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Journal of Taibah University for Science xxx (2014) xxx–xxx
Review Article
Abstract
Polymer science is, of course, driven by the desire to produce new materials for new applications. The success of materials such
as polyethylene, polypropylene, poly(vinyl chloride) and polystyrene is such that these materials are manufactured on a huge scale
and are indeed ubiquitous.
It is widely recognized that ultraviolet rays (UVR) in sunlight (wavelengths between 280 nm and 400 nm) is an important factor
causing photodegradation to some organic substances such as polymers.
UV radiation causes photooxidative degradation which results in breaking of the polymer chains, produces free radical and reduces
the molecular weight, causing deterioration of mechanical properties and leading to useless materials, after an unpredictable time.
In order to protect against the damaging effects of UVR on polymers, addition of UV light absorbers, excited state quenchers,
hindered amine light stabilizers (HALS), hydroperoxide decomposers, radical scavengers, pigments, fillers and antioxidants are an
effective and convenient solution in practice.
This review highlights the thermal and photodegradation of poly(vinyl chloride), the sites for initiation of the thermal degradation,
the mechanism of the photodegradation, the discoloration of PVC by heat and light and the influence of stabilizers on the rate of
degradation.
© 2014 Taibah University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. The origin of PVC and its subsequent development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Stereo regularity of poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Production of poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
6. Uses of poly(vinyl chloride) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
∗ Corresponding author.
E-mail addresses: emad yousif@hotmail.com (E. Yousif), nah.chemistry@yahoo.com (A. Hasan).
Peer review under responsibility of Taibah University
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Isotactic PVC
H Cl H Cl H Cl H Cl H Cl H Cl
H H H H H H H H H H
Syndiotactic PVC
H Cl Cl H H Cl Cl H H Cl Cl H
H H H H H H H H H H
Atactic PVC
H Cl H Cl Cl H H Cl Cl H Cl H
H H H H H H H H H H
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Dicomposition initiator: I 2R
CH=CHCl + H3C-CHCl
CH2-CH2Cl + CH=CHCl
(disproportionation)
CH2-CHCl + R CH2-CHCl-R
(combination with primary radical)
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VCM
CH2CHCl CH2CHCl-ClHC-CH2
head-to-head
1,2-Cl-shift
CH2Cl
VCM VCM etc.
CH2CHCl-CH-CH2Cl CHCl-CH-CH2CHCl CH2CHCl
MB
VCM
VCM etc.
2nd Cl-shift CH2-CH=CH-CH2Cl + ClH2C-CHCl CH2CHCl
CHCl-CH2Cl
V CM V C M e t c.
CH2-CH-CHCl-CH2Cl CH2-CH-CH2-CHCl CH2CHCl
EB
VCM
VCM etc.
CH2-CH=CH-CH2Cl + ClH2C-CHCl CH2CHCl
ideal structure of PVC is a linear structure formed • Chloromethyl (MB) [47–49] and 1,2-dichloroethyl
by head to tail addition of monomer molecules to branches (EB) [50], result from one or two successive
the growing polymer chain [31]. Thermo gravimet- 1,2-Cl shifts respectively, followed by regular chain
ric analysis on low molecular model compounds growth as is shown in Fig. 6.
such as 2,4,6-trichloroheptane, 2-chloropropane and • The 2,4-dichloro-n-butyl branch (BB) is formed via a
2,4-dichloropentane, corresponding to the regular head- 1,5-backbiting mechanism [51], Fig. 7.
to-tail structure of PVC containing secondary chlorines • Long chain branching (LCB), results from hydrogen
only, shows that these model compounds are stable abstraction, from a chloromethylene or a methylene
up to at least 200–300 ◦ C. Commercially available unit of a polymer chain, by a growing macroradical or
PVC, on the other hand, would already degrade around possibly a chlorine atom [37,52], Fig. 8.
120 ◦ C, if it were not stabilized before processing • Diethyl branches (DEB) [53,54], seem also to be
[32–34]. present in PVC fractions produced at very high VCM
conversions and therefore when monomer supply is
almost exhausted, Fig. 9.
11. The causes for the low thermal stability of • Oxygenated structures, Fig. 10.
PVC
12. Thermooxidative degradation of poly(vinyl
The main problem around PVC is its low ther- chloride)
mal stability caused by the presence of defects in the
molecular structure. Various defect sites in the polymer The following processes proceed during thermoox-
chain are thought to be responsible for this instabil- idative PVC degradation [55]:
ity. Possible defect structures in PVC chains are allylic
chlorine [35,36], tertiary hydrogen and chlorine atoms • Oxygen absorption.
[37,38], end groups such as double bonds [39–41], • Hydrogen chloride extraction.
oxygen-containing groups, peroxide residues [42,43], • Extraction of various volatile products.
and head-to-head structures [44]. In addition to these • Decrease of mass and molecular mass of the polymer.
abnormalities, the steric order of the monomer units
(tacticity) may have some influence on the degrada- 13. Chemical degradation of poly(vinyl chloride)
tion [45,46]. Some of them seem to affect the thermal
stability while others are completely harmless. The fre- Many factors, such as temperature, humidity and solar
quently occurring branches and the most important types radiation cause degradation in polymers [56]. Plastic
of branches concerning the thermal stability of PVC are materials when exposed to sunlight slowly loose their
described below: physical and mechanical properties due to degradation
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CH2-CHCl-CH2-CHCl-CH2-CHCl CH2-CCl-CH2-CHCl-CH2-CH2Cl
VCM etc.
CH2-CHCl-CH2-CH2Cl
CH2-CCl-CH2-CHCl-CH2-CHCl
BB
R + CH2-CHCl-CH2-CHCl
- RH
CH2-CCl-CH2-CHCl CH2-CHCl-CH-CHCl
VCM etc. - Cl
VCM etc.
H
Cl
CH2-CHCl-C-CHCl CH=CH-CHCl
CH2-C-CH2-CHCl
CH2 LCB IA
CH2 LCB
CH2CHCl
CH2-CCl-CH2-CHCl-CH2-CH2Cl + CH2=CHCl CH2-CHCl-CH2-CCl-CH2-CHCl-CH2-CH2Cl
b a
CH2CH2Cl CH2CH2Cl
VCM etc.
CH2-CHCl-CH2-CCl-CH2-CCl-CH2-CHCl CH2-CHCl-CH2-CCl-CH2-CCl-CH2-CH2Cl
CH2CH2Cl
DEB
H Cl
- HCl
O
O O
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[57]. Poly(vinyl chloride) is a polymer which is very determined primarily by two factors: their ability to
sensitive to the weathering action and this restricts its absorb UV light in the wavelength range under consid-
outdoor applications. This occurs mainly because of eration and their participation in the formation of active
changes in mechanical properties and color [58]. particles (radicals) which cause degradation of the poly-
mer chains. The alkene unsaturated (C C) bonds (both
14. Photodegradation of poly(vinyl chloride) internal and terminal) cannot be the primary initiators
of PVC photodegradation under the action of sunlight
There is a great interest at present in the photodegra- with (λ > 250) nm because they absorb only the UV light
dation of polymeric systems, and this is reflected in at (λ < 200) nm. The absorption by conjugated (C C)
the large number of research papers and other scien- bonds (dienes, trienes, etc.) shifts toward the longer
tific publications that appear each year in this subject wavelengths [64]. The color changes from white to yel-
area. A major reason for this interest is that macro- low, brown, and finally to black while the properties of
molecular materials have increasingly wide commercial the material deteriorate [65].
applications where outdoor durability is an important The exposure of vinyl chloride polymers to light at
consideration. In this context, all commercial organic 250–350 nm develops typical signs of degradation in
polymers will degrade in air when exposed to sunlight, polymer samples [55]:
although there is a very wide range of photo-oxidative
susceptibilities. It is usually the absorption of near ultra- 1. discoloration from natural to dark-brown or black,
violet (UV) wavelengths which leads to bond-breaking 2. surface cracking,
reactions and the concomitant loss of useful physical 3. brittling or softening of the material,
properties and/or discoloration [1]. Under UV irradia- 4. variation of the mechanical properties (tensile
tion, and in the presence of oxygen and moisture, PVC strength, ultimate elongation, impact strength, and
undergoes a very fast dehydrochlorination and perox- elasticity modulus),
idation process with the formation of polyenes [58]. 5. change of transparency,
Degradation also causes a drastic change in the mechan- 6. formation of a deposit on the material surface.
ical properties of the polymer, which is accompanied by
a decrease or increase in its average molecular weight
as a result of either chain scission or crosslinking of the Degradation of PVC due to weathering is a free-
polymer molecules, respectively [42,59–61]. radical mechanism started by the absorption of sufficient
energy to break chemical bonds. Weak sites suscepti-
15. Photooxidative degradation of poly(vinyl ble to degradation, as well as mechanisms of yellowing,
chloride) oxidation, bleaching and surface erosion, have been
investigated and described in several papers [66,67].
Long term exposure to sunlight leads to the degra- The photo-oxidation of PVC can be described by the
dation of plastic materials [62]. UV energy absorbed following sequence [68,69]:
by plastics can excite photons, which then create free
radicals. While many pure plastics cannot absorb UV 1. Photolytic formation of polyenic sequences with
radiation, the presence of catalyst residues and other growing conjugation lengths by multistep photo-
impurities will often act as free radical receptors, and chemical excitations. This photolysis can be initiated
degradation occurs. It only takes a very small amount by excitation of chromophoric defects with the struc-
of impurity for the degradation to occur. In the presence ture of ␣-chlorinated dienes. These reactions lead to
of oxygen, the free radicals form oxygen hydroperox- a marked discoloration and the so-formed polyenic
ides that can break the double bonds of the backbone sequences are readily photo-oxidized in the pres-
chain leading to a brittle structure. This process is ence of molecular oxygen; photobleaching is then
often called photo-oxidation. However, in the absence observed to occur.
of oxygen there will still be degradation due to the 2. Photochemical oxidation that can be initiated by Cl*
cross-linking process [63]. Poly(vinyl chloride) has poor formed along with the polyenic sequences and that
light stability in the wavelength range of 253–310 nm, leads to the formation of the following main products:
presumably due to the presence of unsaturated (C C) ␣,␣ -dichloroketones, -chloro-carboxylic acid, and
bonds, carbonyl, hydroperoxide, and hydroxyl groups in acid chlorides.
polymer chains. The relative activity of one or another 3. Cross-linking of PVC by recombination of the in-
chromophore in initiating PVC photodegradation is chain macroradicals.
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*
hv
H2C-CH H2C-CH H2C-CH + Cl
Cl Cl
[I]
H2C-CH + O2 H2C-CH Cl Cl Cl
O-O 2 H2C-C H2C-C-O-O-C
[I] [II]
O-O
Fig. 12. Formation of peroxy radical. peroxide bridge
Cl
H2C-C
O-O
[V]
Cl Cl
H2C-C + H2C-CH H2C-C + H2C-C
O-O Cl O-OH Cl
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Tertiary alkoxy radicals are also proved to be sta- 18. Protection against environmental
bilized by -scission which may involve either (C Cl) degradation in polymers
bond cleavage to form ketone or/and (C C) bond cleav-
age to form polyene [70], see Fig. 18. Polymeric materials, synthetic, semisynthetic and
The overall mechanism now suggested for the natural are photodegradable when exposed to the envi-
photooxidation of PVC to account for the main pri- ronment [75–77], because of the fact that polymers are
mary products can be summarized by the reaction not pure compounds. For example, they commonly con-
shown in Fig. 19, [71] where P• represents radical tain additives (e.g., stabilizers, pigments, fillers, finishing
∼(CH CH)n ·CHCH2 ∼ or ∼CH2 ·CClCH2 ∼. The two agents, etc.) and impurities (e.g., oxidation products,
major chain process which develop simultaneously are catalyst residues, etc.) which may very well influence
clearly apparent [72]. or even dominate the photochemistry of the polymeric
system [1].
16. Dehydrochlorination of poly(vinyl chloride) Plastics are commonly protected against such deteri-
oration by the addition of antioxidants, light and heat
The dehydrochlorination most likely proceeds by a stabilizers [78]. Ultraviolet light stabilizers are used
chain mechanism involving radical intermediates [27]. widely in plastics, cosmetics, and films. The main pur-
The presence of hydrochloride, the reaction product, and pose of UV stabilizer is to prevent polymers from
oxygen in the surrounding accelerates dehydrochlori- photodegradation or photocrosslinking caused by ultra-
nation. That is why it is worthwhile, first, to consider violet light presented in sunlight and artificial light
the reaction of noncatalytic dehydrochlorination. Dur- source [79].
ing processing, storage and utilization, PVC degrades Physical or chemical stabilization against envi-
as it is exposed to high temperatures, high mechanical ronmental degradation in polymers may be achieved
stresses or UV light. Degradation of the polymer occurs by blocking any of the steps in the deterioration
by successive elimination of hydrogen chloride (HCl), process. Since the effects of UV radiation are the most
which is called dehydrochlorination [73], see Fig. 20. serious threat to environmental durability, a number
The reaction of dehydrochlorination proceeds in PVC at of techniques have been developed to counter them.
a noticeable rate in a high-temperature range 150 ◦ C [5]. UV radiation may be excluded by various coatings or
Cl
H2C-C
t io
n O
ac [VI]
bstr
a
en
rog
H yd
Cl O
H2C-C O CH2-C-Cl + CH2-CH2
OH C Cl
Cl
O CH=CH
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h *
~CH2 CHC l~ ~CH2 CHCl~
(PVC) (PVC*)
O2
~CH 2CHCl~
(PVC)
O OH
O O
hydroperoxide
~CH 2CH~ ~CH2 CH~
(x2)
h
O2
OH
~ CHCH 2~
O
O h O O
~CH 2 CH~ (x2) ~CH 2CH~ ~CH2 C~
aliphatic
~CH2 CHCl~ ketone
H2 O
(PVC)
~CHCHCl~
(radical B)
OH aliphatic
~CH 2 CH~ alcohol
H2 H2 H2 H2 H2 H2 H H2
C C C C Cl Δ C C C C Cl
CH CH CH C CH C CH C + n HCl
H2 H n H2
Cl Cl Cl Cl Cl
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O H O H O
CH2-C-CH2-C CH2-C-CH2-C CH2-C-CH=CH
- HCl
Cl Cl Cl
paints. Fillers such as carbon black may also be used the various types of additives used are in combinations,
as screening agents, or the radiation may be absorbed or are compounded into the original polymer to be pro-
harmlessly by chemical agents which dissipate the duced as a special grade for UV protection. It may be
photon energy without chemical change. Radical attractive to add antioxidants to some plastics to avoid
scavengers may be employed to terminate chain radicals photo-oxidation, but care must be taken that the antioxi-
and halt the propagation steps, and various deactivators dant chosen does not act as an UV absorbent, which will
are available that serve to stabilize the hydroperoxide actually enhance the degradation process [81].
groups formed during photolytic oxidation (see Eqs. (1)
and (2)): 20. Additives, reinforcements and fillers
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of additives into synergistic “packages” is becoming (6) Inherent light stability of the UV absorber.
popular, also formulation of liquid systems, rather than (7) Permanence of the UV absorber.
powder, for ease of mixing. The choice of additives must (8) Chemical reactivity of the UV absorber in the pho-
also be dictated by health and safety considerations. todegradation process.
Much work is underway to reformulate PVC additives (9) The UV light and thermal exposure conditions of the
(incidentally the largest % of additives are used in PVC) polymer formulation.
to eliminate heavy metals such as lead, barium and cad-
mium. The optimum amount of UV absorber varies with
each chemical type and application, but in most cases
21. Factors governing choice of stabilizer is in the 0.25–1.0% concentration range. Other factors
to consider while selecting the proper type and amount
It is very important that the UV stabilizer (or com- of UV absorber are color contribution, FDA sanction
bination of UV stabilization) should be selected to suit for food packaging applications, and, of course, add-
the exact application. It is therefore important to identify on cost. The UV absorbers are incorporated into plastic
where an end use product will be used and the required substrates by dry blending, extrusion compounding, and
durability. Other factors that affect the choice of UV sta- then conversion into the final product by various pro-
bilization package include product dimensions, type and cesses such as injection molding, blown film extrusion,
color of pigments present and application information multifilament spinning, and sheet extrusion. Also, UV
such as food contact. absorber dispersions can be prepared and dyed onto tex-
tile fabrics, which will not only UV-stabilize the polymer
22. UV light absorbers substrate but also improve the color stability of the dyes
used to color the fabric. The use of UV absorbers as
A UV light absorber is a type of light stabilizer UV screeners is practiced in a multitude of applications,
which functions by competitive absorption of the UV such as sunglasses, interocular lenses, auto windshield
light energy, causing the photodegradation of a polymer films, solar control glazing films, photographic products,
formulation. The UV absorber competes with all chro- greenhouse films, product packaging, and cosmetic sun-
mophores in the formulation and dissipates the absorbed screens. In each application, the polymer type, the UV
energy as heat. The chromophores are UV light absorb- absorber type, the thickness of the plastic product, and
ing chemical groups in the polymer formulation. These the concentration of the UV absorber need to be con-
may include the polymer itself and other additives, such sidered to meet the reduced UV percentage transmission
as halogenated flame retardants, fillers, and pigments. In requirements of the application [83].
effect, the UV light absorber inhibits the first step in the
polymer photodegradation process, which is photoiniti- 23. UV stabilization mechanisms and strategies
ation. The UV light absorber can be used in combination
with other types of light stabilizers which are designed The initial emphasis in light stabilizer development
to inhibit the other, subsequent steps in the photodegra- was the inhibition of the photoinitiation processes. This
dation processes. Also, UV light absorbers may function UV stabilization strategy consisted of the incorporation
as UV screeners in plastics, coatings, and cosmetic sun- of additives into the polymer or coating formula-
screens to reduce or eliminate the transmission of UV tion, which either absorbed UV light energy or acted
light energy, protecting UV-sensitive substrates. as quenchers of the photoexcited states of the chro-
The factors involved in the effectiveness of the com- mophores. In the former case the UV absorber competes
petitive UV light absorption stabilization mechanism are with the chromophores for the harmful UV light energy,
as follows: which is preferentially absorbed by the UV absorber
and dissipated harmlessly as heat [1]. In this competi-
(1) The UV wavelength region causing photodegrada- tive absorption mechanism, the UV absorber must have
tion of the polymer formulation. relatively high absorptivity at the wavelengths of UV
(2) UV absorptivity of the polymer formulation in this light to which the polymer is photosensitive (activation
region. spectra maxima). In the latter case, the quencher returns
(3) UV absorptivity of the UV absorber in this region. the excited states to ground states by energy transfer
(4) Thickness of the polymer. processes. In both cases, radical formation is inhibited
(5) Concentration and dispersion of the UV absorber. and the outdoor service life of the polymer is extended,
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H3C CH3
N CH3
H3C
G
Fig. 27. HALS ring structure.
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Denisov
H3C CH3 H3C CH3
Cycle H3C CH3
UV light
N CH3 N CH3 N
H3C Oxygen H3C H3C CH3
G O O-R
H3C CH3
N R-OOH R-OO
H3C CH3
H
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18 E. Yousif, A. Hasan / Journal of Taibah University for Science xxx (2014) xxx–xxx
O O OH
OC16H33
OC8H17
HO
Fig. 32. 2-Hydroxy-4-n-octyloxybenzophenone.
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O2 HO
P POO
N N
-e +e
G N C
H
S
P POO
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HO HO *
N N N N
hv
N C N C
H H
S S
G G
S0 S1
O * H *
O
N N Proton N N
H transfer
N C N C
H H
S S
G G
S1 S1
IC
O * H *
O
N N N N
H
N C N C
H H
S S
G G
S0 S0
Proton
transfer
HO HO *
N N N N
N C N C
H H
S S
G G
S0 S0
+ heat
Fig. 36. Mechanism of photostabilization of PVC through absorption of UV light and dissipation light energy as heat (IC).
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HO HO *
N N N N
hv
N C N C
H H
S S
G G
S0 S1
O * H *
O
N N Proton N N
H transfer
N C N C
H H
S S
G G
S1 S1
ICS
O * H *
O
N N N N
H
N C N C
H H
S S
G G
T1 T1
Proton
transfer
HO HO *
N N N N
ICS
N C N C
H H
S S
G G
S0 T1
+ heat
Fig. 37. Mechanism of photostabilization of PVC through absorption of UV light and dissipation light energy as heat (ICS).
Tin carboxylates stabilize PVC by two mechanisms, films blended with a concentration range of 2–2.5% by
depending on the metal. Strongly basic carboxylates, weight of this complex was investigated [131].
which have little or no Lewis acidity, are mostly HCl It has been found that Cr(III) and Fe(III) chelates
scavengers, Fig. 42. enhanced the ratio of C C cleavage via depression in the
IR spectroscopy has shown that metals carboxylates average molecular weight Mw of the studied PVC films.
associate with PVC molecules at the surface of primary However the Zn(II) chelate increased the photostabiliza-
particles and are, consequently, very effective in the tion of the polymer via lowering of the quantum yield
substitution of allylic chlorine. In this mechanism, the φcs of the scissions and indices of carbonyls, hydroxyls
stabilizer is classified as a primary stabilizer. It has been and polyenes.
postulated that metals stabilizers associate with chlorine The photostabilization of PVC was studied using
atoms at the surface of PVC primary particles which a new four heterocyclic compounds containing 1,3-
explains their high efficiency in PVC stabilization [130], oxazepine and 1,3,4-oxadiazole, see Fig. 46.
Fig. 43. These compounds stabilize PVC by different mech-
Metal chelate complexes generally known as photo- anisms such as UV absorber, screener or by radical
stabilizers for PVC through both peroxide decomposer scavenger. These stabilizers provide good long-term sta-
and excited state quencher. Therefore, it is expected that bility and are usually referred to these mechanisms. The
these complexes act as peroxide decomposers through most probable mechanisms involved in a photostabiliza-
the following proposed mechanism, Fig. 44. tion is the hydroxyl group of the additive might acts as
The effect of the tetradentate ligand [H2 L] radical scavenger for photostabilization process. There-
of the N2 O2 type, N{2[3(1-carboxyiminoethyl)-1- fore this Schiff bases, besides acting as UV absorber may
phenyl]butilydene-2-amino propionic acid}, and its also act as radical scavenger additives [122].
metal complexes with Cr(III), Fe(III), Cu(II) and Zn(II), Methyl methacrylate–butadiene–styrene (MBS) ter-
Fig. 45, on the photodegradation of poly(vinyl chloride) polymer has been developed for improving impact
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HO Cl Cl Cl Cl Cl Cl Cl Cl
N N
N C
H HO
S
G N N
PO/OH N C
H
S
O G
N N
N C + POH/H2O
H Cl Cl Cl Cl Cl Cl Cl Cl
S
G
Fig. 40. Mechanism of photostabilization of PVC through the interac-
tion between PVC and Schiff base compounds.
O
N N O
N C
H NH
S
G
O
R
O Sn O
O
N N R O
N C
H HN
S
G
R= -CH3 , -CH2CH2CH3 and O
HO HO *
N N N N
hv
N C N C
H H
S S
G G
HO
HO *
N N N N
N C N C
H
S S H
G G
+
heat
Fig. 39. Mechanism of photostabilization of PVC through absorption of UV light and dissipation light energy as heat.
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O O
NH NH H OP
O
O
R O
R
O Sn O O Sn O
R O
R O
HCl NH
O NH
O O
NH O
NH
OH OH
O
O O R
R + O
O Sn
O Sn +
NH OOP
Cl NH
HCl R R
O
O
R OH
Cl
Sn Fig. 44. Mechanism of photostabilization of complexes as peroxide
Cl
+ O decomposer.
R
NH
Polymer modification can influence the properties of
O
the macromolecule [134]. Recently, scientists does able
Fig. 42. Mechanism of photostabilization of complexes as HCl sca- to modified PVC by introduction aromatic and hetero-
vengers. cyclic moieties through halogen displacement reaction.
PVC, thus modified, showed improved overall pho-
O tochemical stability and optical properties. The facial
NH
chlorine displacement from PVC indicated the possi-
bility on easy anchoring of ligands to PVC matrix. In
O view of paucity of any information on PVC in this line,
R
Cl we undertook the synthesis of PVC-heterocyclic com-
O Sn O
pounds.
Cl The influence of introducing benzothiazole and ben-
R O
zimidazole as a pending groups into the repeating unit
Cl
NH of PVC has been studied on the bases of photostability
O
measurements.
Yousif et al. prepared five modified polymers by the
Fig. 43. Mechanism of photostabilization of complexes as primary covalent modification of commercial PVC with benzoth-
stabilizers. iazole and benzimidazole binding units.
H H
O
N N N N
N N
M M
COOH COOH O O O O O
O
O O
N{2[3(1-carboxyiminoethyl)-1-phenyl] 5,7,11,Trimethyl-9-phenyl-1,3-dioxa-6,10-diaza O
butilydene-2-amino propionic acid} -cyclododeca-6,9--diene-4,12-dione H H
M= Zn (II) and Cu (II)
Diaqua-5,7,11-Trimethyl-9-phenyl-1,3-dioxa-
6,10-diaza-cyclododeca-6,9-diene-4,12-dione
chloride
M= Cr (III) and Fe(III)
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O N N * N
N N
hv
+ heat
N S S S
HS
O
H O
O N N * N
hv
+ heat
N N N
POO
27. Conclusion
OOP
H
Competing interest
Fig. 47. Mechanism of photostabilization of PAA as radical scavengers
through energy transfer and forming unreactive charge transfer and The authors declare that they have no competing
stabilize through resonating structure. interests.
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Please cite this article in press as: E. Yousif, A. Hasan. Photostabilization of poly(vinyl chloride) – Still on the run, J. Taibah
Univ. Sci. (2014), http://dx.doi.org/10.1016/j.jtusci.2014.09.007