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POLITEHNICA UNIVERSITY of Bucharest

Faculty of Engineering in Foreign Languages


Chemical Engineering

DIPLOMA WORK
Suspension polymerization of vinyl chloride

Graduate:
Denis-Maria tefnescu

Scientific Coordinator:
Prof. Dr. Eng. Celina-Maria Damian

Bucharest
2016
1

Preface

This work is branched into six parts. The first part is about polymers and respectively
polyvinyl chloride fundamentals. This embraces a brief discussion of the history and discovery
of polyvinyl chloride, main applications and main producers of polyvinyl chloride in the world
and also the physical properties of polyvinyl chloride.
The second part is about the techniques used for polyvinyl chloride synthesis as: bulk
(mass) polymerization, emulsion polymerization and suspension polymerization. Also, there
will be presented the suspension polymerization scheme.
The third part of the work deals with the polyvinyl chloride recycling (mechanical
recycling and chemical recycling). It will be further presented an analysis of the options to
chemically recycle the wastes rich in polyvinyl chloride.
The forth part of the work is about the technological dimensioning. There will be
calculated the number of batches, reactors, the thermal balance, the material balance, and so
on. Further on, it will be reviewed the technological flux and the technological predimensioning.
The fifth part of the work deals with a briefly described application of the polyvinyl
chloride.
The last part of the work is related to the considerations about the impact on the
environment, and economical consideration.

Acknowledgement

In writing this work, I have had to lean on materials from different sources. These
sources will be mentioned as references on the final page of the work. I express my apologizes
for any materials and ideas which I have negligently failed to acknowledge.
I would like to express my special thanks of gratitude to my professor Celina-Maria
Damian, who gave me the opportunity to choose this interesting yet helpful project about the
suspension polymerization of vinyl chloride, which also helped me in doing a lot of research and
I came to know so many new things.
I would also like to thank my other professors from the Polymer Science and
Engineering department for ambitioning me to study the beauty of polymers.
I take full responsibility for any lapses and errors that may be contained in this work.

TABLE OF CONTENTS

Introduction
Chapter 1: Technical Documentation
1.1. History of polyvinyl chloride
1.2. Applications of polyvinyl chloride
1.3. Additives
1.4. Properties of polyvinyl chloride
1.5. Leading producers in the world
1.5.1. Polyvinyl chloride industry in Europe
1.6. European Regulatory

Chapter 2: Technological procedures


2.1. Chemistry of the polyvinyl chloride synthesis
2.1.1. Free radical polymerization of vinyl chloride characterization
2.1.2. The mechanism of the free radical polymerization
2.1.3. Free radical polymerization influencing factors
2.2. Bulk polymerization of vinyl chloride
2.3. Emulsion polymerization of vinyl chloride
2.4. Suspension polymerization of vinyl chloride
2.5. Advantages and drawbacks of suspension polymerization process
2.5.1. Advantages
2.5.2. Drawbacks
2.6. Technology of the suspension polymerization of vinyl chloride process

Chapter 3: Polyvinyl chloride recycling


3.1. Mechanical recycling
3.2. Chemical or feedstock recycling

Chapter 4: Technological dimensioning


4.1. Projection recipe
4.2. Batch number calculation
4.3. Reactors number calculation
4.4. The calculation of the fabrication recipe
4.5. Material balance
4

4.6. Technological flux to obtain polyvinyl chloride in suspension technique


4.7. Thermal balance
4.7.1. Heating the reaction mixture at 20-58oC
4.7.2. Taking over the reaction head
4.7.3. Cooling the reaction mixture from 58 to 20oC
4.7.4. Thermal balance on the dryer
4.7.5. Thermal balance on the heating radiator
4.7.6. Verification of the thermal transfer area of the reactor
4.7.7. Calculation steps for the partial thermal coefficient, alpha 1
4.7.8. Calculation steps for the partial thermal coefficient, alpha 2
4.8. Calculation of the diameter of the reactor

Chapter 5: Polyvinyl chloride application briefly described PVC


Pipes
5.1. Generalities
5.2. Manufacturing
5.3. Advantages and drawbacks for using PVC Pipes

Chapter 6: Considerations regarding the impact on the environment


and the economy
6.1. Considerations regarding the impact on the environment
6.2. Economical consideration

BIBLIOGRAPHY

Introduction
Polyvinyl chloride (PVC), or using the IUPAC name poly (1-chloroethylene) or poly
(chloroethanediyl) is one of the most important thermoplastic polymers and it has been very
successful in the world for more than 50 years, being the most used plastic material recognized
internationally on the market due to its wide range of applications. It is obtained by the
polymerization of the vinyl chloride through all the known procedures: bulk polymerization,
suspension polymerization, emulsion polymerization, and solution polymerization at an
industrial level being applied only the first three procedures. [1] Polyvinyl chloride is a solid
plastic with no specific smell. It is usually white, but it can also be colorless or amber. It can also
be a powder. Polyvinyl chloride can become more flexible by adding phthalates and it can
become plastic by adding Bisphenol A (BPA) [2].
Thus, the purpose of this work is to mainly present the suspension polymerization of
vinyl chloride technique which refers to a polymerization in an aqueous medium and the
dispersed phase is the monomer. The polymer resulted from this kind of system figures out a
solid dispersed phase. [3]
H

Cl

The structure of vinyl chloride and


respectively of polyvinyl chloride
(PVC)

C-C

C=C
H

Cl

This work is divided in six parts: the technical documentation, the alternate
technological techniques, the recycling of polyvinyl chloride, the technological dimensioning,
an application of the polyvinyl chloride briefly described, and also the references.
The first part, Technical documentation is about the history, applications,
additives, properties, leading producers in the world and also about the European
Regulations.
The following part is about the technological procedures through bulk
polymerization, emulsion polymerization and suspension polymerization which will be
described in details.
The third part is about the recycling of polyvinyl chloride which is chemical or
mechanical recycling.
The next part is about the technological dimensioning which will include the
computations of batches, reactors, material balance, the technological flux and the thermal
balance.
In fifth part is presented an application of the polyvinyl chloride, briefly described.
In the sixth part there are presented the considerations regarding the impact on the
environment, and also the economical consideration.
The last part of the project is related to the references.
6

CHAPTER 1: Technical documentation


1.1. History of polyvinyl chloride
Polyvinyl chloride (PVC) is one of the earliest fabricated materials. The polyvinyl
chloride as its monomer, vinyl chloride, was accidentally discovered on at least two
opportunities in the 19th century. The first incident happened in 1838 by the French physicist
and chemist, Henri Victor Regnault (Figure 1.1.), who mainly studied gases and experimented
with vinyl chloride gas. Once, he left a sample at direct sunlight and then he was surprised to
find a white solid in the flask, which turned out to be the polyvinyl chloride. The second incident
happened in 1872 by the German chemist, Eugen Baumann (Figure.1.2.).

Fig 1.1. Henry Victor Regnault


Source: www. wikipedia.com

Fig. 1.2. Eugen Baumann


Source: www.wikipedia.com

The most compelling discovery occurred when the American aerospace manufacturing
BF Goodrich Company hired Waldo Semon (Figure 1.3.), an industrial scientist, who due to all
his experiments, produced polyvinyl chloride and he was the first who discovered a method to
plasticize polyvinyl chloride in 1926. Semon assumed that polyvinyl chloride is a water
resistant coating for fabrics. Sales blown quickly with a fast increase of the product range.
Sales accelerated during the Second World War when the polyvinyl chloride replaced the
classical material to insulate wiring on military ships.

Fig. 1.3. Waldo Semon, American industrial scientist


Source: http://archive.wired.com/geekdad/2009/05/the-grandfather-of-the-potato-cannon/ , 2009: page 1

In the 1950s more and more companies begun to synthesize polyvinyl chloride all
around the world. Also, more and more innovative uses of the polyvinyl chloride had been found
and a lot of methods had been found out to increase the polyvinyl chloride durability.
As every year passing, the polyvinyl chloride became essential to the construction
industry due to its resistance to chemicals, light and corrosion, being the best option for building
applications not just because of its resistance, but also for its low cost, for its excellent durability
and processability. Today, polyvinyl chloride is the third largest-selling plastic in the world after
polyethylene and polypropylene. [4]

1.2. Applications of polyvinyl chloride


Polyvinyl chloride has a wide range of applications, being the most used plastic material
in the world and an extremely durable and chemical resistant material, which resists attack or
degradation from a wide range of chemicals, making it the ideal material in many industrial
applications. In everyday life, polyvinyl chloride is all around us, from constructions to medical
devices, from childrens toys to credit cards, and so on.

Fig. 1.3. The production of PVC products


Source: http://www.pvc.org, page 1

Typical applications for polyvinyl chloride:


1.
2.
3.
4.
5.
6.

Everyday life applications;


Construction Buildings applications;
Medical applications;
Electrical applications;
Automotive applications;
Art and design.

1.
Everyday life applications. Polyvinyl chloride is used in the clothing industry
where it can replace leather which offers a great flexibility at an affordable price. Polyvinyl
chloride is also used for furniture (the rigid one is used for handles and panels, and the flexible
one is used for coverings and floorings). Also, polyvinyl chloride is used as a material for cards
(credit, debit and phone cards). Because it is a thermoplastic, the numbers on the cards can be
easily printed just by adding heat. Polyvinyl chloride is also used for sports equipment ranging
from rugby and football to golf and sailing;
2.
Construction Buildings applications. Polyvinyl chloride is the most used
material for constructions because it is strong and it has a low weight, it has good mechanical
strength, it is easy to be cut and shaped, it is resistant to corrosion, weathering, abrasion and
shock. In applications such as windows, studies indicate that more than 60% of them have the
life time of approximately 40 years. Polyvinyl chloride is also used in constructions because of
its low price and because it is safe. It is a non-toxic polymer, and thus, it meets all international
standards for safety and health; [4]
3.
Medical applications. Polyvinyl chloride is used for medical applications for
more than 50 years. Examples of medical applications: heart and lung bypass sets, tubing for
dialysis, surgical gloves, inhalation masks, blood bags, etc. The most important thing to take into
consideration when using medical application is the non-toxicity of the material, making the
polyvinyl chloride one of the non-toxic materials. Also, polyvinyl chloride is characterized by a
high biocompatibility and a high transparency to allow continuous monitoring of fluid flow;
4.
Electrical applications. Because polyvinyl chloride has good insulating
properties, it is perfect for wiring and cables used in household goods such as cookers and
fridges. Also, coloured wires can be made from polyvinyl chloride which is important to
identify the wires for different purposes; [5]
5.
Automotive applications. The most important polyvinyl chloride applications for
automotive are the following: dashboards, door panels seating, arm rests, body side protection
strips, weather strips, underbody coatings, sealants, floor modules, cable insulation, etc.
Nowadays, because of the polyvinyl chloride, vehicles last longer. The life-time of a vehicle is
now 17 years in comparison to 11 years in the 1970s. This is an advantage because if a
vehicle lasts longer means saving more natural resources. Polyvinyl chloride is also important

because it saves lives. It is used in shock-absorbing vehicle components, diminishing injury in


case of impact;
6. Art and design. Polyvinyl chloride is frequently used by designers. It begun to be a
good, modern alternative to classic materials such as: glass, metal and ceramics, polyvinyl
chloride being both flexible and rigid, durable and with low weight, and it can be shaped and
colored easily. [4]

There are three types of polyvinyl chloride:


-

Rigid polyvinyl chloride (PVC-D);


Plasticized polyvinyl chloride (PVC-M);
Chlorinated polyvinyl chloride (PVC-C).
Rigid polyvinyl chloride PVC-D

Rigid polyvinyl chloride is obtained through vinyl chloride in suspension or in


emulsion with the K value 50 - 60 in the compounds, without any plasticizer. The K value
was introduced by Fikentscher to correlate relative viscosity with the average polymerization
degree. The K values are used in PVC industries.
Due to its properties, PVC-D is used in: constructions, component pieces for the pumps
which function in corrosive conditions, gramophone disks, isolating pieces for the electro
technical industry, pieces for the photographic industry, and pieces with diverse destination.
Theres also an auxiliary type of polyvinyl chloride: Semi rigid polyvinyl chloride with a
5-10% amount of plasticizer.
Plasticized (flexible) polyvinyl chloride PVC-M
Plasticized polyvinyl chloride is obtained through PVC in suspension or in emulsion with
the K value 55 - 66 in compounds with 10 60% plasticizers.
This kind of polyvinyl chloride is used at: fabricating buffer elements for radios
and telephones, toys, foot-wear industry, pieces for installations, etc.
Chlorinated polyvinyl chloride PVC-C
Chlorinate polyvinyl chloride is a polyvinyl chloride with a chloride additive of 6470%. This type of polyvinyl chloride is used at: component pieces and shutters for the
apparatus in the chemical industry, pieces in galvanotechnics, electrical component pieces
which work in corrosive medium, etc. [6]

10

1.3. Additives
Types of additives
The composition of polyvinyl chloride, depending on the application, can vary because
different quantities of additives are integrated into the polymer:
- Stabilizers;
- Plasticizers;
- Fillers;
- Lubricants;
- Pigments;
- Flame retardants.
The most used and important additives which need to be added are stabilizers (lead,
cadmium), and plasticizers (phthalates).
Stabilizers
The stabilizer is a chemical compound which inhibits a reaction between two or more
chemicals. It can be told that is the antonym of a catalyst. Polyvinyl chloride needs stabilizers in
order to avoid the degradation by heat and light.
Lead stabilizers are the most used (lead sulphate, lead phosphite). Lead compounds are
also cost-effective. They are used mainly in pipes, profiles and cables.
Cadmium stabilizers are mostly used for window frames. Calcium stabilizers had never
been used for foods or toys because according to Council Directive 67/548/EEC they are
dangerous for the environment.
Calcium/zinc and barium/zinc are the most frequently used stabilizers.
Organotin compounds can be also used as stabilizers. They are mixtures of mono- and diorganotin compounds. They are used for bottles, roofing, etc.
Plasticizers
A plasticizer is a substance added to a synthetic resin to produce plasticity and flexibility
and also to reduce brittleness.
Plasticizers or dispersants have been used to make things soft and flexible for thousands
of years. They are colorless and odorless liquids which cant be simply treated just like additives.
Plasticizers are usually organic liquids of high boiling points or low melting solids. They are also
miscible with the polymer. Nowadays, over 90% of the plasticizers used in Europe are used in
flexible polyvinyl chloride applications (automotive, construction).
The most common plasticizers used are the phthalates or to be more specific, the
ortophtalates. For example, in 1997, 93% of the plasticizers used for PVC were the phthalates.
The optimal plasticizer must satisfy three conditions: compatibility, performance and
efficiency. In addition, it should be nontoxic, tasteless, nonflammable, odorless and heat stable.
In conclusion, without any additives PVC would not be a very useful substance, but its
compatibility with a wide range of additives results in a wide range of applications. [7]
11

Fillers
Fillers can enhance resin and increase stiffness and strength. They prevent inhibition in
dies and neutralize the products of degradation. Fillers can also be used to add color, opacity,
and conductivity to a compound.
Fillers in percentage:
-

80% of all the fillers used in PVC is calcium carbonate;


12% of all the fillers used in PVC is titanium dioxide;
5% of all the fillers used in PVC is calcinated clay;
The remaining percent of all the fillers used in PVC are other materials, including glass
and talc. [8]

Fillers are inorganic materials having a lower refractive index than the true pigments.
The majority of fillers are naturally occurring minerals (calcite, chalk, dolomite, kaolin, talk,
diatomaceous earth, barite, quartz), although some of them are obtained synthetically by
precipitation reactions. The most important filler in volume terms is calcium carbonate shown
also in the above percentages. In the form of the crystalline calcite and the amorphous chalk,
calcium carbonate covers about 80-90% of the overall demand for fillers in Western Europe.
Fillers are used essentially for cost reduction, but also for modifying the properties in
paints. In general, fillers increase the solidity, the volume and the specific weight. [9]
Also, an excellent additive, developed by additives manufacturer Vin Industries, called
roAid have been developed to increase filler loading (i.e. increase the amount of filler Calcium
carbonate) in PVC pipes. Usually, when increasing the filler loading, the physical properties of
the product diminish, but with the help of ProAid additive, the physical properties of the product
are maintained. ProAid comes in the form of white granules. [10]
Lubricants
Lubricants are of two types: internal lubricants and external lubricants.
Internal lubricants diminish the friction forces between the polyvinyl chloride chains
and further on lowering the melt viscosity. These internal lubricants are very compatible with the
polyvinyl chloride due to their polarity.
External lubricants lower the adhesion between the polyvinyl chloride and the metal
surface. Compared to internal lubricants, most of external lubricants are non-polar (paraffin,
polyethylene waxes). [11]
As for the polyvinyl chloride, in 2012, Clariant, a Swiss specialty chemicals company,
has rolled out a new generation of lubricants. This lubricant offers great performance and
efficiency. The chemically modified lubricant was produced from soya bean oil and not from
fatty acid derivatives used in the past for lubrication. Therefore, this lubricant offers superior
technical performance in polyvinyl chloride processing. This lubricant, called Licocare acts as
both external and internal lubricant. [12]
12

Pigments
Because design is important, pigments must be added to color the specific polyvinyl
chloride material, permanence and stability being the most desired properties.

1.4. Properties of polyvinyl chloride


In a few words, polyvinyl chloride is a general purpose plastic. It is strong and rigid,
resistant to a variety of bases and acids but it might be damaged by some solvents and
hydrocarbons.
Molecular formula: (C2H3Cl)n
Appearance: white, brittle solid
Solubility: insoluble in alcohol but soluble in THF (Tetrahydrofuran)
Polymer type: thermoplastic, amorphous. It has polar groups and thus contributing to ease of
coloring, printing and adhesion. [21]
In the following table (Table 1.1.) there will be presented some important properties of
the polyvinyl chloride:
Property
Density
Tensile strength
Compression
strength
Bending
strength
Rockwell durity
Elongation at
break
Thermal
expansion
coefficient
Specific heat
Electrical
resistivity
Dielectric
constant (50 Hz)
Dielectric loss
factor
Water
absorption

Unit
3
G/cm
2
N/mm
2
N/mm
N/mm

PVC-D
1.35 1.45
34 62
55 90

PVC-M
1.15 1.35
7 25
7- 12

PVC-C
1.5 1.6
42 62
-

70 100

100
82 86
3.5 7.5

65 85
2-4

Plastifying
function
40 100
200 450

-5 o

5 18.5

7 25

Cal/g C
Ocm

0.2 0.28
16
10

0.3 0.5
11
13
10 10

15
16
10 10

3.2 3.6

59

3.2 3.6

0.007 0.02

0.008 0.15

0.02

0.4

0.8

10 / C
o

0.1

Table 1.1. Polyvinyl chloride properties


13

1.5. Leading producers in the world


With every year passing, the chemical industry of polyvinyl chloride has been
developed, such that the polyvinyl chloride production increased gradually. In 1977 the world
wide PVC production was approximately 26 million tones, this increasing and reaching 29.9
million tons in 2009 and in 2011 at approximately 47.5 million tones. It is expected that in the
year of 2020 the polyvinyl chloride production will reach 59 million tones. Most of these
increases occurred in China, which now has approximately 40% of the worlds total of
polyvinyl chloride.

Fig. 1.7.: Worldwide PVC consumption in 2012, broken down by region


Source: https://www.vinnolit.com, page 2

Asia is by far the biggest market, followed by Europe and North America.

Fig. 1.8.: China PVC Production and consumption


Source: http://www.dce.com.cn, page 1

14

1.5.1. Polyvinyl chloride industry in Europe


Industry of polyvinyl chloride in Europe is strongly committed to resist. Within Vinyl
2010s attempts to begin something new, it is regularly trying to upgrade products and
production processes, invest in technology, and minimize waste.

At European scale, the polyvinyl chloride industry is expressed by four associations:


ECVM (the European Council of Vinyl Manufacturers): The 13th European PVC resin
producing companies, which produce 100% of the European PVC resin production;
ESPA (the European Stabilizers Producers Association): The 11th European companies
which produce stabilizers, 98% of the stabilizers produced in Europe;
ECPI (the European Council for Plasticizers and Intermediates): The 7th European
producers of plasticizers and intermediates;
EuPC (the European Plastics Converts): 50,000 companies in Europe which produce 45
million tons/year of plastic products. [13]

Figure 1.9. Areas of use of PVC in Europe


Source: http://www.safeinfusiontherapy.com

After the Vinyl 2010 success, the industry of the polyvinyl chloride of Europe has set
new targets to develop Vinyl 2020 (VinylPlus). The targets in VinylPlus are: the recycling of
800,000 tons/year of polyvinyl chloride by 2020, where 100,000 tones are treated by innovative
technologies. [14]

15

1.6. European regulatory


Regulation 1272/2008 (EC) on classification, labeling and packaging of substances and
mixtures at concentrations higher than 0.1% of additives in the product, and there are necessary
product safety tests on individual health amending and repealing Directives 67/548/EEC and
1999/45/EC, amending Regulation (EC) no. 1907/2006. This Regulation should ensure a high
level of human and environmental protection and also the free movement of chemical
substances, mixtures and specific articles while enhancing competitiveness and innovation.
Regulation 1907/2006 (EC) on Registration, Evaluation, Authorization and Restriction
of Chemicals REACH is a European Union regulation intended to ensure a high level of
protection of human and environmental health, manage and control the potential risk for the
human and environmental health due to using the chemical products in the European Union,
given the free circulation of substances, mixtures and articles.
Regulation (EU) 453/2010 regarding the information in the safety data sheet must be
written clearly and concisely. Safety data sheet must be prepared by a competent person who
shall take into account the specific need and users knowledge as far as they are known.
Suppliers of substances and mixtures shall ensure that the competent persons have
received appropriate training, including refresher training.
Directive 2002/72/EC of 6 August 2002 relating to plastic materials and articles made of
plastic materials intended to come into contact with food stuffs. It has been established under
this Directive that the substances from the food packages must not migrate in another
environment more than 60 milligrams in a pound.
Directive 2005/84/CE of the European Parliament and of the Council from 14
December 2005, making of the twenty-second amendment to Directive 76/769/EEC on the
approximation of laws, regulations and administrative provisions of the Member States relating
to restrictions on the marketing and use of certain dangerous substances and preparations
(phthalates in tows and childcare articles).
According to this directive, using certain phthalates in toys and childcare articles made of
plasticized materials or including parts made of plasticized materials, should be prohibited as the
presence of certain phthalates could constitute a health hazard to children. Toys and childcare
articles that can be placed in the mouth, although not made for that purpose, may, in certain
circumstances, constitute a health hazard to young children if those articles are made of
plasticized materials, or include parts of plasticized materials containing certain phthalates.
Regulation (EC) no. 282/2008 of 27 March 2008 on recycled plastic materials and articles
intended to come into contact with foods and amending Regulation (EC) no. 2023/2006,
16

aims to create a more efficient and practical system for reusing plastics in food packaging.
Directive 2001/95/EC of the European Parliament and of the Council of 3 December
2001 on general product safety, both producer and distributor should cooperate with the
competent authorities in action, aimed at risk prevention, and to inform them when they
conclude that certain products supplied are dangerous. The condition on supplying this
information must be stabilized by the present directive to ease its efficiency, meanwhile
avoiding an excessive burden of economical operators and authorities.
Within the limits of the respective activities, the producers adopt measures
corresponding to the characteristics of their supplied products which must permit:
a) To be informed about the risks these products must present
b) To choose appropriate measures, including, if necessary, to avoid these risks, retire from
the market, warning in an appropriate and efficient way the consumers.
Directive 2005/84/EC of the European Parliament and of the Council of 14 December
2005 to make the 22nd change of the Directive 76/769/EEC of the Council about the
approximation of the laws of the Member States and of the administrative provisions relating to
restrictions on the use of certain substances and dangerous preparations (phthalates in toys and
in childcare articles) on the market.
Using phthalates in toys and in childcare articles made out of plasticized materials or
including pieces from plasticized materials should be forbidden because the presence of some
phthalates could be a risk for the childrens health.
Children, as human beings continuously developing, are vulnerable especially at toxic
substances for reproduction. Consequently, it must be reduced as much as it can be, the
exposure of children at all the emitting sources of these substances which can be concretely
avoided, especially the emissions coming from the articles which children place them in their
mouth.
While evaluating the risks or at the Directive 67/548/EEC of the Council on 27 June
1967, packaging and labeling the dangerous substances, di(2-ethylhexyl)phthalate(DEHP),
dibutylphthalate(DBP) and butyl-benyl phthalate(BBP) had been identified as toxic substances
for reproduction. [15]

17

CHAPTER 2: Technical procedures


2.1. Chemistry of the polyvinyl chloride synthesis
2.1.1. Free-Radical polymerization of vinyl chloride characterization

The majority of the monomers are polymerized by free-radical polymerization, the


reaction rate being influenced by the steric effects.
The free-radicals are classified as follows:
-

Highly reactive radicals: This kind of radicals has a very short life. These radicals are
also unconjugated and they dont have steric stabilization;
Medium reactivity radicals: This kind of radicals has an average life-time. These
radicals can be: Relatively unstable radicals and relatively stable radicals;
Unreactive radicals: This kind of radicals has a very long life-time due to the high steric
hindrance. They are not capable to initiate chain growth. In this way, unreactive radicals
are considered inhibitors (i.e.: triphenyl-methyl, diphenyl-picryl-hydrazyl, etc.).

The free-radical polymerization of vinyl chloride is a chain addition process with four
steps: initiation (the monomer molecule is transformed in a radical), propagation (chain
growth), chain transfer (side reaction), and termination (two radicals give an inert polymer
chain).
The general scheme of the four steps:
Initiation:
I

kd

kd = dissociation rate constant


kp = propagation rate constant
ktr = chain transfer rate constant
kt = termination rate constant

R + M

RM

Propagation:
kp
M + M

MM

Chain transfer:
ktr

M + X

M +X

Termination:
2

kt

= Primary radical
X = any substance present in the
system including the monomer, the
dead polymer and the initiator.
[16]

18

Vinyl chloride is an unconjugated monomer with low reactivity which gives radicals
with high reactivity. Because of this, its radical polymerization is accompanied by powerful
chain transfer reactions with the monomer and the polymer.
Due to the intense chain transfer reactions with the monomer, the molecular mass of the
polymer which has been resulted doesnt depend on the initiator concentration.
The molar mass of the polyvinyl chloride depends, though, on the temperature. The
molar mass increases while degreasing the temperature, presenting a maximum of
approximately -30o C. Vinyl chloride is a gas with the boiling point equals to -14oC, and
consequently, the polymerization reactions of vinyl chloride always take place under pressure,
such that, the vinyl chloride to be liquid at the working temperature.
Polyvinyl chloride is insoluble in liquid vinyl chloride, but it blows up with a maximum
30% of liquid monomer.
Compared with the usual polymerizations in solution, in the case of bulk and also
suspension polymerization of vinyl chloride, an autoacceleration effect occurs since the
beginning of the polymerization. [17]
2.1.2. The mechanism of the free-radical polymerization
a) Initiation
In the initiation step there are two reactions to take into account:
-

Generation of the free radicals


kd
2Cl

Addition of the primary radicals to the monomer unit. It is rapid and exothermal.

Cl2

H H

Cl+ CH2=CH-Cl

C-C [16]
H Cl

The reaction rate for initiation is described as follows:


vi = d[M]/dt = 2kd f [I]
Where f is the efficiency, kd is the dissociation constant, [I], [M] and [M] are the
concentrations of the initiator and active growing chain. [25]

19

Initiation mechanisms:
-

Initiation with Thermo-Labile Substances: because the thermo-labile compounds have


in their molecule a weak bond, these compounds are able to endure homolysys in the
frequent temperature range for polymerization (40-130oC);
Redox initiation: Electron transfer process between an oxidant and a reducer is used to
generate radicals so that the redox initiation takes part. An advantage of the redox
initiation is that there are obtained important reaction rates at low temperatures
(0-40oC);
Physical initiation: means that by using an energy source on the monomer, the
propagating radical is generated;
Chemical initiation: can be photochemical, radiochemical, plasma-chemical, mecanochemical, and thermal initiation.

b) Propagation
In the propagation stage, by addition of the active center, the chain growth occurs. In the
propagation stage there is no consumption or generation of radicals, so, the number of radicals
is conserved. For the propagation stage, an important characteristic is that it has high reaction
rates and respectively a high polymerization degree is formed almost immediately after the
initiation of polymerization.
All types of additions may happen in free-radical process, but in the case of the
polyvinyl chloride, only the monosubstituted vinyl monomers: head to tail addition or head
to head addition may happen:
-

Monosubstituted vinyl monomers: head to tail addition or head to head addition.


H H H H

CH2-HC

+ CH2=CH-Cl

kp

C-C-C-C
H Cl H Cl

Cl

H H H H

CH2-HC
Cl

+ CH2=CH-Cl

kp

C-C-C-C [16]
H Cl Cl H

The reaction rate for propagation can be described as follows:


vp = kp[M][M]
20

Where kp is the propagation rate constant, [M] is the concentration of the monomer, and [M]
is the concentration of the active growing chain.

c) Termination:
In the termination stage the active centres are deactivated and thus an inactive polymer
(dead polymer) is formed.
Termination mechanisms:
-

Combination

Rx + Ry

ktc

Px+y

H H H H

CH2-HC +

CH2-HC
Cl

Cl

C-C-C-C
H Cl Cl H

Disproportionation

Rx + Ry

ktd

Px + Py

CH2-HC +

CH2-HC

Cl

ktc

ktd

CH2-CH2 + CH=CH
Cl

Cl

Cl

Combination with primary radical

CH2-CH-Cl + R

CH2-CH-Cl-R

[16]

The reaction rate for termination can be described as follows:


vt = -d[M]/dt = 2kt[M]2
Where [M] is the concentration of the active growing chain, kt is the termination rate constant,
[M] is the concentration of the monomer. [25]

21

d) Chain transfer
Chain transfer is a side reaction between free radicals and transfer agents and this also
leads to a dead polymer and another radical:
CH2-CH-Cl+ CH2=CH-Cl

CH2-CH2Cl + H2C=Cl

CH=CHCl +H3C-CHCl

Chain transfer constant, ktr:


vtr ktr X
X

C
vp k p M
M

Note: X is the molar concentration of the transfer agent.


Due to the chain transfer reaction it will occur the interruption of the chain growth and the
molecular mass of the polymer is reduced. [16]

2.1.3. Free-Radical Polymerization influencing factors


a) Temperature:
-

The polymerization rate increases with temperature,


When lowering the reaction temperature the influence of chain transfer can be
diminished,
When temperature increases the polymerization degree becomes lower,
Values of the rate constants are very influenced by the temperature, according to
Arrhenius law:
Kj0 = pre-exponential factor
Ej = activation energy
Ej
R = universal gas constant

T = absolute temperature
k j k j 0 e RT
j(index) = type of reaction(initiation,
propagation, termination, transfer)
The average polymerization degree decreases while temperature increases,
Also, an increase of the temperature leads to a higher concentration of the active centres.

22

b) Pressure:
- A high concentration of the monomer can be obtain when working at high or moderate
pressure,
- Collision can happen if pressure is higher than the probability of termination,
- Polymerization degree will become higher at high pressures.
c)
-

Chain transfer:
The molecular weight is diminished,
Branching may appear,
Cross-linking may also appear and thus limiting the maximum conversion,
If chain transfer is absent, the polydispersity of the formed products is between 1.5 and
2.
Interruption of the chain growth happens while chain transferring,
Another effect of the chain transfer with the polymer is the increase of the polydispersity
index of the final polymer,
Activation energies in the chain transfer reaction are higher than in the propagation
reactions,
If chain transfer is absent, the length of the macromolecular chain depends on the
termination mechanism,
The chain transfer reaction may be neglected at low conversions,
Chain transfer can be diminished by lowering the reaction temperature.

d) Inhibitor:
- Polymerization must be inhibited, because in initiation, unreactive (inert) species will
appear,
- To prevent premature or unwanted polymerization, monomers are always stored in the
presence of inhibitors,
- To reduce the plant operation costs, contact inhibitors are used,
- Except the prevention of the premature polymerization, inhibitors are also used to stop
the polymerization at limited conversion, by adding small amounts in the reactor after
the process has reached the wanted stage,
- An induction time must be observed until the inhibitor is fully consumed,
- Inhibitors also may lead to a higher consumption of initiator during the process.
e) Initiator concentration:
- Influences the polymerization degree,
- During polymerization, the initiator concentration may vary. [16]

23

2.2. Bulk polymerization of vinyl chloride


Bulk polymerization definition: Bulk polymerization is accomplished by adding a
soluble initiator to a pure monomer in liquid state. The initiator must be dissolved in the
monomer. This reaction is initiated by heating and exposure to radiation. As the reaction
advances, the mixture becomes more and more viscous.
By a technological point of view, the bulk (mass) polymerization of the vinyl chloride
presents the advantage of obtaining a high purity product and a product with a porous structure,
capable to absorb and to mix very well with the plasticizers. The unreacted monomer is easily
bear away because it is a gas in normal conditions and thus, the obtained polymer is sieved, its
drying being unnecessary.
Generally, at the beginning of the bulk polymerization process, the reaction mass
consists only of the monomer and the initiator, or only the monomer. The initiator must be
soluble in the monomer.
The biggest difficulty in carrying on this process is the removal of the reaction heat. The
high temperature leads to intense transfer reactions with the monomer and the polymer and also
to dehydrochloruration. From this reason, polymerization is carried on in the presence of some
acid chloride acceptors.
The polymerization process is carried out in two phases: prepolymerization and the
polymerization.
In the first phase, the reaction is carried on in autoclave reactors with stirrers, being
necessary an intense stirring to obtain some uniform particles and to realize a corresponding
thermal transfer. Polymerization is carried on until 8-10% conversion is reached.
In the second phase, the polymerization reaction is carried on until 60-85% conversion
is reached, polymerization taking place on the polymer particles surface formed in the first
phase.
Carrying on the polymerization process in two phases permit the obtaining of different
types of products, the particles characteristics being determined by the operating mode of the
first phase, and the molecular mass of the second phase.
The phases of the technological process are the following: prepolymerization (in vertical
jacketed autoclave reactors), polymerization (in special reactors: vertical helix anchor reactor,
ball mill reactor, triple helix reactor), separation of the polymer and sieving.
Bulk polymerization doesnt need filtration and drying of the polymer which is a great
advantage, by simplifying the whole process. [18]

The stages of the evolution of the primary particle of polyvinyl chloride in bulk
polymerization are presented in figure 2.1.:

Figure 2.1.: Evolution of the primary


particle of polyvinyl chloride in the
suspension polymerization.
Source: Technology of polymer synthesis course, Dr. Eng.
Celina Maria Damian, 4th year.

24

I: Polymer germs
II: Increased polymer particles
III: Particle fusion. [19]
A procedure has been investigated to obtain polyvinyl chloride with a higher molecular
weight in good yields. The procedure is called: bulk polymerization of vinyl chloride with halftitanocene/MAO catalyst (Methylaluminoxane catalyst). It is known that in polymerization the
molecular weight is limited by the chain transfer because of the large transfer constant. It has
been investigated the polymerization of vinyl chloride with transition metal complexes and thus
the chain transfer and the molecular weight of the polymer can be controlled by using the bulk
polymerization with half-titanocene/MAO catalyst. [20]

2.3. Emulsion polymerization of vinyl chloride


Emulsion polymerization definition: is a radical polymerization that starts with
an emulsifier, water, monomer, and surfactant
Emulsion polymerization of vinyl chloride is on the second place in the production of
polyvinyl chloride, due to the advantages it presents:
- Easy assumption of the reaction heat,
- The possibility to ensure a constant temperature in the whole reaction mass,
- High reaction rate even at low temperatures,
- High stability of the latex.
These factors lead to the obtaining of a more homogeneous product regarding to the
distribution of the molecular masses and offers the possibility of leading the process in a
continuous system.
The drawbacks of the procedure, which led to the limitation of applying this process
compared to the suspension one, are the following:
- High amount of emulsifier,
- In the final product there will be electrolytes and other impurities, which aggravate the
dielectric properties of the polymer, decrease the transparency, the clarity of the polymer
and also the adhesion for the metals and increase the capacity of water absorption,
- The decrease of the stability of the polymer.
The most important factors which influence the polymerization process are the
following:
- The nature and the concentration of the emulsifier,
- The pH,
- The stirring,
- The temperature,
- The nature and the concentration of the initiators.
25

The quality of the finished product depends in a great measure in the way of separation
and drying of the polymer.
The nature and the concentration of the emulsifier has an important influence over the
polymerization process because it determines the number and the type of the micelles and thus
the final dimensions of the particles.
As tension-active agents are used: sodium salts of the carboxylic acids (caprylate,
laurate, palmitate), sodium salts of the fatty alcohols sulfates (caprylate sulfate, lauryl sulfate,
stearyl sulfate), sodium salts of the sulfonic acids (capryl sulfonate, lauryl sulphonate) or the
non-ionic emulsifiers (polyvinyl alcohol).
As initiators there are used: potassium persuflate, ammonium persulfate or the
oxygenated water.
To carry on the process at lower temperatures, a redox system is used, as reducers being
used the ferrous sulfate, metabisulfite or the sodium sulfite.
The phases of the technological process are the following: preparation of the aqueous
phase, polymerization of the vinyl chloride, degasing of latex, separation and drying of the
polymer, sieving and depositing the product. The polymerization takes place in an autoclave
reactor equipped with a stirrer. Also, the unreacted monomer is removed with steam and the
polymer separation is made by water evaporation in atomizers.
The washed polyvinyl chloride has a higher purity which determines the lowering of the
water absorption capacity, the lowering of the ash content and superior dielectric characteristics.
[18]

2.4. Suspension polymerization of vinyl chloride


Generally, the suspension polymerization is a heterogeneous procedure where the
monomer is dispersed in a continuous liquid phase. An important detail is that the monomer
must be immiscible with the dispersion medium (usually water).
The suspension polymerization is also called microbulk polymerization, due to the
resemblance between the two. In both of the processes there are observed the same stages, and
the kinetic of the process presents the same typical autoacceleration phenomena presented in the
figure 2.2.. [18]

Figure 2.2.: Evolution of the primary particle of polyvinyl chloride while suspension
polymerization
Source: Technology of polymer synthesis course, Dr. Eng. Celina Maria Damian, 4 th year.

26

I: Polymer germs
II: Increased polymer particles
III: Particle fusion
IV: Porous conglomerate formation. [19]
The fourth step corresponds of a monomer conversion of 75-80% and it represents the
moment when polymerization stops. Over this conversion, transfer reactions are intensified with
the apparition of branched polymer:

CH2-CH-CH2-CH
Cl

Cl

+ R
-RH

CH2-C-CH2-CH
Cl

Cl

+ VC

CH2-C-CH2-CH
Cl

Cl

After the aggregation stage of the granules, the suspension particle starts to contract.
While continuing the polymerization, the monomer within the particle and that from the vicinity
of the surface, is consumed. The superficial pores are blocked up and the ones from the interior
are closed, the porosity dramatically decreasing. It results that the porosity of the particles of
polyvinyl chloride is determined by the conversion degree, decreasing with the increasing of the
conversion and presenting a sharp variation at the end of the process.
Porosity is one of the most important characteristics of this material because only
polyvinyl chloride with porous structure can absorb the plasticizers. From this reason, to obtain
a high porosity of the particles it is necessary the reaction to be carried out at limited
conversions.
The suspension agent and initiator nature have an important effect also on the structure
and on the morphology of the polyvinyl chloride. As suspension agents, solid materials as
powders and water soluble macromolecular compounds can be used. In the case of solid
suspension agents one of the most important factors which determine the stabilizer quality is the
wetting capacity also in the aqueous phase and in the oily stage. If the powder is wetted only in
one single phase then it is dispersed only in that phase and it doesnt confer stability to the
suspension.
The most used suspension agents in the case of vinyl chloride are the following:
magnesium hydroxide (prepared in the reaction medium), polyvinyl alcohol, methylcellulose
and the styrene copolymers with the maleic anhydride.
The porosity of the polyvinyl chloride particles obtained through the polymerization
process in suspension, is substantially increased by using along with the suspension stabilizer,
some small quantities of ionogen tensio-active substances as salts of alkaline-earth metals of the
fatty acids.
As initiators there are used: peroxides, hydroperoxides, azoderivatives and recently
percarbonates. Besides the majority of the initiators used at vinyl chloride polymerization
(benzoyl peroxide, lauroyl peroxide, peroxidicyclohexyl hydroperoxide), polycarbonates have a
27

break temperature substantially decreased (45-550C), which confers them various advantages in
their utilization:
- Sensible shortening of the polymerization time,
- Increasing of the reactor productivity,
- Small induction periods or no induction periods,
- Poor consumption,
- Decreasing of the number of long branches,
- Increasing of the molecular mass due to the lower temperature polymerization.

Suspension polymerization of vinyl chloride permits an easy evacuation of the released


heat along the polymerization process, which offers the possibility to obtain a narrower
distribution of the molecular masses of the polymer.
The temperature in the polymerization reactor may be maintained at the prescribed
temperatures (+- 0.50C), a very important fact because it forms the determinant factor of the
molecular mass, of the molecular masses distribution and of the thermostability of the polymer.
By suspension polymerization there are obtained particles with the diameter between 50200 m which permits an easily separation of the polymer on the centrifuge.
The main deficiency of this procedure is the extremely high difficulties which appear
when the procedure is realized in a continuous system. From this reason, lately, the tendency is
that the suspension polymerization of vinyl chloride is to be realized in very big reactors (until
200 m3).
The phases of the technological process are the following: the preparation of the raw
materials, the polymerization, demonomerization, filtration, centrifugation, drying, sieving and
depositing.
Vinyl chloride is industrially obtained by the radical polymerization of vinyl chloride
presented in Chapter 2, section 2.1.1.

nCH2=CH
Cl

R

[18]

CH-HC
Cl

28

2.5. Advantages and drawbacks of the suspension polymerization process


2.5.1. Advantages
-

The high specific surface of the droplets can be easy and efficiently cooled when they
come in contact with the aqueous phase,
High productivity,
Better heat control,
The purity of the product,
Low cost of the separation of the polymer, [16]
Because water it is used as a heat exchanger is more economical than the solvents used
in solution polymerization,
Easy heat control because water acts as a heat transfer medium. [3]

2.5.2. Drawbacks
-

High investment cost,


Low reactor productivity because the dispersion medium is present,
Few monomers are water soluble solution,
Autoacceleration occurs, [16]
Very little contamination occurs (traces of catalyst, suspension agent, dispersing agent)
and thus separation and purification must be done, [3]
Aggregation may occur if the glass transition temperature is less than the polymerization
temperature,
Difficult to control polymer size. [22]

2.6. Technology of the suspension polymerization of vinyl chloride process


Vinyl chloride polymerization in suspension permits the easy evacuation of the released
heat while the polymerization process, which offers the possibility to obtain a polymer with a
narrow distribution of the molecular masses.
By suspension polymerization are obtained particles with the diameter between 50-200
which permits the easy separation of the polymer on the centrifuge.
The technological process contains the following stages: preparation of the raw
materials, polymerization, de-monomerization, filtration, centrifugation, drying, sieving and
deposing. The scheme of the suspension polymerization of the vinyl chloride is presented in
figure 2.3.

29

Figure 2.3. The scheme of the suspension polymerization of vinyl chloride installation
30

Legend:
1-Vinyl chloride filter
2-Vinyl chloride measuring vessel
3-Initiator solution preparation vessel
4-Solution batcher
5-Demineralized water buffer vessel
6-Methyl cellulose preparation vessel
7-Centrifuge
8-Methyl cellulose solution buffer vessel
9-Methyl cellulose solution batcher
10-Polymerization reactor
11-Gasometer
12-Compressor
13-Condenser
14-Recovered vinyl chloride buffer vessel
15-Distillation column
16-Recovered vinyl chloride buffer vessel
17-Filter
18-Buffer vessel
19-Filtrating sieve
20-Centrifuge
21-Buffer vessel
22-Screw transporter
23-Firstlevel pneumatic drier
24-Blower
25-Air filter
26-Heating battery
27-Cyclone
28-Pneumatic dryer 2nd level
29-Bags filter
30-Bunker
31-Vibrating sieve
32-Rough polyvinyl silo
33-Depositing bunker

31

CHAPTER 3: POLYVINYL CHLORIDE RECYCLING


Polyvinyl chloride has been vastly used since the middle of the 20th century. Polyvinyl
chloride is versatile, clear (transparent), easy to be mixed, durable, strong, resistant to
chemicals, fats, oils, sun light, flame and disaggregation. It has flowing characteristics and
stable electric properties.
Polyvinyl chloride is on the third place in the world production and consumption of
plastics. Up to 33 millions of tons of polyvinyl chloride are produced every year and this
number increases annually. Approximately 57% of the polyvinyl chloride mass is chloride, so it
is needed less petroleum in comparison with many other polymers.
Because of the additives including heavy metals (Lead, cadmium), polyvinyl chloride is
difficult to be recycled. Nowadays, less than 1% of the polyvinyl chloride is recycled.
To identify polyvinyl chloride on different materials it might be seen stamped the 3
number or the V letter on the plastic itself or within the recycling symbol (fig. 3.1.): [23]

Fig. 3.1. Recycling symbol


Source: http://www.greenlivingtips.com/articles/PVC-and-the-environment.html

As reported by the results of an ECVM (The European Council of Vinyl Manufacturers)


quiz and by the received information from the European Union member states, approximately
520 ktons of pre-consumer and post-consumer polyvinyl chloride wastes are recycled every
year:
-

Approximately 80% (420 ktons) from the polyvinyl chloride wastes are pre-consumer
wastes.
Recycling post-consumer polyvinyl chloride wastes is still at a low level in Europe. In
the year 2000, almost 100 ktons of polyvinyl chloride wastes had been recycled
Recycling post-consumer polyvinyl chloride consists in bigger parts of cables and
packages.
The high quality mechanical recycling for post-consumer wastes (pure recycled PVC
materials) exist for singular groups of products (bottles, pipes) but only in low
quantities.

32

In the following table (Table 3.1.) there will be presented the applications for recycled rigid
polyvinyl chloride:
Wastes
Bottles

The type of the new product


Non-alimentary bottles
Pipes
Profiles
Injection-Moulding
Pipes
Pipes
Window profiles Window profiles
Table 3.1.: Applications for recycled rigid polyvinyl chloride
In the next table (Table 3.2.) there will be presented the applications for recycled flexible
polyvinyl chloride:
Wastes
Flooring
Cables

The type of the new product


Flooring
Industrial flooring
General purpose compounds
Roofing membranes Membranes liner
Table 3.2.: Applications for recycled flexible polyvinyl chloride
Polyvinyl chloride can be recycled in two ways:
- Mechanical recycling
- Chemical recycling

3.1. Mechanical recycling


Mechanical treatment processes have the purpose to automatically separate pure
fractions of polyvinyl chloride and other materials and also to produce recycled materials with a
defined particle dimension. Generally, the mechanical treatment process consists in cutting the
units for lowering the dimension, and separating units to extract some dimensions or materials
form the main flux of materials (e.g. magnetic drums for the separation of ferrous metals).
The evaluations of the life cycle of polyvinyl chloride and plastic materials recycling are
valid only for a limited number of products and recycling ways. Thus, from the available results
from recent studies, the particular study determined the following general evaluation:
- For production wastes and post-consumer wastes from which the polyvinyl chloride can
be easily extracted, mechanical recycling assures an environmental advantage;
- Mechanical recycling of mixed plastic fractions assure environmental advantages only if
there is possible to sort plastic materials which can be used in typical applications for
plastic materials.
The general situation concerning the ecological and health risks associated with the
mechanical recycling of polyvinyl chloride can be summed up as follows:
33

Collecting, sorting and treatment of plastic wastes are not associated with some new
risks about the workers and environment exposure at harmful substances;
Some products made out of polyvinyl chloride as window frames, pipes and cables,
contain heavy metals as stabilizers which are toxic (Cadmium and lead compounds).
Risks evaluation has been a controversy thing. Heavy metals compounds are fixed in the
polyvinyl matrix and thus, the release of the toxic substances in the environment is not
possible, but few releases can take place while the production of the stabilizers,
polyvinyl chloride mixing, wastes evacuation and accidental fire takes places. Generally,
the quantities which can be released by this way are few in comparison with other heavy
metal emission sources;
In the past, polychlorurated biphenyls (PCB) had been added in the polyvinyl cables
compositions to obtain a higher tension cables and thus to increase the isolation yield
and also for lower tension cables. A fraction from the cables included in the electric or
electronic apparatus are recycled in recycling systems for electronic wastes.

3.2. Chemical or feedstock recycling


Generally, polyvinyl wastes can be available in two forms: as fraction of mixt plastic
waste (MPW with a lower amount of polyvinyl chloride), or as a fraction of plastic materials
rich in polyvinyl chloride.
An analysis of the options for the chemical recycle of MPW and of wastes rich in
polyvinyl chloride, inclusively the cement kilns from 1999 will be presented in the following
table (Table 3.3.):
Technology
Status
Capacity
Future potential
Mixed plastic waste
Texaco (NL)
Pilot/on hold
Uncertain
Polymer cracking
Pilot/on hold
Uncertain
(UK)
BASF (D)
Closed in 1996
15 ktpa before 1996
VEBA (D)
Closed by 2000-01-01 87 ktpa before 2000
Blast furnaces
Operational (D)
162.5 ktpa in 1998
5 Mio tpa in the EU
SVZ (D)
Operational
110 ktpa in 1998
Cement kilns
Operational
3 Mio tpa in the EU
PVC-rich waste
BSL (D)
Operational
15 ktpa in 1999
Linde (D/F)
Pilot under constr.
2 ktpa in 2001
15 ktpa > 2005?
NKT (DK)
Pilot under constr.
< 1 ktpa in 1992
15 ktpa in the future?
Table 3.3.: Analysis of the options for the chemical recycle of MPW and of wastes rich in
polyvinyl chloride, inclusively the cement kilns

34

Country codes:
NL = Netherlands
UK = United Kingdom
DK = Denmark
D = Germany
F = France
Acronyms:
BASF = Baden Aniline and Soda Factory
VEBA = Vereinigte Elektrizitts- und Bergwerks AG (German: United Electricity and Mining)
SVZ = Sekundrrohstoff Verwertung Zentrum
BSL = BIOSERVICE Scientific Laboratories
NKT = NKT Cables
Units:
Ktpa = Kilo-Tonnes Per Annum

For the mixt plastic wastes it is assigns that:


- Texaco processes, cracking of polymers, VEBA and BASF mainly produce liquid or
gaseous organic compounds which replace the primary resources based on petroleum or
gas;
- SVZ process, blast furnaces, and cement kilns use MPW as a replacement for coal;
- Mechanical recycling uses MPW as a replacement for the primary resin made from
plastic. The high quality mechanical recycling it isnt taken into account because we
need a pure waste;
- Municipal Solid Waste Incineration (MSWI) uses the caloric value of the MPW to
produce heat and electricity. [24]

35

CHAPTER 4: TECHNOLOGICAL DIMENSIONING


4.1. Projection recipe
Let there be projected an installation to obtain polyvinyl chloride through the suspension
procedure, having the following projection data:
Production capacity: 20,000 t/year;
Reactor capacity: 14.5 t;
Batch duration: 13.5 h;
Fabrication recipe:

Water/Vinyl Chloride: 2/1;


Initiator (Lauroyl peroxide): 0.2% from the monomer;
Suspension stabilizer (-methylcellulose): 0.067% from the monomer (as a solution
1.7%);
Butyl stearate: 3% from the monomer;
Mersolate: 0.0004% from the reactor capacity

Reactor feeding temperature: 20oC;


Reaction temperature: 58oC;
In the centrifuge washing water is introduced with a 3.5% flow from the output PVC flow;
After centrifugation, the PVC exists with a humidity of 40% and after drying the humidity is
0.25%;
Final conversion of the monomer: 90%;
Technological losses:

Polymerization: 0.1%
Filtration: 0.2%
Centrifugation: 0.3%
Drying: 0.2%
Sieving: 0.5%
Packaging: 0.3%;

36

4.2. Batch number calculation

The calculation of the number of days worked per year, Nd:

Nd = Nc (Nr + Nn)
Where:
Nc Number of calendar days (days/year);
Nr Number of revision days (there are proposed 30 days/year);
Nn Number of non-working days or accidental stopping (there are proposed 5
days/year).
Nd = 365 (30 + 5) = 330 days/year
The calculation of the time worked per year, Nh:
Nh = Nd 24 = 7.92 103 h/year
The calculation of the number of batches, Nb:

Where:
nh Batch duration (h)

By approximation there are 586 batches/year.

4.3. Reactors number calculation


The calculation of the batch capacity, Cb:
Cb = Crpvc(1-Pp)(1-Pf)(1-Pc)(1-Pd)(1-Ps)(1-Pp)
Where:
Cr Capacity of the reactor (kg);
pvc Parts by weight of vinyl chloride (%);
Vinyl chloride conversion (%);
Pp Polymerization losses (%);
Pf Filtration losses (%);
37

Pc Centrifugation losses (%);


Pd Drying losses (%);
Ps - Sieving losses (%);
Pp Packaging losses (%);

Amount of polyvinyl chloride per batch:


(

The calculation of the reactor capacity per year, Cr:


Cr = Cb Nb
Where:

Cb Batch capacity (kg/batch)


Nb Number of batches per year (batches/year)

Cr = 4.074 586.667 = 2.39 103 tons/year


The calculation of number of reactors, nr:

Where:

Cp Production capacity (tons/year)


Cr Reactor capacity (tons/year)

38

4.4. The calculation of the fabrication recipe


Amount of monomer (vinyl chloride):
mvc = 4.6 t = 4600 kg

Where:

vc - Density of vinyl chloride (kg/m3)


mvc - Mass of vinyl chloride (kg)

Vvc - Volume of vinyl chloride (m3)

Vvc = 4600/834.933 = 5.509 m3


The water/vinyl chloride ratio is 2/1, then the amount of water is calculated:
mwater = 9200 kg
Vwater = 9.2 m3
The initiator (lauryl peroxide) is 0.2% from the monomer, then the amount of the
initiator is calculated:
minitiator = 92 kg
Vinitiator = 0.101 m3
The suspension stabilizer (-methylcellulose) is 0.067% from the monomer (as a 1.7%
solution), then the amount of suspension stabilizer is calculated:
mstabilizer = mvc 0.067
mstabilizer = 4600 0.067 = 308.2 kg
mstabilizersolution = mstabilizer 0.017 = 5.239 kg

39

Amount of necessary water to obtain -methylcellulose solution calculation:


mwater = mstabilizer mstabilizersolution = 302.961 kg
Using the same formula as for vinyl chloride, we calculate the volume for -methylcellulose:
Vstabilizer = 302.96/910 = 0.333 m
The butyl stearate is 3% from the monomer, then the amount of butyl stearate is
calculated:
mstearate = 0.03 4600 = 138 kg
Mersolat is 0.0004% from the monomer, then the amount of Mersolat is calculated:
mmersolat = 410-6 14500 = 5810-3 kg

TOTAL MASS OF MATERIALS AND THE VOLUME OF MATERIALS:


mtotal = mvc + mwater + minitiator + mstabilizer + mstearate + mmersolat
mtotal = 4600 + 9200 + 92 + 308.2 + 138 + 0.058 = 14338.258 kg
Vtotal = Vvc + Vwater + Vinitiator + Vstabilizer
Vtotal = 5.509 + 9.2 + 0.333 + 0.101 = 15.143 m3

4.5. Material balance


I.

POLYMERIZATION STAGE

vinyl chloride

polyvinyl chloride

lauroyl peroxide

unreacted monomer

water + stab. solution


butyl stearate
mersolat

POLYMERIZATION
STAGE

mersolat
water + stab. solution
losses

- MC
40

Input

U.M.

Vinyl chloride solution

Kg/b

Lauroyl peroxide

Value

Output

U.M. Value

4600

PVC suspension

Kg/b

4.366 103

Kg/b

92

Unreacted monomer

Kg/b

459.54

Water

Kg/b

9205.239

Mersolat

Kg/b

0.058

Butyl stearate

Kg/b

138

Water + stab. sol.

Kg/b

9498.892

Mersolat

Kg/b

58 10-3

Losses

Kg/b

14.343

Methyl cellulose

Kg/b

308.2

TOTAL

Kg/b

14344.343 TOTAL

Kg/b 14344.343

Legend: b = batch; stab. sol = water from the stabilizer solution

II.

HOMOGENIZATION FILTRATION

polyvinyl chloride
mersolat

polyvinyl chloride

MC
water

mersolat

HOMOGENIZATION

- MC

FILTRATION
(In this stage it occurs the passing
from a discontinuous process to a
continuous one)

Input

U.M.

Polyvinyl chloride

Kg/b

Mersolat

Value

water
losses

Output

U.M

Value

4.366 103

Polyvinyl chloride

Kg/b

4.366 103

Kg/b

0.058

Mersolat

Kg/b

4.283 10-3

MC

Kg/b

5.234

MC

Kg/b

0.387

Water + stab.sol

Kg/b

9.499 103

Water + stab.sol

Kg/b

700.2
41

TOTAL

III.

Kg/b

13870

Losses

Kg/b

2.055

TOTAL

Kg/b

13870

CENTRIFUGATION WASHING

Knowing that in the centrifuge it is introduced washing water with a flow equal to 3.5%
from the polyvinyl chloride output flow and after centrifugation the polyvinyl chloride exits
with a 40% humidity, the following scheme is drawn:

polyvinyl chloride
mersolat

polyvinyl chloride (40% humidity)


residual water

CENTRIFUGATION

MC

MC
WASHING

water + wash. water

losses

Input

U.M.

Polyvinyl chloride

Kg/b

Mersolat

Value

Output

U.M

Value

322.733

PVC (40% humid)

Kg/b

536.275

Kg/b

4.283 10-3

Residual water

Kg/b

498.458

MC

Kg/b

0.387

MC

Kg/b

0.386

Water + washing water

Kg/b

713.496

Losses

Kg/b

3.104

TOTAL

Kg/b

1036.62

TOTAL

Kg/b

1036.62

42

IV.

DRYING

Knowing that after drying, the humidity of polyvinyl chloride is 0.25%, the following
scheme is drawn:

polyvinyl chloride (40% humidity)

polyvinyl chloride (0.25% humidity)


DRYING

water
losses

Input

U.M.

PVC (40% humid)

Kg/b

TOTAL

V.

Output

U.M

Value

PVC (0.25% humid)

Kg/b

322.895

Kg/b

Water

Kg/b

212.953

Kg/b

Losses

Kg/b

1.072

TOTAL

Kg/b

536.275

Kg/b

Value
536.275

536.275

SIEVING

polyvinyl chloride

polyvinyl chloride

SIEVING

losses

Input

U.M.

Polyvinyl chloride

Kg/b

Value
322.895

Kg/b
TOTAL

Kg/b

322.895

Output

U.M

Value

Polyvinyl chloride

Kg/b

321.281

Losses

Kg/b

1.606

TOTAL

Kg/b

322.895

43

VI.

DEPOSITING

DEPOSITING

polyvinyl chloride

polyvinyl chloride

drying losses

Input

U.M.

Polyvinyl chloride

Kg/b

321.281

Drying losses

Kg/b

0.646

TOTAL

Kg/b

321.926

VII.

Value

Output

U.M

Value

Polyvinyl chloride

Kg/b

321.926

TOTAL

Kg/b

321.926

PACKAGING

polyvinyl chloride

polyvinyl chloride

PACKAGING

losses

Input

U.M.

Polyvinyl chloride

Kg/b

Value
321.926

Kg/b
TOTAL

Kg/b

321.926

Output

U.M

Value

Polyvinyl chloride

Kg/b

320.961

Losses

Kg/b

0.966

TOTAL

Kg/b

321.926

44

VIII.

ANNUAL BALANCE ON THE INSTALLATION

Input

U.M.

Value

Output

U.M.

Value

Vinyl
chloride

Kg/year

2.429 107

PVC

Kg/year

2.288 107

Lauroyl
peroxide

Kg/year

4.858 105

Vinyl
chloride

Kg/year

2.426 106

Water

Kg/year

4.86 107

Mersolat

Kg/year

305.322

MC

Kg/year

1.627 106

Water

Kg/year

5.086 107

Butyl stearate

Kg/year

7.286 105

Residuals

Kg/year

2.531 104

Mersolat

Kg/year

306.24

Washing
water

Kg/year

8.052 105

TOTAL

Kg/year

7.654 107

Kg/year

7.654 107

45

4.6. Technological flux to obtain polyvinyl chloride in suspension technique


Lauroyl peroxide solution

-Methyl cellulose solution

POLYMERIZATION

Regeneration of
unreacted monomer
24,290 tons /year

HOMOGENIZATION
FILTRATION

Demineralized water

CENTRIFUGATION
WASHING

Hot air
DRYING

Residual water
purification

Filtration

SIEVING

DEPOSITING

PACKAGING

22,880 tons/year

46

4.7. Thermal balance


Given data:
Specific heat:
Cp(water) = 1 kcal/kgdegree
Cp(monomer) = 0.31 kcal/kgdegree
Cp(polymer) = 0.24 kcal/kgdegree
Cp(butyl stearate) = 0.45 kgcal/kgdegree
Cp(lauroyl peroxide) = 0.45 kgcal/kgdegree
Temperature:
t1 = 200C
t2 = 580C
4.7.1. Heating the reaction mixture at 20-580C
-

Heating of water 1h

mwater = 9504 kg
Necessary heat for water-stabilizer is calculated with the following formula:
Qwater = mwater Cp(water) (t2 t1)
Where:

mwater - Total amount of water (kg)

Cp Specific heat of water (kcal/kgdegree)

t2 The reaction temperature (0C)

t1 Feeding temperature of the reactor (0C)

Qwater = 9.504 103 1 (58-20) = 3.611 105 kcal/s


Knowing the thermal heat capacity of steam at 1500C:
rsteam = 505 kcal/kg

47

The steam flow should be calculated with the following formula:

Where:

Qwater Necessary heat (kcal/s)


rsteam Thermal heat capacity (kcal/kg)

Dsteam 1 = 729.45 kg/h

Heating of monomer 1h

Using the same formula as for water, the necessary heat for monomer is calculated:
Qmonomer = 4600 0.31 (58-20) + 138 0.45 (58-20) + 92 0.45 (58-20) = 5.812 104 kcal/s

Vinyl chloride

Butyl stearate

Lauroyl peroxide

Using the same formula as for water, the steam flow is calculated:
Gsteam2 = 117.393 kg/h
Dsteam2 = 117.393 kg/h

Heating of the reactor

Qreactor = 3000 0.12 (58-20) = 1.368 104 kcal/s


-

Total flow of steam to heat the suspension at 20-580C:

48

= 874.474 kg/h

4.7.2. Taking over the reaction heat


Given data:
Constants:
kd = 5.5 10-5 s-1
kp = 322.22 mol-1 s-1
kt = 5.8 107 mol-1 s-1
Efficiency:
f = 0.7
Mixture volume:
Vmixture = 15.143 m3
The enthalpy is calculated:

Molar concentration:
I = 0.01 mol/l
Number of monomer moles is calculated with the following formula:

Where:

mvc Amount of vinyl chloride (kg)


M Molecular mass of vinyl chloride (kg/kmoles)

nmonomer = 4600/62.5 = 73.6 kmoles

49

The molar concentration is calculated with the following formula:

Where:

nmonomer Number of monomer moles (kmoles)


Vmixture - The volume of the mixture (m3)

Cm = 73/15.143 = 4.86 mol/l

The reaction rate is calculated with the following formula:

Where:

kp Propagation constant (mol-1 s-1)


Cm Molar concentration (mol/l)
f Efficiency
kd Dissociation constant (mol-1 s-1)
kt Termination constant (mol-1 s-1)

Vr = 1.79 10-4 mol/l s

The heat of polymerization is calculated with the following formula:


Qpolymerization = H Vr Vmixture 1000 3600
Qpolymerization = 2.242 105 kcal/h
The water flow is calculated with the following formula:

Gwater1 = 2.242 104 kg/h


Dwater1 = 2.242 104 kg/h
Observation: Water enters with 100C and exits with 200C
50

4.7.3. Cooling the reaction mixture from 58 to 200C


Qmixture = mpvc Cp(polymer) (58-20) + mwater Cp(water) (58-20) = 4.01 105
= 4.01 104 kg/h
Material balance on the dryer
The drying of a solid material supposes on one side, the heat transfer from the drying agent
to the following material to be dried and on the other side on the humidity transport, under the
form of a liquid or a vapour, through a particle or a solid layer, followed by the humidity
transport in the drying agent. Drying of the polymer stage it is done in a pneumatic dryer.
The wet material flow is calculated with the following formula:
G1 = (mpvc(40% humid) Nr) + m1
Where:

mpvc(40% humid) Mass of PVC with 40% humidity (kg)


Nr Number of reactors

G1 = (536.275 9) + 1622 = 6448 kg/h

The water flow which should be eliminated by drying is calculated with the following
formula, knowing that:
u1 = 30
u2 = 12

Where:

G1 - Wet material flow (kg/h)


u1 Initial humidity of the material (kg water/kg wet material)
u2 Final humidity of the material (kg water/kg wet material)

U1 = 1319 kg/h

51

The wet material flow is calculated with the following formula:

Where:

G1 - Wet material flow (kg/h)


u1 Initial humidity of the material (kg water/kg wet material)
u2 Final humidity of the material (kg water/kg wet material)

G2 = 5129 kg/h
Air flow necessary for drying, is calculated with the following formula, knowing that:
x1 = 0.008
= 0.25

Where:

G1 - Wet material flow (kg/h)


x1 Content or air humidity when entring in the drier (kg water/kg dried air). It is
considered 0.008.

- Content of solid-air mixture (kg solid/kg air). It is considered 0.25.

L = 2.559 104 kg/h


The content of air humidity when exiting the drier is calculated with the following formula:

Where:

x1 - Content or air humidity when entring in the drier (kg water/kg dried air). It is
considered 0.008.
U1 - Thewater flow which should be eliminated by drying (kg/h)
L Air flow necessary for drying (kg/h)

52

4.7.4. Thermal balance on the dryer


Knowing that:
t1 = 1600C
t2 = 500C
The enthalpy of air entering in the dryer is calculated:
H = t1 + x1 (2500 + 2 t1) = 182.56 Kj/kg
Where:

t1 Temperature of the entering air in the dryer, 0C. It is considered 1600C


x1 - Content or air humidity when entring in the drier (kg water/kg dried air). It is
considered 0.008.
t2 Temperature of the exiting air in the dryer, 0C. It is considered 500C

In such a manner, the thermal balance equation can be written:

Where:

mair mass of air for drying (kg)


specific heat of air at 1000C
increment of air heat from 1300C to 700C
- mass of PVC with 40% humidity (kg)
specific heat of polyvinyl chloride at 400C

- difference of temperature between the inputand output temperature


of PVC

quantity of water from PVC, kg


- vaporization heat of water at 1000C

53

4.7.5. Thermal balance on the heating radiator


For dryer to work properly, the humidity of polyvinyl chloride must be reduced from 40%
to 30% by mixing it with polymer with 0.25% humidity.
The equation of the thermal balance:

Where:

msteam necessary amount of steam for heating (kg)


vaporization steam heat at 1600C, the steam temperature is constant
mair mass of heating air (kg)
- difference of input and output temperatures of air
- specific heat of air at 750C
kg

4.7.6. Verification of the thermal transfer area of the reactor


Known data:
Densities:
vc = 911 kg/m3
water = 1000 kg/m3
Viscosities:
vc = 0.001072 Pa s
water = 0.001 Pa s

54

Heat capacities:
Cpcv = 950.4 J/kg
Cpwater = 4185 J/kg
Thermal conductivity:
cv = 0.19 W/m K
water = 0.5999 W/m K
The mixture density is calculated with the following formula:

The mixture viscosity is calculated with the following formula:


mixture = 0.3332 vc + 0.6668 water = 1.024 10-3 Pa s
The mixture heat capacity is calculated with the following formula:
Cpmixture = 0.3332 Cpvc + 0.6668 Cpwater = 3.107 103 J/kg
The mixture thermal conductivity is calculated with the following formula:
mixture = 0.3332 cv + 0.6668 water = 0.463 W/m K

4.7.7. Calculation steps for the partial thermal coefficient, alpha 1:


The Reynolds number for the mixture is calculated with the following formula:
( )

Where:

n rotational speed of the stirrer (rad/s)


d diameter of the reactor (m)
mixture density of the mixture (kg/m3)
mixture Viscosity of the mixture (Pa s)

55

The Prandtl number for the mixture is calculated with the following formula:

The Nusselt number for the mixture is calculated with the following formula:

( )

After all these steps, the partial thermal coefficient, alpha 1, is calculated using the following
formula:

4.7.8. Calculation steps for the partial thermal coefficient, alpha 2:


The external diameter is calculated:
dexterior = d + 4 10-2 = 2.057 m
The area is calculated with the following formula:

The water flow is calculated with the following formula:

Where:

Gwater2 Water flow from the cooling of the mixture (kg/h)

The speed is calculated with the following formula:


m/s
56

The Reynolds number is calculated with the following formula:

The Prandtl number is calculated with the following formula:

The Nusselt number is calculated with the following formula:

After all these steps, the partial thermal coefficient, alpha 2, is calculated using the following
formula:

Knowing that =0.02, the total thermal coefficient is calculated:

Area is calculated:

57

4.8. Calculation of the diameter of the reactor

Where:
V volume of the reactor (m3)
d diameter of the reactor (m)
z ratio between the height and the diameter of the reactor (m)

Volume of the cylindrical part, Vc:


H = 1.2 x 2.017 = 2.42 m

Where:
d diameter of the reactor (m)
H height of the reactor (m)

Where:
z - ratio between the height and the diameter of the reactor (m)
58

Volume of the ellipsoidal part, Ve:

Total volume, Vtotal:


Vtotal = Vc + Ve
Vtotal = 11.125 + 1.074 = 12.199 m3

Chapter 5: Polyvinyl chloride application briefly described PVC


Pipes
5.1. Generalities
Polyvinyl Chloride is the most widely used plastic for piping. For a solid PVC pipe with
its specific shape to be obtained, some chemicals are introduced to one another. First, ethylene
is created by heating the natural gas. This process is called cracking. Second, electrolytes are
used to splice sodium chloride which is found in the form of rock salt and chlorine and sodium
hydroxide are produced.
For the monomer (vinyl chloride) to be produced, chlorine and ethylene are introduced.
The molecules are bonded from each molecules end, and the result of this process is the
polyvinyl chloride polymer. The PVC powder which is compounded is melted and molded into
piping, and thus the PVC tube is created which becomes a very rigid and solid plastic. PVC is
the most preferred material for piping, plumbing and wiring because it is less likely to be
broken during earthquake and it can combat some pressure that many metals cannot tolerate.

5.2. Manufacturing
Pipes are manufactured by using an extruder. PVC is routed by using a double screw
stem extruder or a parallel double screw extruded. PVC pipe extruder is used to make the
diameter of the pipe. The PVC pipe extruders speed is approximately 20 meters / minute. THE
PVC tube is passed through a vacuum pump. The PVC tubing is divided into sections of
individual pipes by using a ring cutting machine, and then the pipes are cooled. After a brief
inspection, the PVC pipes are send for a last inspection, for labeling and then shipping. [26]

59

5.3. Advantages and drawbacks for using PVC pipes


The advantages of plastic pipes:
-

They are light, tough and resistant to chemical attack / corrosion,


They are available in large lengths,
They provide long service life,
They are easy to be installed,
They are cost effective,
They have good elastic properties,
Less friction is offered due to the smooth internal surface,
Due to less friction, it saves the energy in the conveyance of water,
They can be found in various breed of design and colors.
The drawbacks of plastic pipes:

Pipes are not installed in high temperature,


They are easily cracked,
The strength of plastic pipes reduces at higher temperatures. [27]

Fig. 5.1. PVC Pipes Fittings


Source: http://www.fastflowpipes.com/wp-content/uploads/2014/10/SWR_PVC_Pipes_Fittings.jpg

Fig. 5.2. PVC Pipes


Source: http://img.tradeindia.com/fp/1/604/045.jpg

60

CHAPTER 6: Considerations regarding the impact on the

environment and the economy


6.1. Considerations regarding the impact on the environment
In the polymer synthesis processes, we cannot speak about the by-products and the
wastes as in other chemical industry branches. Nevertheless, in the case of the vinyl chloride
polymerization, it can be considered as a by-product, the PVC crust deposed on the reactors
walls. This crust, though, it is sieved and used as an inferior quality PVC.
As a waste to be considered is the suspension water, which is treated in treatment plants,
until it fulfills the necessary conditions to be discharged in the natural waters network or in the
urban sewerage network.
Another waste to be considered is the PVC contaminated air from the dryers. The
polymer is totally recovered by passing the air through colons and bag filters, until it reaches its
own qualities discharged in the atmosphere.

6.2. Economical consideration


For the production capacity of 29410 tons / year, the costs are approximately 1722694
RON, from which the costs for the raw materials have the largest share, as follows: costs for
raw materials 1009296 RON, energy and water costs 337928 RON, costs for amortizations and
adjustments 82226 RON.
These costs are from the year 2006, when due to Oltchim SA, the prices of the raw
materials suffered a spectacular raise.
The raising of the oils price influences the costs of the raw materials to obtain polyvinyl
chloride, because ethylene is the raw material to obtain vinyl chloride.

61

BIBLIOGRAPHY
[1] Braun, Dietrich, PVC Origin, Growth, and Future, Dautesches Kunststoff-lnstitut,
Schlossgartenstrasse 6, Darmstadt Germany, 2001
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https://toxtown.nlm.nih.gov/text_version/chemicals.php?id=84
[3] Ebewele, Robert O. Polymer science and technology, CRC Press, Boca Raton, New
York, 2000
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[5] School of Chemistry, available on: http://www.chm.bris.ac.uk
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62

[25] Radical Polymerization, available on:


https://en.wikipedia.org/wiki/Radical_polymerization
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63