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INTRODUCTION
Poly (vinyl chloride) (PVC) is one of the most fascinating, interesting,
universal and oldest thermoplastics of all. On one hand it is the polymer
which comes into contact with a baby’s skin only a few minutes after its
birth, in many countries the bracelet on which the name and the birthday of
the newborn are noted is made of PVC. A lot of other medical items such as
oxygen tents and blood bags are also based on PVC because of the chemical
and physical properties of PVC not offered by other materials. On the other
hand many PVC products, for example toys as children or more durable
items as u-PVC windows, cladding, electrical insulation on wires and cables,
resilient flooring, pipes for land drainage, sewage and drinking water are
with us throughout our lives. Even the coffins that we are finally buried in
are probably covered in PVC foil or veneer and lined with flexible PVC
film.
In this project an attempt has been made to improve the thermal and
physical property of the PVC pipe by optimizing the additives such as
stabilizer for reducing the cost of PVC pipe.
MARKET DATA
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Literature Survey
During the fifty years following the end of World War II, PVC has
become the second most widely used plastic in the world. Today more than
20 million tonnes are Manufactured each year. In Europe the total
consumption of PVC products was estimated at approximately 7.4 million
tonnes in 1998, which corresponds to ca. 5.5 million tonnes of PVC polymer
(ECVM). About one third of the total production of PVC polymer is used for
the production of flexible PVC products, the remaining two thirds fall into
the category of rigid PVC products.
Virgin PVC is thermally and photochemically unstable and depending on
requirements and desired characteristics of the application, a number of
additives are applied to reduce these problems prior to manufacture of PVC
products. The quantitatively important classes of additives are heat
stabilizers, plasticisers, and inert fillers, the latter generally added to reduce
cost and get more volume for a given amount of polymer Other classes of
additives for specific applications include pigments, impact modifiers,
different PVC converters, thus even in the same application (e.g. window
profiles, pipes, films) the composition of the PVC material varies. In the
following sections the most commonly used additives are described in brief.
The effect of additives on the properties and characteristics of the product is
summarised in the following overview:
Table:
and the final application. The most important group of stabilisers are
metal salts (i.e. calcium and zinc stearates, basic lead sulphate and
lead phosphite)
• organo metals (i.e. mono- and diorganotin, tin thioglycolate)
• organo phosphites (i.e. trialkyl-phosphites)
• epoxy compounds (i.e. epoxidised soya bean oil, sunflower oil and
linseed oil)
• antioxidants, polyols (i.e. BHT, pentaerythritol)
Free hydrogen chloride (HCl) evolves and discoloration of the resin occurs
along with important changes in physical and chemical properties. The
evolution of HCl takes place by elimination from the polymer backbone;
discoloration results from the formation of conjugated polyene sequences of
5 to 30 double bonds (primary reactions). Subsequent reactions of highly
reactive conjugated polyenes crosslink or cleave the polymer chain, and
form benzene and condensed and/or alkylated benzenes in trace amounts
depending on temperature and available oxygen (secondary reactions).
Dehydrochlorination of PVC in the Absence of Air (Primary Degradation)
Any mechanism of degradation has to explain a series of experimental facts.
Structural irregularities, such as tertiary or allylic chlorine atoms, increase
the degradation rates measurably at the beginning of the process by a rapid
dehydrochlorination that starts the degradation process (Scheme 3.1). Initial
rates of degradation are proportional to the content of these irregularities.
However, PVC degrades even if these irregularities are eliminated by special
polymerization conditions or treatments because of the dehydrochlorination
of normal monomer units (random elimination) (Scheme 3.1). It is estimated
that after allowing for the differences in concentrations and reaction rates,
the rate of random degradation in commercial PVC because of normal chain
secondary chlorine atoms has the same order of magnitude as does
degradation that results from structural irregularities. Cis-ketoallylic
structures, although very reactive in dehydrochlorination (Scheme 3.1), are
not present in commercial PVC but can be generated by thermal oxidative
processes. After the reactive irregularities initially present are exhausted,
degradation continues because of the elimination initiated from normal
monomer units. These findings indicate that thermal degradation in PVC is
an intrinsic property of this polymer and that changes in synthesis conditions
Not all allylic chlorine atoms preexisting and/or formed in the degradation
process accelerate degradation. Single double bonds can be identified in
degraded PVC by NMR spectroscopy. Double bond sequences, once formed,
do not increase by continuation of degradation. There are allylic chlorides
with some forms of alkenic double bonds that are stable under degradation
conditions . The conjugated polyene sequences are generated in apparently
parallel processes from the first moment of degradation. For relatively low
conversions, their concentrations increase linearly with time. Zero order rate
constants calculated as slopes of these lines decrease exponentially with the
increase of the number of double bonds in the sequence. In the thermal
degradation of solid PVC, an induction period is observed, and then for
higher conversions, the degradation rate increases with time, indicating an
autocatalytic process. Hydrogen chloride formed in the degradation
increases both the degradation rate and the mean number of double bonds in
the polyene sequence, and consequently plays an essential catalytic role in
PVC degradation . Some local configurations and conformations of the
polymer chain of PVC, such as the conformation GTTG (G for Gauche T for
Trans) at the end of certain isotactic sequences, favor degradation. These
conformations exhibit a high local mobility relative to the remaining
structures in PVC and possess some chlorine atoms with very high degrees
of freedom. Both features make possible the adoption of the conformation
enabling the elimination reaction. It follows that dehydrochlorination is
possible only for specific local conformations. Along the same line, PVC
molecules at the surface of primary particles in the solid state have a much
higher conformational mobility than molecules in the interior. PVC
degradation consequently is expected to take place predominantly at the
surface of primary particles. It is well known that dehydrochlorination of
PVC proceeds violently in the presence of Lewis acids such as FeCl3,
ZnCl2, ,AlCl3, SiCl4, GeCl4, SnCl4, BCl3, and GaCl3. This process is
responsible for the very fast discoloration of PVC in the presence of Zn or
Sn carboxylates that act as stabilizers till the corresponding halides are
formed and fast dehydrochlorination starts. The reaction mechanism of a
complex chemical process such as PVC degradation defines the sequence of
elementary reactions leading from reactants to products and describes each
The first elimination from a monomer residue from the chain (-CH2-
CHCl-) or a structural irregularity such as a tertiary chlorine atom (-CH2-
CCl<) forms an active intermediate or a stable monoalkene. This active
The major problem with this mechanism is that the chlorine atom is known
to be so reactive as to be non-selective. Data on model compounds showed
that the allylic hydrogen atom, (>C=CH-CH2-CCl<), has only slightly
formation of a double bond randomly along the polymer chain via a 1,2-
unimolecular elimination of HCl through a four-center transition state
(Scheme 3.5) or a
The second and third steps of the processes constitute the chain
elimination, regardless of the initiation site. In the second step, an HCl
molecule is eliminated from a cis _-alkyl-allyl chlorine through a six-center
transition state, generating a conjugated diene or polyene.
straight line. This suggests that both processes may have the same
mechanism: a 1,2-elimination of hydrogen chloride from a synperiplanar
conformation involving backbone chlorine through a transition state of four
centers. In the same way, it was shown that the chain reactions may have the
same mechanism as the elimination from cis _-alkyl-allylic chlorides
(chloroalkenes): a 1,4-elimination of hydrogen chloride through a transition
state of six atoms from a cis allylic structure. Only the cis-allylic system
with one double bond that has a relatively low activation enthalpy of
dehydrochlorination is reactive in chain propagation in the degradation
process. Trans conjugated polyenes are much more stable in the absence of
HCl. To dehydrochlorinate, they require a 1,2-elimination at the one end that
has a much higher activation enthalpy. This process is similar to a random
initiation and is much more likely statistically to occur at a different place in
the polymer molecule or on a different polymer molecule entirely. In this
way, a chain reaction, once interrupted, does not continue, and the sequences
of conjugated polyenes remain as such in the system. Trans conjugated
polyenic systems are known to be very stable relative to their cis isomers
because of their favorable conformation that allows polymer packing to
occur.
polyenes longer than four to five double bonds and maintain very good early
color in the polymer. These stabilizers are called primary stabilizers.
• Scavenging the hydrogen chloride generated by degradation is another way
to stop the process as the HCl is a catalyst for the chain propagation reaction
and the initiation step. However, the diffusion of HCl is quite slow because
HCl is associated with the double bond where it was generated. When HCl
diffuses away from the reaction center, the zipper degradation reaction stops.
The stabilizer should scavenge HCl with high effectiveness to avoid its
catalytic effect in chain initiation that starts another zipper
dehydrochlorination chain. Because this type of stabilizer cannot prevent the
dehydrochlorination in its early stages, polyenes longer than four to five
double bonds are formed. PVC discolors and the initial color is not
maintained. However, by scavenging HCl, this type of stabilizer avoids the
autocatalytic degradation and consequently, overall degradation is much
slower. These stabilizers provide very good long term stability and are
usually referred to secondary stabilizers.
To have good stabilization of PVC with good early color and long term
stability, the two types of stabilizer should be combined appropriately for
each particular PVC formulation. Stabilization is complicated by the fact
that primary stabilizers become strong Lewis acids by reacting with the HCl
that catalyzes the initiation and propagation of PVC degradation. To avoid
this, secondary stabilizers should react efficiently with HCl to protect the
primary stabilizers. Another possibility is to include compounds called
costabilizers in the system. Costabilizers form relatively stable complexes
with the chloro derivatives of primary stabilizers (the Lewis acids) and
suppress their degradative effect.
The most important classes of stabilizers and how they act in PVC
stabilization is briefly discussed below.
Alkyltin Stabilizers:-
The most commercially important alkyltin derivatives are the mono and
dimethyl-, butyland octyltin alkyl thioglycolates, mercaptopropionates and
alkyl maleates. All these compounds react with HCl to form the
corresponding tin chlorides (Scheme 3.10). However, their stabilization
effect does not correlate with the amount of HCl reacted nor with the rate of
this reaction. It has been established that in the stabilization of PVC with
alkyltin alkyl thioglycolates, alkyl thioglycolates are released by reaction
with HCl . These alkyltin compounds consequently function as secondary
stabilizers, but this is not the main mechanism of their action.
increased and becomes the dominant process in PVC stabilization. The early
color is very considerably improved.
Diketones Stabilizers:-
Diketones and similar compounds with active methylenes react in the
presence of Zn carboxylates as catalysts with allylic chlorides generated by
PVC degradation by a Calkylation process . The stabilization effect
increases with the CH acidity of these compounds .
Hydrotalcites Stabilizers:-
Among these, the liquid thioglycolates are the predominant group on the
market. Mono- and diorganotin mercaptides are often used in combination,
because these mixtures improve initial color as well as the long-term heat
stability of PVC (synergistically) . This is shown in Fig. 3.2.
Organotin Carboxylates:-
Only carboxylates carboxylate with the following structures are of practical
interest (Scheme 3.19):
Optimum results are obtained when they are combined with small amounts
of phenolic antioxidants, particularly in plasticized PVC, impact-modified
PVC, and PVC copolymers. Because stabilizers containing maleic acid
occasionally lead to eye and mucous membrane irritations, there have been
many attempts to replace them with other systems. For many years,
organotin stabilizers free of maleic acid have been on the market. These
consist of a combination of organotin carboxylates, e.g., laurates, and a
small amount of an organotin mercaptide. Just as with sulfur-free organotin
stabilizers, when used in a suitable formulations, this combination gives
rigid PVC high transparency and excellent weathering stability. In the melt,
PVC stabilized with alkyltin maleates tends to stick to hot contact areas of
the processing equipment. However, this problem can be prevented by
suitable lubricants. Organotin carboxylates work especially well in the
manufacture of rigid or plasticized PVC articles for outdoor use, as for
example, transparent and translucent double-walled panels for greenhouses,
siding, and window profiles, particularly when pigmented.
Recommended Formulations
Sr.no Ingridient %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 1.6
7 Dibasic lead sterate 0.8
8 Calcium sterate 0.8
9 Lead sterate 0.4
Experimental Work
In this project we have processed the PVC pressure pipe of different
compounding minimizing the percentage of stabilizer and we have taken the
thermal stability test as well as other standard test for determining the
properties of PVC pipes.
We have made various batches of different composition which is
given below.
BATCH –A
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Steraic Acid 0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 0.7
7 Dibasic lead sterate 0.5
8 Calcium sterate 0.5
9 Lead sterate 0.2
BATCH –B
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 0.8
7 Dibasic lead sterate 0.55
8 Calcium stearte 0.55
BATCH –C
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 0.9
7 Dibasic lead sterate 0.6
8 Calcium sterate 0.6
9 Lead sterate 0.3
BATCH –D
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 1.
7 Dibasic lead sterate 0.65
8 Calcium sterate 0.65
BATCH –E
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 1.1
7 Dibasic lead sterate 0.7
8 Calcium sterate 0.7
9 Lead sterate 0.4
Compounding
Compounding temperature 110 -120°C
Compounding time 15 min
Pipe Dimension
diameter of pipe 25mm
length of pipe 3m
thickness of pipe 1.5mm
weight of pipe 450 gm
Test for compounds.
Theory:-
Resin sample is heated and emitted vapour are passed through a tube
containing canes red paper . The liberation of HCL is indicated by the colour
change.
Principle :-
During the degradation of PVC ,HCL is liberated which changes the
colour of canes red paper to blue.
Apparatus:-
i. Red indicator paper : 6 mm X50 mm.
ii. Stop-watch with accuracy of 0.2 sec.
iii. Oill bath : Capable of maintaining the temperature to the accuracy of
1°C in the range of 120 to 210°C ( Chetan Electrical Worksmake ).
iv. Stirrer with variable speed (Remi make).
v. Test tube : 18 + 1 mm diameter ,150 + 2 mm length.
vi. Rubber stopper : With a hole to accommodate 2+3 mm diameter tube.
vii. Silicon oil : Viscosity of 50 + 5cp
Safety:-
Carry out the experiment in the fuming chamber with glass door shut.
Wear safety glasses during test.
Procedure :-
1) Heat the oil bath to test temperature (180°C) and maintain in it
0+2°C.
2) Fill the test tube with sample PVC resin up to 50+2 mm depth ( do
Reversion Test:
A 20 cm peace of pipe on which two marks are made 100 mm apart,
and is placed in oven at 150 °C for 1 hour After the stipulated time is over
the reduction in length of 100 mm mark is measured. The Shrinkage is less
than 5% than the sample was passed the reversion test was accepted for the
ISI test.
Batch Shrinkage
A 2%
B 3%
C 4%
D 3%
E 3%
Water absorption:-
The 4.5 cm length of pipe is cut and weight. The beaker of 500 ml is
taken then the distilled water of 250ml is taken into this beaker. And the
piece of pipe is immersed for 24 hr. and this pipe is weighted after
Each specimen shall be drawn with longitudinal parallel line not less
then 50 mm. the weighted striker shall be allowed to fall freely on the mark
line. If the specimen does not fail by cracking or splitting, the specimen shall
be rotated to the next longitudinal line and so on. The process shall be
repeated until all the marked lines have been tested or until a failure is
recorded. If 14 strikes are made without failure pipes shall be deemed to
have passed the test.
Test
A B C D E
Batch
Thermal 102 114 110 117 115
stability
(in min)
Conclusion
Worldwide demand for plastic pipe is forecast to increase more than
four percent per year through 2007, continuing to outpace gains for overall
pipe demand. This continues increase in production would not been possible
without the improvement in processing of PVC pipe with changes in
additives proportion during compounding.
This makes us to thing that why not we make the pipe which gives
good individual properties in PVC pipe system with economical aspect.
After thermal stability test and other test for various properties we have
concluded that % of stabilizer used in batch B improved the properties such
as thermal stability which reduces the percentage of stabilizer to about 30
percent.
Thus the batch B is giving similar properties like standard formulation
so it reduces the cost of processing to two percent.
References
BOOKS:
1) PVC Technology by A.S.ATHALYE & Dr.PRAKASH TRIVEDI first
edition 1994 page no: (197-199), (168-169),(92-120).
2) PVC Stabilization by JERRY WYE PITCH 4th edition page no (12-
30),(198- 220),
3) PVC Technology by W.Y.Titow Elsevier applied science publication,
London and new York page no 4-23,37-49,59-65
4) Plastic material 5th edition (1995), J.A. Brydson butter worth
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