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Kursus Kaedah Penyelidikan, UTeM, Mei 2010

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CHAPTER 5 DEGDRADATION OF POLYMERS
DR. MOHD WARIKH BIN ABD RASHID

FKP

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Kursus Kaedah Penyelidikan, UTeM, Mei 2010

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OUTLINE CONTENT

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Introduction Photoinduced Degradation Thermal Degradation Chemical Degradation Biological Degradation Stabilizers

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etc – of a polymer or polymer-based product under the influence of one or more environmental factors such as heat. such as cracking and chemical disintegration of products or more rarely. colour. or deliberately lowering the molecular weight of a polymer for recycling. Mei 2010 ‹#› 5. light or chemicals such as acids. UTeM. the changes in properties are often termed “aging” 3 • • . desirable as in biodegradation. shape. These changes are usually undesirable.Kursus Kaedah Penyelidikan.1: Introduction • Polymer degradation is a change in the properties – strength. alkalis and some salts.

Polymeric molecules are very large (on the molecular scale). Degradation can also be induced deliberately to assist structure determination. Any loss in chain length lowers tensile strength and is a primary cause of premature cracking. 4 • • . Mei 2010 ‹#› Cont • In a finished product such a change is to be prevented or delayed. UTeM.Kursus Kaedah Penyelidikan. and their unique and useful properties are mainly a result of their size. Degradation can be useful for recycling/reusing the polymer waste to prevent or reduce environmental pollution.

These make up nearly 98% of all polymers and plastics encountered in daily life. UTeM. Each of these polymers has its own characteristic modes of degradation and resistance to heat. Mei 2010 ‹#› Cont’ • Today there are primarily seven commodity polymers in use: polyethylene (PE). polypropylene (PP). polyvinyl chloride (PVC). light and chemicals. 5 • • .Kursus Kaedah Penyelidikan. polyethylene terephthalate (PET). polystryrene. polycarbonate and poly(methyl methacrylate) (Plexiglass).

UTeM. PET is sensitive to hydrolysis and attack by strong acids while polycarbonate depolymerizes rapidly when exposed to strong alkalis. polypropylene (PP) and poly(methyl methacrylate) are sensitive to oxidation and UV radiation. Mei 2010 ‹#› Cont’ • Polyethylene (PE). while PVC may discolour at high temperature due to loss of hydrogen chloride gas and become very brittle.Kursus Kaedah Penyelidikan. • 6 .

Many natural and synthetic polymers are attacked by ultra-violet radiation and products made using these materials may crack or disintegrate.Kursus Kaedah Penyelidikan. X-rays and gamma rays are usually involved in such reactions. Electromagnetic waves with the energy of visible light or higher. Mei 2010 ‹#› 5. UTeM. such as ultraviolet light. 7 .2: Photoinduced Degdradation • • • Most polymers can be degraded by photolysis to give lower molecular weight molecules.

8 .2: Continue • • • The problem is known as UV degradation and is a common problem in products exposed to sunlight.Kursus Kaedah Penyelidikan. Mei 2010 ‹#› 5. when the problem is known as phototendering in textiles such as curtains or drapes. Continuous exposure is a more serious problem than intermittent exposure. since attack is dependent on the extent and degree of exposure. UTeM. Many pigments and dyes can also be affected.

complete product disintegration can occur. The exposed surfaces of products may then discolour and crack. producing carbonyl groups in the main chain. UTeM. • .2: Continue • • Common synthetic polymers which may be attacked include PP and LDPE where tertiary carbon bonds in their chain structures are the centres of attack.Kursus Kaedah Penyelidikan. which then react further with oxygen in the atmosphere. The ultra-violet rays activate such bonds to form free radicals. although in bad cases. Mei 2010 ‹#› 5.

UTeM.2: Continue • In fibre products like rope used in outdoor applications. so giving an early warning of the problem. 10 . Mei 2010 ‹#› 5.Kursus Kaedah Penyelidikan. product life will be low because the outer fibres will be attacked first and will easily be damaged by abrasion for example: discolouration of the rope may also occur.

UTeM. where attack occurs by oxidation of bonds activated by the UV radiation forming carbonyl groups in the polymer chains.Kursus Kaedah Penyelidikan. Mei 2010 ‹#› 5. 11 .2: Continue • The problem can be detected before serious cracks are seen in a product using infra-red spectroscopy.

Mei 2010 ‹#› 5. Other plastic products which failed included PP mancabs used at roadworks which cracked after service of only a few months. Many similar cones also failed because an anti-UV additive had not been used during processing.2: Continue • In the example shown. the product was a road cone made by rotational moulding in LDPE. carbonyl groups were easily detected by IR spectroscopy from a cast thin film. 12 • • . UTeM.Kursus Kaedah Penyelidikan. which had cracked prematurely in service.

2: Continue • UV attack by sunlight can be ameliorated or prevented by adding anti-UV chemicals to the polymer when mixing the ingredients. 13 . UTeM. Mei 2010 ‹#› 5. • The chemicals used are similar to those used in sunscreen cosmetic products.Kursus Kaedah Penyelidikan. prior to shaping the product by injection moulding for example: • UV stabilizers in plastics usually act by absorbing the UV radiation preferentially and dissipating the energy as low level heat. which protect skin from UV attack.

• Indeed unless correctly prevented. UTeM. of plastics as much as the possibility of mechanical property loss. significant thermal degradation can occur at temp. • Thermal degradation can present an upper limit to the service temp.3: Thermal Degradation • Thermal degradation of polymers is molecular deterioration as a result of overheating. 14 . much lower than those at which mechanical failure is likely to occur. Mei 2010 ‹#› 5. the component of a long chain backbone of the polymer can begin to separate (molecular scission) and react with one another to change the properties of the polymer.Kursus Kaedah Penyelidikan. • At high temp.

general reduction in most other desirable physical properties. Mei 2010 ‹#› 5.Kursus Kaedah Penyelidikan. UTeM. cracking.3: Continue Introduction • The chemical reactions involved in thermal degdradation lead to physical and optical property changes relative to the initially specified properties. chalking. • Thermal degradation generally involves changes to the molecular weight (and molecular weight distribution) of the polymer and typical property changes include reduced ductility and embrittlement. 15 . colour changes.

propagation.3: Continue Mechanism • Most types of degradation follow a similar basic pattern. The conventional model for thermal degradation is that of an autoxidation process which involves the major steps of initiation.Kursus Kaedah Penyelidikan. branching and termination. Mei 2010 ‹#› 5. UTeM. this creates a highly reactive and unstable polymer ‘free radical’ (R) and a hydrogen atom with an unpaired electron (H) 16 . • Initiation: involves the loss of a hydrogen atom from the polymer chain as a result of energy input from heat or light.

Kursus Kaedah Penyelidikan. – The hydroperoxide can then split into two new free radicals. – The process can therefore accelerate depending on how easy it is to remove the hydrogen from the polymer chain.3: Continue • Propagation: – involve a variety of reactions and one of these is where the free radical (R) reacts with an oxygen (O₂) molecule to form a peroxy radical (ROO) which can the remove a hydrogen atom from another polymer chain to form a hydroperoxide (ROOH) and so regenerate the free radical (R). UTeM. 17 . (RO) + (OH). which will continue to propagate the reaction to other polymer molecules. Mei 2010 ‹#› 5.

Kursus Kaedah Penyelidikan. UTeM. Mei 2010 ‹#› 5. 18 .3: Continue • Termination: – the termination of thermal degradation is achieved by ‘mopping up’ the free radicals to create inert products. – This can occur naturally by combining free radicals or it can be assisted by using stabilizers in the plastic.

Then according to the chain reaction mechanism. However. UTeM. the polymer loses the monomer one by one. the molecular chain doesn’t change a lot in a short time. the end of polymer chain departs and forms low free radical which has low activity. The reaction is shown.Kursus Kaedah Penyelidikan. this process is common for polymethymethacrylate (perspex): CH2-C(CH3)COOCH3-CH2-C*(CH3)COOCH3→ CH2-C*(CH3)COOCH3 + CH2=C(CH3)COOCH3 19 .3: Continue Ways of Polymer Thermal Degradation (i) Depolymerisation – – – Under thermal effect. Mei 2010 ‹#› 5.

this is because it forms new free radical which has high activity can occurs intermolecular chain transfer and disproportion termination with the CH2’ group. could be occurred at any position of the backbone. Mei 2010 ‹#› (ii) Random Chain Scission – The backbone will be break down randomly. CH2-CH2-CH2-CH2-CH2-CH2-CH2’→ CH2-CH2-CH=CH2 + CH3-CH2-CH2’ or CH2’+CH2=CH-CH2-CH2-CH2-CH3 20 .Kursus Kaedah Penyelidikan. – The molecular weight decreases rapidly and cannot get monomer in this reaction. UTeM.

– When polymer was being heated.Kursus Kaedah Penyelidikan. – For example the PVC eliminates HCL under 100-120°C. UTeM. CH2(Cl)CHCH2CH(Cl)→CH=CH-CH=CH+2HCl 21 . the side groups are stripped off from the chain before it is broken into small pieces. Mei 2010 ‹#› (iii) Side-Group Elimination – Groups that are attached to the side of the backbone are held by bonds which are weaker than the bonds connecting the chain.