Report

Tailoring

“polystyrene acrylates emulsion Resin”

based on charateristics of the final polymer

Course Polymer

Submitted By Ahmed Ibrahim Mostafa Alzohiry

Code No. 201401919

Submitted To Dr. Sahar El Marsafy

Contents :

1- Introduction
a- Brief explanation about Emulsion polymerization
b- Why emulsion polymerization needed
c- Characteristics of resins for tailoring “synthesis

2- Methodology
a- Choosing the right monomers for the required polymer to tailor the
application properties.
b- Determining the right procedure for synthesis the polymer

3- Synthesis procedure of poly-styrene acrylate emulsion resin

4- Discussion about the process

5- Application &Markets

6- Conclusion
Introduction
Emulsion Polymers are tremendously versatile, They provide low cost, low emissions,
zero VOC, good shelf-life. Due to these benefits, the use of emulsion polymers is
increasingly used in paints and coatings serve growing needs in diverse sectors and
applications.
Emulsion Polymers formed by free-radical polymerization of monomers emulsified into
water. Emulsion polymerization has a specific mechanism and kinetics, which makes it
different from many other polymerization techniques.
Organic monomers are emulsified under the aid of stabilizers into water that serves as a
continuous matrix.
 The addition of radical-forming initiators to the aqueous phase starts the
polymerization, which happens outside of the monomer droplets
 But in the aqueous phase, monomer micelles or monomer swollen polymer particles,
depend on mechanism and phase of the process.
The monomer droplets just serve as a reservoir from which monomer molecules are
delivered. With this mechanism, very high degrees of polymerization can be achieved at
high-solids content, whilst the overall viscosity of the system stays within reasonable
terms for processing.

From an application point of view, polymer emulsions are waterborne systems.

 Waterborne systems are based on water – not organic solvent – as the main carrier.
 They found increasing interest over the past decades due to their favorable profile in
terms of emission control.

Emulsion Polymers are very versatile products.

 They are commercially available as dispersion of polymer particles in water.
 These milky-white liquids range from water-thin to thick paste-like in viscosity.

These two properties, together with a pH, define the standard qualities of any
commercial emulsion polymer.
 - Some key factors for characterizing emulsion polymers are:
1. Solid content
2. Particle size
3. Coagulum in a product
4. Rheology/Viscosity
5. Glass transition temperature
6. Residual monomer/VOC
7. Molecular weight

#1 Solid Content
The solid content is defined as the dry residue of all solid material after evaporation of
water, containing polymer, stabilizer and organic or inorganic auxiliaries, divided by the
total mass of the dispersion. Commercial emulsion polymers contain between about 45
and 65% solids according to that method.

#2 Particle Size
The real particle size of any given polymer dispersion is often difficult to attain. The
results differ from the physical method used or even depending on the specific
equipment provided. A well-defined, narrow, mono-disperse particle size distribution is
the exemption for the products to be discussed here.Most of the emulsion polymers
exhibit broad or multi-disperse, often skewed distributions. Also, the shape of the
particles that are not necessarily ideal spheres and the particle morphology need to be
considered. Often only a few characteristic numbers, such as the average number or
average weight are calculated, from the measured values to characterize the dispersion.
As the polymer particles have a more or less extended interface layer, composed from
adsorbed or grafted stabilizers, and electrolytes the “dry” core diameter needs to be
distinguished from a hydrodynamic diameter in the swollen, wet state. The preparation
of the dispersion before testing is often crucial. Some dispersions tend to form
agglomerates, that can bias some methods, towards higher average particle sizes.

#3 Coagulum in a Product
The coagulum present in a commercial product is measured by washing a measured
sample of a diluted emulsion polymer product through a sieve with a defined mesh size.
The coagulum is calculated as the weight of the dry residue on the sieve divided by the
total amount of dispersion ran through.
#4 Rheology/Viscosity
The viscosity or rheology of an emulsion polymer is a complex property that depends
on:
 Solid content
 Particle size distribution
 pH
 Particle surface charge, and
 Organic content in aqueous phase amongst others1

The viscosity or thickness in practical terms is defined as resistance to flow. High

viscosity liquids are relatively immobile when subjected to shear (a force applied to
make them move), whereas low viscosity fluids flow relatively easily. The shear
rate is defined as the speed with which a material is deformed.
 In some processes relevant for the application of polymer emulsion, such as spraying
or nozzle application for adhesives, the shear rate is high.
 Other processes, for instance, during pumping or formulation leveling, the associated
shear rate is low.

The viscosity remaining constant and independent from the shear rates applied defines
Newtonian fluids. Shear-thinning materials exhibit decreasing viscosities when the shear
rate increases. Most polymer emulsions fall into this category.
In some rare cases, emulsion polymer products can also have shear-thickening
properties. Under shear stress, the components of the dispersion re-arrange and the
resistance, and therefore the viscosity is increased. Therefore, the understanding of the
full rheological profile of an emulsion polymer over a wide range of shear is essential.
Just relying on a single point value at one specific set of conditions, as it is often used as
quality check with a simple rotary viscometer, at defined rotations per minute and
sample temperature, is often not sufficient.
Measurement of viscosity and other rheological properties can be made using
either capillary or rotational rheometers, the choice of system depending on:
 The properties of the material being tested
 The data required

#5 Glass Transition Temperature

The glass transition temperature (Tg) of an emulsion polymer product is measured
by Differential Scanning Calorimetry at a dried film.
 It translates into mechanical properties, for example – abrasion resistance or
rigidness of a formed film.
 The Tg of a given product is mainly influenced by the bulk monomers it is made of.
#6 Residual Monomer/VOC
As many emulsion polymer products are used in green applications for reduced
emissions and to replace solvent-borne systems, the residual monomer content as well
as the account of “total volatile organic components (VOC)” is an important
characterization. Gas chromatography is a standard measure to identify the residues of
organic components in Emulsion Polymers.

#7 Molecular Weight
There are many more dimensions to investigate and to fully characterize an emulsion
polymer. Most of them are not easy to access. For instance, the molecular weight of the
polymers is often not thoroughly analyzed.
Due to emulsion polymerization typical high molecular weights, cross-linking or grafting
reactions, the bulk polymer is often not accessible for molecular weight analysis. Only
the soluble part is investigated, separated from the insoluble one. Depending on the
specific question to be solved, also properties like polymer micro-structure, particle
surface charge, or content of aqueous solution (serum) are investigated.
Methodology
A fast amount of monomers can be used in emulsion polymerization to tailor the
application properties. The material properties of the polymer emulsion products in
application, such as:

 Hardness
 Flexibility
 Hydrophilic to hydrophobic properties
 Adhesion and cohesion

…are determined by the diligent choice of the main monomers the emulsions are made
of.
Hence, there are only three distinct monomers and one monomer class, that contribute
to the majority of the bulk polymer material of all emulsion polymers, such as:

 Styrene
 The group of Alkyl (meth) acrylates

Acrylates: The class of acrylates is the most versatile in terms of a polymer property
range. Only in a few applications, when resistance against alkaline conditions is
required, acrylic polymers are not favorable to use.

Styrene-acrylics offer excellent hydrophobic characteristics in combination with a high

glass transition temperature that translates into high durability, abrasion resistance, and
in general good mechanical properties.

Also, based on the high hydrophobicity of styrene, very low particle sizes can be
achieved with Styrene acrylic copolymers in the emulsion, an essential need for certain
applications, such as:

 Primers for the construction industry,

 Binders for paper coatings

The price of styrene is lower than acrylates that makes Styrene acrylics a cost-efficient
alternative to pure Acrylics.
The exact procedure of adding components and the profiles of important process
variables like:

 Temperature
 Monomer, or
 Initiator feeds, etc.
…have a high impact on the properties of the final dispersion.

Independent of the composition of the chemicals used, for instance – particle size,
polymer microstructure, surface charge, or particle morphology can be widely varied
by the process conditions. Therefore, two “chemically” identical emulsion polymers
can have completely different application properties.
The exact types and amounts of auxiliaries, as well as the polymerization process
used, are held as a trade secret of the emulsion polymer producers. Therefore, even
very similar products from different suppliers will not be exactly interchangeable in
all formulations or applications.

According to above I am going to synthesize poly syrene acrylic emulsion resin by some
guessing for the dark confidential areas like auxiliaries added during the process to
make sure the process proceed smoothly as predicted .
Synthesis procedure :

EMULSIFIER PREPARATION
ACRYLIC ACID KG 4.8
STYRENE KG 21.6
BUTYLE ACRYLATE KG 26.4
SOD.DIOCTYL SULPHO SUCCINATTE ESTER KG 0.96
STEARYL ALCOHOL ETHOXILATED 30 EO KG 0.38
H2O KG 16
INITIATOR VESSEL
AMONIUM PERSULPATE KG 0.2
H2O KG 4
BULK
H2O KG 30
STEARYL ALCOHOL ETHOXILATED 30 EO KG 0.1
ANTIFOAM 0.0001
PH STABLILIZER

Vessel 1
Where the Emulsifier is prepared , as shown in the table , the first four materials
(Acrylic Acid, styrene ,Butyle acrylate snd sodium sulpho succinated octyle Ester ) with
the shown percentages . Then , very good stirring until the emulsion become one phase
, checking for some time , making sure that decantation to two layers happen

Vessel 2
Where we dissolve the initiator in water with the quantites shown in table .
(ammonium persulphate dissolved in water )
Vessel 3
It is the bulk reactor , where the whole polymerizztion process takes place . With the
procedure:
1- Charge the amount of water shown in the table
2- As shown charge Stearyl alcohol Ethexilated
3- Heat the reactor to 80
4- Start addition the contents of vessel 1 and vessel2 gradually during 4 hrs .
5- After 4 hrs , emulsion has ended . charge amount of vessel 2 , to perform
the termination step +

Flowsheet for the process

Discussion
emulsion is prepared by shaking strongly the mixture of the first stage . in which
sodium DIOCTYL SULPHO SUCCINATTE ESTER acts as the surfactant , it starts to form
the missel that contain inside the monomers ( styrene , butyle acrylate ) . here we add
some amount of acrylic acid which perform important function for the final rheology of
the finished product of the resin like stability and viscosity through crosslinking
Also, the presence of STEARYL ALCOHOL ETHOXILATED 30 EO , which acts as dispersing
agent to prevent coagulation during addition of the emulsified monomers , for further
polymerization .
Surfactants (emulsifiers) are compounds that are typically amphiphilic, meaning they
have a polar or hydrophilic (i.e. water-soluble) part and a non-polar (i.e. hydrophobic or
lipophilic) part. Because of this, emulsifiers tend to have more or less solubility either in
water or in oil
The process shown In fig 1

Fig 1

The initiator … Ammonium persulfate (APS) is the inorganic compound with the formula
(NH4)2S2O8. It is a colourless (white) salt that is highly soluble in water. It is a strong
oxidizing agent that is used in polymer chemistry. which are activated by thermal
energy; typical polymerization temperatures are in the range of 70–90 °C.
one important note to mention is that , (APS ) is PH depedent , that’ s why we add the
bulk reactor some amount of PH stibilzer . to stabilize PH during polymerization .
polymerization …. After preparation of the emulsion which contain the monomers and
initiator solution . now we focus on bulk reaction where the emulsion polymerization
takes place ,
first we heat the reactor to 80 c which is the appropriate temperatue for the initiator to
break forming free radical .
 during 4 hrs we add gradually the contents of initiator vessel anf emulsion vessel . but
at the very beginning we must add some iniator solution alone to the bulk vessel , so
that when emulsified monomers added . they will find free radical to to start the
propagation process as shown in fig 2

propagation continue through chain growth process until the whole quantity in in the
emulsion vessel end , then we perform the termination process by adding last amount
of initiator solution to take the free electron from the free radical chain to terminate the
process as shown in fig 3

Fig 2

Fig 3
Certainly, any post-polymerization treatments or additions can influence the final
properties as the formulation does, in which the emulsion polymer gets applied. These
factors are not covered here.

Applications & Markets

The whole process in this application is based on creating the convenient polymer that
used as binder in coating for Housing & construction

Conclusions

Due to benefits presented by Emulsion Polymers like low cost, low emissions, zero VOC,
good shelf-life. They found their place in the field of coating and paints . so that using
the technique of emulsion polymerization , this reports is present the process for
selecting the rightful monomers based the final properties of the resin . facing some
problems during manufacturing , but solved sequentially , by adding some specialty
chemicals like defoamers , PH stabilizer and dispersing Agent . these additive help so
much to smooth sequential process of emulsion polymerization .
But , Question that arise now , how these additives affect the long term required
properties for the final application performance .