P.
Tassone
November 2016
UNSATURATED POLYESTER RESIN
(AKG/Cimstone project)
PRELIMINARY STUDY
INDEX
1- GENERAL ABOUT UNSATURATED POLYESTER RESIN (UPR)
Resin is derived from coal and oil. The industrial base for the production of
resins is an oil refinery and petro-chemical works which are today easily
found in all the countries. The characteristic smell of polyester resin is
given by styrene, which is added to the polyester base at a late stage in
production.
2- WHAT THEY ARE
The unsaturated polyester resins (UPR) are the product of a condensation
reaction (or esterification) between the bi-functional acids and glycols, one of
which, generally the acid, contains at least one unsaturated double bond.
This polymer is dissolved in a monomer, usually styrene, which also contains
an unsaturated double bond. With the help of heat or by free radicals
chemically activated from a catalyst, which in most cases is of peroxide type,
the polymer and the monomer react through the double bonds (cross-linking
reaction) to form a solid structure.
The unsaturated polyester resins of the most common industrial use are of
the following types: ortophtalic, isophthalic, di-cyclopentadyenic, epoxy polyester and vinylester. In this project we will deal exclusively with the first
type.
The double carbon-carbon bond present in the polymer chain, which is
subsequently made to react with a similar double bond present in the
monomer used as a reactive diluent, is the key factor in an unsaturated
polyester resin. In all commercial resins this double bond is brought from
maleic anidhrite or from fumaric acid. The molar ratio of maleic anhydride or
fumaric acid with respect to all the other ingredients of the polyester
determines the frequency of reactive double bonds along the polymer chain.
In the simplest case the reaction between Monopropylenglycol, Isophtalic
acid and Maeic anydrithe to give an unsaturated polyester polymer is here
described:
3- UPR PRODUCTION
The unsaturated polyester resins can be synthesized with different
techniques, schematically listed as follow:
1 . fusion reaction in single stage;
2 . fusion reaction in double stage;
3 . reaction with azeotropic distillation;
4 . reaction in the presence of catalysts.
Most of the commercial resins of orthophthalic type are industrially
manufactured according to the first technique, whose fundamental steps are
here described.
The single-stage reaction involves simply loading all the raw materials
together, and these are heated and reacted at a temperature of 190-200 C
under agitation. The esterification process is accelerated by effective removal
of water of reaction; the progress of the process is followed by measuring the
increase in viscosity of the polymer and the reduction of the acid groups
present, as determined by titration. The reaction is allowed to proceed until
the desired final acid number. Upon reaching the final acid number the
temperature in the reactor is lowered to 115-120 C and the polymer thus
synthesized is diluted in the monomer to be rendered usable at a viscosity
suitable for handling. The addition of small amounts of inhibitor makes the
resin stable for several months.
It is necessary to specify that in the simpler process, reactor and blender
coincide and the intermediate storage is not necessary.
5
4- INDUSTRIAL PRODUCTION PLANT
A short description of the industrial plant is also necessary.
The main part of the plant consists of the reactor, where the raw materials are
made to react at the planned temperature: in the medium size, it is a reactor
of 25 ton in stainless steel, jacketed and provided with an internal coil for the
circulation of diathermic oil and one for the cooling water. The reactor
contains a shaped blades stirrer and a system of breakwater for effective
handling of the fluid in its interior, even at higher viscosities. The loading of
raw materials in the reactor is scheduled through pipes coming from the
storage vessels of the raw materials.
The reactor is positioned below the distillation column; this separates water
from glycols and conveys the components of higher boiling point in the
reactor.
At the side of the distillation column packed is positioned a second column
that constitutes the "short path" for the removal of fluids still distillable during
application of the vacuum, in the terminal stage of the reaction.
The two columns are surmounted by a heat exchanger tube bundle for the
condensation reaction water, which is collected in a Florentine equipped with
speculum for visual control of the amount of reaction water recovered.
Various systems of connection and bypass are designed to have maximum
flexibility in the conduct of the condensation reaction. A sampling valve on the
reactor is used to perform viscosity measurements and titration during the
process.
All components of the plant are designed and constructed both to perform the
esterification reaction under slight pressure of inert gas, which can be placed
both on the surface and in depth, which under vacuum up to a pressure of 3040 mbar residues.
The system is automated with regard to the control systems of temperature
and pressure.
The discharge of the polymer at the end of the reaction takes place through a
jacketed pipeline that conveys the mass in a dissolver in which has been
previously downloaded from its containment tank the expected amount of
reactive diluent. The blender is jacketed and provided with a cooling coil in
which the water is circulated. An effective agitation system allows the heat
exchange optimally even in the dissolver.
5- LAY OUT OF A FACTORY
The layout of the plant, in an area of 3000 5000 sqm (according to the
dimension of the plant and the roads connected), forecasts the following
parts:
-
building construction on three or more floors
storage area for services gas (Nitrogen)
storage area either for solid raw materials and liquid raw materials
storage area for the finished product
area of unloading by hydraulic pumping of liquid raw materials directly
from the trucks
area of loading by hydraulic pumping of the finished product directly into
the trucks
small laboratory
dressing room
offices.
The plant needs of the following services:
-
thermal station
discharge gas treatment station
discharge line for waste water
compressed air station/vacuum
Nitrogen storage and pipe-lines.
6- STAFF OF THE FACTORY
Concerning the minimum number of persons necessary to follow the
production process it is possible to summarize the following, considering a
continuous process in three shifts.
-
1 manager responsible for the production
12 operators (9 divided in three shifts + 1 shift of rest)
1 operator for the unloading/loading operations
1 mechanic
1 electrician
1 chemist
1 software specialist (whether the automation of the process needs
him).
In case of a lower the degree of automation of the manufacturing process this
number can increases.
Whether working in autonomy the Factory needs also of a purchasing
department and of an administration and human resources department.
7- ECONOMIC ANALYSIS
The economic analysis necessary for a complete feasibility study should
disclose:
- All costs involved in starting a new industrial plant (capital investment).
- Cost of construction:
Main process units
Surrounding infrastructure
Contingency
- Working capital
- Plant commissioning and start-up
- All costs surrounding the production of UPR:
Raw materials acquisition & utilities generation (manufacturing
variable costs)
Labor wages, maintenance, operating charges, overhead, taxes and
insurance (manufacturing fixed costs)
Administration, research and product distribution (corporate overhead
costs)
Without more detailed information the investment can be quoted between 1.5
and 2 millions EURO according to the capacity of the plant (in this case an
evaluation has been made for a small capacity plant, i.e. a plant equipped
with only one reactor of 10 cubic meters, that according to my opinion is the
smallest capacity to justify an industrial plant) and the degree of automation
required.
Building construction and thermal station installation are excluded by this
calculation.
It is worth saying that it is possible to find into the market part of the plant
(particularly the reactor) of Chinese manufacturing at very cheap price.
Finally, as a rule of thumbs, it is possible to evaluate the final cost of the UPR
produced by such a plant considering the real costs of all the raw materials
entering a formulation added by 20% as cost of the process.
10
8- PRODUCTIVITY
The production of UPR is a discontinuous process in batch.
Assuming a reactor of 10 cubic meters of real capacity, the productivity can
easily calculated taking into consideration that a standard production process
needs about 10 - 12 hours/batch.
As already described the UPR is obtained dissolving the polymer in Styrene:
for a resin suitable for the Cimstone needs this ration is 65:35.
Therefore if we assume a yearly production run for 5 days on 7/week in 12
months, there are
365 -105 = 260 days available
they corresponds at 6240 hours, and therefore in the worse condition (12
hours/batch)
6240 / 12 = 520 batches
The production of polymer results in:
520 x 10 = 5200 cubic meters
which corresponds at a production of UPR in the ratio 65:35 of Styrene of:
5200 / 0.65 = 8000 cubic meters
and considering a specific weight for the resin of 1.12:
8000 x 1.12 = 8960 ton
I wish to remind that the average consumption of resin for the Cimstone
factory in the year 2015 has been of 3500 tons and the same amount can be
estimated for the year 2016.
It is clear that such a dimension for this production plant, in the working
conditions described (i.e. 5 on 7 working days/week and 12 hours/batch) is
able to feed 2 lines of an engineered stone production factory of the size of
Cimstone, leaving available the remaining 20% for the market.
In the following table are reported the productivities for three different types of
reactors of real capacity respectively of 10, 15 and 20 cubic meters, in two
working conditions, i.e. 5 days on 7/week for 12 months/year and 7 days on
11
7/week for 11 months/year. Considering a consumption of 7000 ton/year for
two production lines in the Cimstone factory the amount of resin that could be
destined to the market is reported in the last column.
REACTOR
CAPACITY
(M3)
WORKING
DAYS
(WEEKLY)
RESIN
PRODUCTION
(TON/YEAR)
RESIN
FOR THE MARKET
(%)
10
5/7
8960
20
10
7/7
11510
40
15
5/7
13440
48
15
7/7
17265
59
20
5/7
17920
61
20
7/7
23020
70
12
9- RAW MATERIALS
The main raw materials necessary for the production can be chosen between
the followings.
Glycols:
Monopropylen glycol
Monoethylen glycol
Di-ethylen glycol
Acids:
Maleic anidrithe
Ortophtalic anidrithe
Monomers:
Styrene.
The chemical formulation of these products is reported in the table of the
following page.
The inhibitors used to avoid any undesired hardening of the resin either
during the condensation process and the dissolution with styrene are for
example:
- Hydrochinone
- Toluen Hydrochinone
- Terz- Butyl Catecol.
Other raw materials that could be taken into consideration are:
Di-propylen glycol
Butyl glycol
Tri-methylolpropane
Fumaric acid
Adhypic acid
Copper nafthenate.
About raw material costs nothing is possible to say because it is impossible to
have today information about an industrial cost of each raw material in Turkey
considering that they are connected with the oil cost variation.
13
RAW MATERIALS
CHEMICAL STRUCTURE
CH
HO
OH
CH2
Monopropilenglycol
CH3
Monoetilenglycol
Diehtylenglycol
CH2
HO
HO
CH2
CH2
CH2
OH
CH2
CH2
OH
Maleic anidrithe
O
O
Phtalic anidrithe
Styrene
14
10- OTHER APPLICATIONS (*)
The global unsaturated polyester resin market was valued at US$ 7.17 Billion
in 2014, and is expected to reach US$ 9.87 Billion by 2020.
The orthopthalic segment is one of the most significant types in the
unsaturated polyester resin market.
Unsaturated polyester resins are known for their commercial usage in
fiberglass reinforced plastics (FRP). Other than that, on the basis of end-user
industry, this market is sub-divided into:
building & constructions,
marine,
wind energy,
electrical & electronics,
pipes & tanks,
engineered stones,
automotive/transportation.
Major use of these resins is for applications and products, such as:
putty for different applications,
boat and ship building,
manufacturing of wind blades,
electrical windmills,
automotive applications,
sanitary wares,
fiberglass reinforced plastics,
non-reinforced plastics.
(source: MARKETS and MARKETS)
15