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Nazarbayev University
Polymer Syntheses
Eugene F Douglass, MS, PhD Polymer
Science - Professor
Presented by Click to enter name
Chapter 1
Polymerization of Hydrocarbons
Introduction
Free Radical Polymerization
Cationic Polymerization
Anionic Polymerization
Coordination Catalysts
Miscellaneous Methods
Introduction
Addition polymerization
Initiation
Propagation
Termination
Radical coupling
Disproportionation
Chain transfer
Techniques
Bulk
Solution
Suspension
Emulsion
Precipitation
Experimental Techniques
Recipe
Dry and inhibitor free styrene 50 g in test tube
1.0 g Benzoyl Peroxide
1-2 Hours at 80C in water bath, until it become syrupy
Add toluene to dissolve and remove, ppt in Methanol to give
solid polystyrene
Calculate % yield.
Get IR for analysis
Concept
Start
Propagation
Propagation
Termination
Monomer droplets and micelles compete for the free radicals, most
enter micelles
Polymerization occurs within micelles, new monomer dragged by
equilibrium forces from monomer droplets through aqueous phase
until monomer supply is exhausted.
Polymerization terminates upon entry of another free radical into
micelles unless replenished by more free radical and monomer.
Experimental Techniques
Recipe
Dry and inhibitor free styrene 71.2 g
128.2 g of distilled water
31.4 ml of 0.680% Potassium Persulfate
100 ml of a 3.56% soap solution
Purge system with Nitrogen gas to remove dissolved air
(oxygen).
Raise temp to 80C using mantle, stir well for 2-3 hours
Describe results, put material to dry in evaporating dish
Emulsion Polymerization
Emulsion Polymerization
4 mL of deionized water
2 mL of monomer
Purge with nitrogen gas for about 1 minute
Shake flask vigorously to form emulsion
Place in an 80oC oil bath for one hour, shaking periodically
Add DI water and NaCl to the flask to break emulsion
Remove polymer from flask and wash repeatedly with DI water
Dry polymer in oven
Styrene
Methyl Methacrylate
Ethyl Acrylate
Butyl Acrylate
Hydroxyethyl Acrylate
Acrylic Acid
Methacrylic acid
Different comonomer blends make different copolymers
Some added all together at once, others added one at a time.
Propylene
Acetylene
Ethylene
Methacrylic Acid
Propylene route
Acrylamide
Cyanoacrylates
Poly(Methyl Methacrylate)
Bulk Polymerization
Acrylic Copolymers
Thermoplastic acrylics
Acrylic Solutions
Acrylic Copolymers
Thermosetting acrylics
Acrylic Solutions
Acrylic Copolymers
Thermosetting acrylics
Thursdays lab
http://matse1.matse.illinois.edu/polymers/a.html
300 ml of 0.6 M (5%) ethyl acrylate, CH2 = CHCOOCH3 (To
prepare: mix 16 ml of ethyl acrylate with 284 ml of water.)
5 ml of 0.1 M potassium bromate, KBrO3, (To prepare:
dissolve 0.4 g KBrO3 in water and dilute to 25 ml. This will
be enough for 5 demonstrations.)
5 ml of 0.45 M sodium hydrogen sulfite, NaHSO3 (freshly
prepared) (To prepare: dissolve 0.47 g NaHSO3 in water and
dilute to 10 ml. This will be enough for 2 demonstrations.)
http://matse1.matse.illinois.edu/polymers/a.html
Procedure:
Swirl the flask to mix the contents thoroughly and allow the reaction to
proceed for about 15 minutes, shaking the flask occasionally during this
time. As the particles grow, the mixture quickly takes on a milky
appearance.
Polyacrylonitrile - PAN
Polyacrylonitrile
Nitrile resins
70:30 Acrylonitrile and MA formed in presence of butadieneacrylonitrile rubber (10-15%).
Polyacrylamide
Polyacrylamide
Poly(2-cyanoacrylate)s
Methyl and ethyl 2-cyanoacrylate form the basis of the socalled super glues
Anionic polymerization easily occurs due to two electron
withdrawing groups on double bond. Weak bases such as
water bring about rapid polymerization
UV Curable polymers/coatings
Suspension polymerization
Suspension polymerization
Procedure
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
In a laboratory hood, equip a 500-ml three-necked flask with a sealed stirrer and motor,
condenser, thermometer, and an addition funnel.
Add 150 ml of a 1% solution of sodium poly (methacrylate) in water and a buffer solution of
0.85 g of disodium phosphate and 0.05 g of monosodium phosphate in 5 ml of water
Add a dispersion of 0.5 g of dibenzoyl peroxide in 50 g of inhibitor-free methyl methacrylate to
the reaction flask.
Measure 25 ml of the 5% aqueous solution of sodium poly(methacrylate) into the addition
funnel.
Place the assembled reaction flask in the water bath, attach the stirring motor, and begin
stirring.
Adjust the stirrer speed so that droplets of monomer form that are 2-3 mm in diameter.
Heat the flask with the water bath at 80-82C for 45 to 60 min (see Notes 3 and 4).
Collect the solid particles on a funnel fitted with cheesecloth.
Bundle the particles in the cheesecloth, and place the bundle in 1 liter of boiling deionized
water. Remove the bundle and wash two more times in fresh boiling deionized water.
Open the bundle. Dry the product under reduced pressure at 60-70C.
Polyamides
Procedure
1.
2.
3.
4.
Polyamides
Condensation polymer
Raw Materials
Adipic acid
Hexamethylenediamine
Raw Materials
Azelaic acid
Sebacic acid
Dodecanedioic acid
-Aminoundecanoic acid
Caprolactam
Preparation
Preparation
Nylon 11 is produced continuously by the heating of aminoundecanoic acid at 200-220C with the continuous removal of
water. Why continuous removal of water?
Nylon 6 is produced by the ring opening polymerization of
caprolactam. 5-10% water by weight, and 0.1% acetic acid is fed
into a reactor containing caprolactam (purged with nitrogen).
Mixture heated at about 250C for 12 Hours, at 15 atm pressure.
Low molecular weight material removed by leaching with water or
heating in a vacuum.
Nylon 12 heating dodecyl lactam at 300C in the prescence of
aqueous phosphoric acid
Polymerization mechanism
Physical Properties
Polyesters
Unsaturated polyesters
Alkyds
Poly(allyl ester)s
Poly(ethylene terephthalate)
Poly(butylene terephthalate)
Cyclohexylenedimethylene terephthalate polymers
Polyester thermoplastic elastomers
Polyarylates
Poly(p-hydroxybenzoate)s
Polyester plasticizer
Unsaturated Polyesters
Raw Materials
Diols
Propylene glycol is the diol most widely used for the manufacture of
linear unsaturated polyesters. Preferred because it forms polyesters
that are compatible with styrene.
Diethylene glycol greater flexibility
Neopentylene glycol (2,2-dimethyl-1,3-propanediol) resistance to
thermal degradation
Diether of propylene glycol and bisphenol A
Raw Materials
Maleic Anhydride
Phthalic Anhydride
Raw Materials
Crosslinking Monomers
Preparation
Typical formulation
Propylene glycol
100 parts by weight
Maleic anhydride
72
Phthalic anhydride
54
The molar ratio of the ingredients shown above is 1.2: 0.67 : 0.33
Excess of glycol is to allow for loss during the reaction and limit the
molecular weight of the polymer.
150-200C for 6 -16 hours and water is continually distilled from the reactor.
Sometimes xylene is added o help remove water by azeotropic distillation,
and p-TSA added as a catalyst to lower reaction time.
It is then moved to a blending tank with about half the weight of polymer of
monomer is added, along with hydroquinone as inhibitor.
This blend is called the Polyester or Unsaturated Resin, which is then allowed
to cool to room temperature and then shipped to the customer
Preparation
Crosslinking
Crosslinking
Cold curing use accelerators, and peroxides like methyl ethyl ketone
peroxide, and cyclohexanone peroxide. Metal salts of fatty acids used
as accelerators.
Raw materials
Polyhydric alcohols
Raw materials
Modifying oils and fatty acids
Alkyd Resins
Short, medium and long oil resins
Drying oil resins most used in coatings
and alkyd paints
Semi-drying - some use in coatings and
alkyd paints for special purposes, like
high gloss finishes
Nondrying plasticizers
Fusion method
Oil hydrolyzed to give free fatty acids
Heat to 240C with a mixture of polyol and dibasic acid.
Simultaneous transesterification of polyol, dibasic acid and fatty acids
occur, with all becoming part of the polymer structure.
Solvent or solution method
Xylene (5% by weight) added to the reaction, mixture heated with a
condenser/separation funnel apparatus, which collects an azeotrope
of xylene and water, which then separates, enabling return of the
xylene to the reaction flask.
Provides good temperature control
Alcoholysis process
Oil heated with the polyol to 240C with a
basic catalyst (Ca(OH)2)
molar ratio, resulting in principal
product of monoglyceride
Add dibasic acid, and then treated the
same as in the fatty acid process, fusion or
solvent method.
Cellulose nitrate
Chlorinated rubber
Silicone resins
Phenolic resins
Amino resins
Post manufacture
Styrene and other vinyl monomers, heated with initiators under reflux
until required viscosity is reached.
Epoxies
Bisphenol A
Epoxies
Epichlorohydrin
Epoxies
Crosslinking agents
Resin
Curing agent
Curing agents
Tertiary amines
Crosslinking agents
Curing agents
Tertiary amines
Crosslinking agents
Curing agents
Polyfunctional amines
Crosslinking agents
Crosslinking agents
Crosslinking agents
Crosslinking agents
Curing agents
Acid Anhydrides
Crosslinking agents
Curing agents
Acid Anhydrides
Crosslinking agents
Curing agents
Acid Anhydrides
Amino resins
Lab Thursday
Raw Materials
Ethylene route
Polyvinyl acetate
Polyvinyl acetate
Properties
Too brittle, too much cold flow to be useful in bulk form for rigid
applications. PVAc mostly finds applications in film form in surface
coatings and adhesives. Tg is often lowered by using a plasticizer or
copolymers.
Polyvinyl acetate
https://youtu.be/B9BHxscvE9g
Lab on Thursday
Lab on Thursday
Lab on Thursday
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Polyvinyl Chloride
Photodegradation - dehydrochlorination
Chlorinated PVC
Polyurethanes
Polyurethanes
Polyurethanes
Polyurethanes
Polyurethanes
Isophorone diisocyanate
Polyurethanes
Isocyanate reactions
Isocyanate reactions
Isocyanate reactions
Isocyanate reactions
Isocyanate reactions
Polyurethane products
Foams
Flexible foams
Diisocyanate, polyol and water two reactions proceed
simultaneously:
Polyurethane products
Polyurethane products
Foams
Rigid foams
Polymeric MDI is preferred diisocyanate
Polyether and polyester foams, also one shot process, different
blowing agents are used, typically low boiling halogenated alkanes are
used. Trichlorofloromethane is most common.
Typical formulation:
Polyurethane products
Foams
Rigid are closed cell structures used for thermal insulation
products 97% of the volume of a typical foam is occupied by
gas.
Flexible foams furniture applications
Integral foams cellular core and a solid skin, molding
applications like automobile parts.
Elastomers
Cast elastomers
Polyurethane products
Foams
Rigid are closed cell structures used for thermal insulation
products 97% of the volume of a typical foam is occupied by
gas.
Flexible foams furniture applications
Integral foams cellular core and a solid skin, molding
applications like automobile parts.
Elastomers
Cast elastomers poured into a heated mold
Cast elastomers
Millable elastomers
Thermoplastic Elastomers
Surface coatings
One component systems
Air curing systems
Urethane oils, drying due to atmospheric oxygen
Moisture curing
Cure with atmospheric water
Heat curing systems
Blocked isocyanates and polyester/polyether prepolymers mixed and
then cured using heat in an oven.
Two component systems
Isocyanate polyol mixed immediately prior to use
Prepolymer polyol systems
Adhesives same types, just between two substrates
Nomenclature
Raw materials
Production
Grignard process
Production
Direct process
Production
Polymerization
Polymerization
Mechanism
Silicone Products
Silicone Products
Silicone Products
Silicone Products
Silicone Products
Resins often have a mixture of methyl and phenyl groups as part of the
backbone.
Silicone Products
Types of resins:
Physical properties
Fluids
Silicone Products
Vulcanized Elastomers
Silicone Products
Vulcanized Elastomers
Fluoropolymers
History early 20th century, polymer
polychlorotrifluoroethylene was considered of limited value.
Commercial interest developed in 1938 when Plunkett
discovered polytetrafluoroethylene at the DuPont company
by accident
Important Homopolymers
Polytetrafluoroethylene
Polychlorotrifluoroethylene
Polyvinyl Fluoride
Polyvinylidene Fluoride
Development
Physical Properties
Outstanding Chemical Resistance
Outstanding Thermal Resistance extremes of temperature
Anti-stick characteristics, non-stick surfaces
Raw Materials
Tetrafluoroethylene
Chlorotrifluoroethylene
Vinyl Fluoride -
Raw Materials
Vinylidene Fluoride
Polytetrafluoroethylene
Suspension polymerization
Physical Properties
White solid
Waxy appearance and feel
Tough flexible material with moderate tensile strength
Tendency to creep under certain conditions.
Physical properties
Physical properties
Polychlorotrifluoroethylene
Suspension polymerization
Physical Properties
White solid
Waxy appearance and feel
Greater tensile strength, hardness and resistance to creep
than PTFE
Lower softening point, less crystalline, can make thin
transparent films by quenching.
Others discussed in book pages 156-166.
Videos
https://youtu.be/vns5TVZ5xzw
https://youtu.be/rtPhlWi8t3I
The End
Presented by (click to enter name)
Polymer Chemistry 1
Nazarbayev University
Principles of Polymerization
Eugene F Douglass, MS, PhD Polymer
Science - Professor
Presented by Click to enter name
Utility
Recipe
Site of Polymerization
Site of polymerization
Progress of Polymerization
Quantitative aspects
Rate of polymerization
rp = kp[M] like before
Other characteristics
Initiators
Water soluble K or NH4+ persulfate, hydrogen peroxide, 2,2azobis(2-amidinopropane)dihydrochloride
Partially soluble ones have also been used
Redox systems advantages include temps below 50C, persulfate with
ferrous, cumyl hydroperoxide or hydrogen peroxide with ferrous,
sulfite or bisulfite.
Surfactant
Anionic surfactants mostly used fatty acid soaps (sodium or
potassium stearate, laurate or palmitate), sulfates and sulfonates.
Nonionic surfactants often used to stabilize final polymer emulsion or
paint.
Other components antifreeze additives, inorganic electrolytes, buffers
Polymer Chemistry 1
Nazarbayev University
Principles of Polymerization
Eugene F Douglass, MS, PhD Polymer
Science - Professor
Presented by Click to enter name
Chapter 3
Topics to Cover
Nature of Radical Chain Polymerization
Structural Arrangement
Rate of Radical Chain Polymerization
Initiation
Molecular Weight
Chain Transfer
Inhibition and Retardation
Energy Concerns
Auto-acceleration
Molecular Weight Distribution
Pressure effects
Process Conditions
Specific Commercial Polymers
Living Radical Polymerization
General Considerations
Thermodynamic
Polymerization will be impossible if reaction is not
thermodynamically feasible, G between monomer and polymer
must be negative
Kinetic feasibility will process proceed at a reasonable rate under a
proposed set of reaction conditions??
Radical, cationic, and anionic used under different conditions, as not all
processes can be used for all monomers or in proposed set of reaction
conditions,
Most monomers will react with free radical polymerization
Some monomers will not react with either cationic or anionic
parameters
Polymer Considerations
Effect of Substituents
Carbon #1
Carbon #2
Head to Tail
Experimental Evidence
Head to Head:
The synthetic approach involves an appropriate choice of monomer for the particular HH
polymer. For example, HH poly(vinyl chloride) is obtained by chlorination of 1,4-poly-1,3butadiene,
Sequence of events
Initiation
Propagation
Sequence of events
Termination
Combination or disproportionation:
[]
= + ,
=
Steady State approximation leads to:
= = 2
1/2
[]( )
2
Initiation
Types of Initiators:
Thermal homolytic dissociation
Redox intiators
Photochemical
Ionizing Radiation Electron beam
Pure thermal
Electrolysis of monomer solutions
Thermolytic Initiators
Azo Compounds
Redox Initiators
1. Peroxides and Reducing agents
Hydrogen peroxide with Fe+2
H2O2 + Fe+2 HO-1 + HO + Fe+3
Other peroxides and Fe+2
ROOR RO-1 + RO
ROOH OH-1 + RO
ROOCOR RCOO-1+ RO
Other reducing agents can also be used including Cr+2 , V+2 ,
Ti+3, Co+2, & Cu+1
You can also use amines as the reductant.
Redox Initiators
2. Inorganic reductants and inorganic oxidants
Photochemical Initiation
Bulk Monomer
Some monomers
M + h M*
M* R + R
Ionizing Radiation
Other methods
Initiator efficiency
Termination
Disproportionation
Coupling
Mode of Termination
Chain transfer
Mn + XA Mn-X + A
Cm generally low
because the reaction
involves the breaking of
the strong vinyl C-H
bond.
Energetic Characteristics
Thermodynamics of Polymerization
Significance of G, H and S
Ceiling Temperature
A temperature at which the propagation step becomes a reversible one.
The net rate of polymer production is zero
Floor temperature
A temperature that occurs in some cases where below this temperature
polymerization is impossible
Course of Polymerization
Auto-acceleration of pMMA
Process conditions
Bulk Polymerization Monomer is used as solvent for growing polymer chains, until
you get precipitation or gel formation. Products: Polyethylene, Polystyrene, and
pMMA.
Heterogeneous polymerization
Water acts as diluent aids in heat transfer away from exothermic reaction of
polymerization
Acrylic Family
Polymerization of Dienes
Functional Polymers
Acetylenic polymers
Polymers are macromolecules built from smaller molecular subunits, called monomers. Synthetic polymers can be classified into two
main types according to the mechanism by which they synthetically grow from monomer to polymer: chain-growth polymers and stepgrowth polymers. In this lab, chain-growth polymerization of styrene monomer using benzoyl peroxide initiator will be performed. The
characteristics of chain-growth polymerizations are (A.,Ravve, 1995):
High molecular weight polymers are formed quickly and the molecular weight of the polymers changes gradually throughout the
reaction,
Long reaction time produces high yields, but affects the molecular weight only slightly. While there are many types of specific chaingrowth polymerization mechanisms, four frequently used types are: free radical, anionic, cationic and coordination.
In our case we use free radical polymerization, which consists of three steps: Initiation, Propagation and Termination. At the
initiation stage of chain-growth free radical polymerization of styrene monomers, the initiator, I, forms free radicals species: , which
then couples with one electron of the carbon-carbon double bonds of the styrene monomer to form another radical. These bonds are
particularly susceptible to radical attack because of their relatively low stability and resonance stabilization of the resulting radical
throughout the phenyl group. In the next stage, propagation, the newly formed radical reacts with another monomer to form another
radical, resulting in a polymer that is one unit longer (Fred W, 1984). The process is then repeated to form a chain of monomers (a
polymer). The propagation step is terminated when two radicals combine together to form a neutral species, known as coupling or
combination or disproportionation, in which hydrogen transfer results in the formation of two molecules: one saturated and one
unsaturated end group (Hart H., 1999).
In this experiment free radical polymerization technique was used. In order to undergo initiation step, styrene was used with NaOH to
remove inhibitor and make it reactive, because styrene is stored with inhibitor to make it more stable for storing. Then, we placed
styrene inside a tube and flushed with nitrogen, this was done to avoid formation of explosive mixture of styrene and air. This is not
enough to make free radicals in initiation step; we need to add some benzoyl peroxide, which is used as initiator. Since, benzoyl
peroxide decomposes with hemolytic cleavage of oxygen-oxygen bond. We need to heat our sample to 80-90 degrees for 90 min. in
order to break down oxygen-oxygen bond and start initiation process. In case of low temperature, this reaction could take weeks. In
case of too high temperature, our product will be not syrupy, but solid like.
Initiation Step
Then during the reaction process we undergo propagation step, when new formed radical reacts with another monomer to form
another radical.
Propagation Step
Then this chain can be terminated by combining two radicals, known as coupling, so our polymer is growing and its chain continues.
Termination Step
Combination or Coupling
After 90 minutes of heating inside the water bath, we added toluene to dissolve the content in a tube. Actually, we might use any
non-polar solvent (like acetone), according to rule like dissolves like. Then all staff was placed inside the methanol (which is polar)
and it stops the reaction and finally solid polystyrene is precipitated.
Reaction conditions were discussed previously. Then what is important is a Pilot plant approach.
Pilot plant:
The technique seems quite similar to which we do in lab; instead amounts are much greater. What is interesting is that by pilot plant
approach they could produce super high molecular weight compounds (over MW: 320,000).
Initiation Step
2R
H
Then during the reaction process we undergo propagation step, when new formed radical reacts with another monomer to form another radical.
RCH2C
2R + CH2 CH
Propagation Step
X
X
H
H
Then this chain can be terminated by combining two radicals, known as coupling, so our polymer is growing and its chain continues.
R CH2CH n CH2C + CH2 CH
R CH2CH2 CH2C
Termination Step
n+1
Combination or Coupling
H
CH2C
X
CCH2
X
H
CH2C
X
H
CCH2
X
Initiation Step
Then during the reaction process we undergo
propagation step, when new formed radical reacts with
another monomer to form another radical.
Propagation Step
Then this chain can be terminated by combining two
radicals, known as coupling, so our polymer is growing
and its chain continues.
Termination Step
Combination or Coupling
If we want to understand experiment more deeply, we need to know the history of Polystyrene. First of Polystyrene is described as a strong plastic,
which is created from the monomer called styrene. Molecular formula is (C8H8) n and it has relatively low melting point ( 240 degree Celsius). Also,
it is one of the most used polymers in the world. According to article in Finanz Nachrichten, the worldwide market worth in 2012 accounted for
11.9 billion US dollars (Finanz Nachrichten, 2013). Moreover, it is predicted that in 2018 the data will be 19.1 billion dollars. For instance, it has
applications in production of cups, packaging peanuts, building materials and many household items.
Polystyrene has a long history of evolution behind it. In 1839, a German apothecary called Eduard Simon discovered polystyrene. Eduard Simon
isolated the substance from natural resin. However, he did not know what he had discovered. It took another German, organic chemist, Hermann
Staudinger, to realize that Simon's discovery comprised of long chains of styrene molecules, was a plastic polymer.
In 1922, Hermann Staudinger published his theories on polymers, stating that natural rubbers were made up of long repetitive chains of
monomers that gave rubber its elasticity. He went on to write that the materials manufactured by the thermal processing of styrene were similar to
rubber. They were the high polymers including polystyrene. In 1953, Hermann Staudinger won the Nobel Prize for Chemistry for his research (Bellis
M., 2015).
Thus, we understand how Polystyrene was invented and what is actual use is. Now, we will shift to the process by which it synthesized in our lab
experiment. The technique is Emulsion polymerization it refers to a unique process employed for some radical chain polymerizations. It involves the
polymerization of monomers in the form of emulsions (i.e., colloidal dispersions) (Sandler, 1998). Below is the simplified representation of Emulsion
Polymerization system.
From this (Fig. 4-1) we might clearly understand that polymer particle swollen with monomer. Then, initiation processes is held in aqueous phase
and at that time micelles forming around growing polymer and dissolved monomer. Also, there are two possibilities for particle nucleation. The first
one is Micellar particle nucleation and the second is Homogeneous particle nucleation. Where in second mechanism precipitated species are
stabilized with surfactant and absorb more monomer (Douglass E., 2015).
From the graph above (Fig. 4-2), we see three different intervals. Those intervals are different rate behaviors, which are observed during the
emulsion polymerization process. In interval I, the nucleation of the particle takes place. At this stage, the monomer convention is about 5-10%
(10171018 particles per liter are formed). Usually during the rest of the batch process, the number of particles is constant, only in case coagulation it
changes significantly.
In Interval II, the system is composed of monomer droplets and polymer particles. We might observe that monomer diffuses from the monomer
droplets through the aqueous phase. The transition occurs at about 7080% conversion. This step ends when the monomer droplets disappear.
The transition from Intervals II to III occurs at about 40% conversion for styrene. This represents that most of the monomer polymerizes during
Interval III. In this interval, the monomer concentration in the polymer particles decreases continuously (JKU, 2015).