R R R R
41
Chemical transformation of the substituent groups
 Dehydrochlorination of PVC (180°C):
+R
CH2 CH CH CH CH CH + Cl
- RH
Cl Cl

CH CH CH CH + HCl
Cl

Autocatalitic reaction => stabilisers are HCl captors (esters

or metallic salts of fatty acids)

 Cyclization of polyacrylonitrile, (175 - 200°C)

CH2 CH2 CH2

CH2
CH CH HC CH

CN CN
C C
N

The reaction continues at higher temperature = > carbon fibres

42
IV.1.b. Destruction by radiation
 Non-selective mechanism
 Scission of C-C and C-H bond
 Chain mechanism
 Resulting in:
 Lowering the molecular mass
 Obtaining lower oligomers
 Some amount of cross-linking

43
IV.1.c. Destruction by UV (photolysis)
 Only polymers with chromophore groups are sensitive to
UV-light (ex. polyacrylonitrile)
 UV-radiation – a factor to be used to enhance natural
polymer degradation => increase sensitivity by adding
photo-sensibilisers:
 Derivatives of transitional metals: Fe(SCN)3, Fe2O3, FeCl3, ZnO
 Compounds with carbonyl groups (ketones, diketones, quinones),
peroxides, azo-derivatives, polynuclear aromatic hydrocarbons
(naphthalene, anthracene)
 In small amounts they do not reduce the service time but allow
subsequent degradation of waste under the influence of natural
factors.

44
IV.1.d.Mechanical degradation
 Fatigue of polymer materials - gradual weakening of
the bonds due to the mechanical stress that leads to a
mechanical cracking, with formation of free radicals
and reduction of the molecular weight. It occurs
during processing and service.
 Main mechanism: homolytic breaking of the chain
 Friction (plasticization) - purpose chain break via
mechanical forces (two-roll mills, internal mixers) in
order to reduce molecular weight (for natural rubber
and some synthetic polymers) => lower masses
facilitate processing

45
IV.2. Chemical degradation of polymers
a. Degradation by proteolytic substances
 Specific for polymers with C-X bonds in the main chain
(polyesters, polyamides, etc.)
 Main reactions: hydrolysis (environmental moisture), alcholysis,
aminolysis, acidolysis
 Reactivity in hydrolysis reactions diminishes in the series:
polyacetals > polyamides > polyesters
 Practical applications: natural degradation of polymer waste,
biological destruction of heteropolymers with enzyme catalysts.
b. Oxidative degradation
 specific for polymers with carbon chains
 scission of the macromolecules in presence of oxygen, ozone or
peroxides, by a chain mechanism involving free radicals.
 Consequences: gradual reduction of the mechanical properties,
due mainly to the diminishing of the molecular weight. In the
advanced stages of the process the polymer becomes friable and
its resistance to impact diminishes significantly.
 Process known as polymer ageing.
 In order to increase the service life, stabilisers are added to
polymer-based mixtures (carbon-black and inhibitors of free-
radical processes). 46