1.

PLASTICIZERS
 HISTORY

 Man has used plasticizers to soften polymers since prehistoric

times. Water was used by potters for molding clay, by painters
applying calcimine, by boat builders and carpenters for
bending wood, by straw and leather craftsmen for shaping
their products and in gelatin desserts.
 Neat’s-foot oil and sperm oil were used as more permanent
softeners for leather, vegetable oil to reduce brittleness of
resins in paint.
 The synthesis of cellulose nitrate by Pelouze in 1833,
cellulose acetate by Schutzenberger in 1865, and PVC by
Buamann in 1872 of fered new polymers for modern industry,
but they were so intractable that their practical utilization had
to await the application of plasticizer technology.
 HISTORY

 Cellulose nitrate was first to challenge the interest of

inventors.
 Cornides (1855) added gum copal, sandaranch, and caoutchouc to it
 Pellen (1856) added castor oil to make coatings for aeronautical
balloons,
 Berard (1858) added linseed oil
 Parkes (1855-1865) mentioned adding various plasticizers including
camphor, castor oil in commercial practice.

None of these, however, was crowned by commercial success.

 HISTORY

 Camphor
 The first one to be used in real plastics was camphor, a colourless
substance, whose smell is reminiscent of many a cold remedy and
that consists of small crystals extracted from the wood of a Chinese
laurel bush known as Cinnamomum camphora.
John W. Hyatt and his brother Isaiah S. Hyatt (1869) working to adapt
cellulose nitrate as a replacement for ivory in billiard balls, choose
camphor as their preferred plasticizer to improve the moldability and
toughness of cellulose nitrate.
This led to formation of the Albany Dental Plate Company (1870) and
the celluloid company (1872) and the production of variety of plastic
and coated products, making cellulose nitrate the leading polymer
and camphor the leading plasticizer, of the 19 th century.
Because of its odour, volatility and flammability, it was far form the
ideal plasticizers and led to the development of better plasticizers.
 HISTORY

 https://books.google.co.in/books?id=cVHBqhdIEisC&pg=PA16
7&lpg=PA167&dq=history+of+plasticizer&source=bl&ots=1L7
0uHBAhi&sig=ACfU3U366QuvAckLVZvJxz665PQIkYGHDw&hl=e
n&sa=X&ved=2ahUKEwiupq7mmsLhAhUPHKYKHdmpC_IQ6AE
wEHoECAkQAQ#v=onepage&q=history%20of%20plasticizer&f=
false
 https://www.azom.com/article.aspx?ArticleID=1224
 PLASTICIZER

 The development of cellulose nitrate plastic in 1846 led to

the patent of castor oil in 1856 for use as the first plasticizer.
 In 1870, camphor became the most favoured plasticizer for
cellulose nitrate.
 Phthalates were first introduced in the 1920s and quickly
replaced the volatile and odorous camphor.
 In 1931 , the commercial availability of polyvinyl chloride
(PVC) and the development of di (2-ethylhexyl)
phthalate (DEHP) began the boom of the plasticizer PVC
industry.
 PLASTICIZER

 Plasticisers are a rather special type of additive.

 Without plasticisers PVC would have been too brittle and
fragile to be used as a plastic.
 without plasticisers most injection moulding compounds
would be entirely unsuitable for that purpose, and without
plasticisers, some blends of rubber simply could not be
produced.
 Not only do plasticisers make plastics extensible, elastic and
flexible at low temperatures, in many cases it is only possible
to process polymer products on a commercial basis by
incorporating a plasticiser.
ADDITIVES
ADDITIVES
 PLASTICIZER

 80-90% plasticizers are used in PVC .

 The Successful addition of a plasticizer will result in the
formation of a product with a degree of flexibility, such as a
cable insulation or sheathing, a floor covering or flexible
profile.
 Ef fect on polymer properties: an important distinction from
other additives.
 Increases polymer flexibility, elongation or workability.
PLASTICIZER CONTD..
 PLASTICIZATION THEORIES

Plasticizer acts as a lubricant, reducing

Lubricity Theory intermolecular friction between polymer molecules
responsible for rigidity of the polymer.

Gel Theory Polymers are formed by an internal three-dimensional

network.

Free Volume Plasticizer lowers the glass transition

Theory temperature (Tg) of the polymer.

Mechanistic Plasticizer molecules are not bound permanently to

Theory the polymer molecules form.
 PLASTICIZATION THEORIES CONTD..

 Lubricity Theory:
Similar to metal parts lubrication by oil
The plasticizer acts as a lubricant to reduce friction and facilitates
polymer chain mobility past one another, consequently lowering
deformation;

 Gel Theory:
This theory extends the lubricity theory
It suggests that a plasticizer disrupts and replaces polymer–
polymer interactions (hydrogen bonds, vander Waals or ionic
forces, etc.) that hold polymer chains together resulting in
reduction of the polymer gel structure and increased flexibility;
 PLASTICIZATION THEORIES CONTD..

 Free Volume Theory

The free volume of a polymer can be described as the “empty
internal space” available for movement of polymer chains. The
free volume of a polymer increases when it reaches the glass
transition temperature (Tg).
At the Tg, the molecular motion begins to occur, which
corresponds to increase in the free volume of the polymer.
These Plasticizers molecules are having low glass transition
temperature than the polymer, so that Tg of the resulting mixture
will be lower.
 GLASS TRANSITION TEMPERATURE (T G )

 The temperature at which the glassy polymer becomes

rubbery on heating and rubbery polymers reverts to glassy on
cooling.
 Polymer in rubbery state are very viscous liquids with
relatively high freedom of rotation round the carbon -carbon
bonds in the backbone within the constraint of tetrahedral
bond angle.
 The temperature is high enough so that most bonds capable
of overcoming potential energy barrier against rotation. This
rotational freedom resulted in very flexible chains.
 T G OF VARIOUS POLYMERS

POLYMER Tg (⁰C) POLYMER Tg (⁰C)

Silicone rubber -123 Poly (methyl acrylate) 5
Polyethylene Poly (n-butyl methyl
-110 acrylate) 22

Polybutadiene -85 Poly (vinyl acetate) 30

Polyisoprene -70 Poly (ethyl methacrylate) 65
Poly (n-butyl acrylate) -56 Poly (vinyl chloride) 82
Poly (ethyl acrylate) -22 Polystyrene 100
Polypropylene -18 Poly (methyl methacrylate) 105
 MECHANISM

 As plasticizers usually possess relatively long alkyl

chains, they have the effect of screening the polymer
chains from each other, thereby preventing them from
re-forming the chain-chain interactions which give the
unplasticized polymer its rigidity.
 CLASSIFICATION

 Majority of plasticizers are Organic Esters.

According to technique of Plasticization

External Internal

Not physically bound to Group constituting a part of

polymer & can evaporate, a basic polymer chain,
migrate or exude from which may incorporate bet.
polymer. chain
 CLASSIFICATION CONTD..

 EXTERNAL PLASTICIZERS
These are high boiling liquid, non-volatile and having low vapour
pressure.
They must dissolve in polymer and reduce Tg of polymer below
room temperature rendering it softer and flexible.
They act as a lubricant between the polymer chains, facilitating
slippage of chain under stress.

 INTERNAL PLASTICIZERS:
 A rigid polymer may be internally plasticized by chemically
modifying the polymer or monomer so that flexibility polymer is
increased
 The process by which Tg of rigid PVC is lowered through co-
polymerization, is called internal plasticization.
 CLASSIFICATION CONTD..

 Other
Conventionally classified as

Primary Secondary

Sufficient level of Limited compatibility &

compatibility to be can exude if used
used give desirable alone.
effect. directly interact Incorporate with
with chain. primary plasticizer.
 CLASSIFICATION CONTD..

 PRIMARY PLASTICIZERS:
 Also called as chemical plasticizers.
 Highly compatible with PVC.
 when added to polymer, will cause the properties of elongation
and softness of the polymer to be increased.

 EXTERNAL PLASTICIZERS
Also called as plasticizing oils.
Less compatible with resin.
They are not used alone but when combined to primary
plasticizers will enhance the plasticizing performance of primary
plasticizer.
 CLASSIFICATION CONTD..

Phthalate Aliphatic Ester Phosphates

di(2-ethylhexyl) DOP or DEHP di(2-ethylhexyl) adipate DOA trioctyl TOP
diisooctyl DIOP di(2-ethylhexyl) azelate DOAZ cresyl diphenyl CDP
diisodecyl DIDP di(2-ethylhexyl) sebacate DOS tricresyl TCP
butylbenzyl BBP triphenyl TPP
butyloctyl BOP Epoxies tri(2-ethylhexyl) TEHP
diisononyl DINP epoxidized soybean oil ESBO
ditridecyl DTDP epoxidized linseed oil ELO Trimellitates
diundecyl DUP epoxy stearate tris(2-ethylhexyl) TOTM

linear C7-C11 711 phthalate 2-ethylhexyl epoxytallate triisoctyl TIOTM

di(2-ethylhexyl)
terephthalate DOTP
CLASSIFICATION CONTD..
 CHOOSING YOUR PLASTICIZER

Effectiveness Considerations
 How Much Plasticizer is Necessary
 Interaction Parameters

Application Considerations :
 Temperature Range
 Degree of Flexibility Desired

Phthalates: the #1 Choice for PVC

 SELECTION CRITERIA

 Choice of plasticizer depends upon the properties

required in final product, the application
technology used to make it !!
 Prize boundaries present for product process,
 Stability in processing & service condition,
 Compatibility & ease of mixing,
 Resistance to water, chemicals, weathering, dirt &
microorganisms,
 Toxicity,
 Effect on Rheological properties.
 PLASTICIZER EFFICIENCY

 The measure of concentration of plasticizer require to

improve a specifies softness to PVC.
 Plasticizer ef ficiency increases as carbon number of alcohol
chain decreases.
 For phthalates,
BBP>DIHP>DOP>DINP>DIDP
 Linear plasticizer is more ef ficient.
 Phthalate and adipate esters are more ef ficient than their
trimellitate equivalent.
 GLOBAL PLAYERS

COMPANY COUNTRY
UPC Technology Corporation Taiwan
Nan Ya Corporation Taiwan
Aekuyung Petrochemicals Korea
Sandung Oilu China
Eastman Chemical Company USA
L G Chem Korea
KLJ Group India
Guandong Chunda Chemical Industry China
BASF SE Germany
Exxonmobil Corporation USA
Evonik Industries AG Germany
 PHTHALATE PLASTICIZERS

 Most widely use as plasticizer.

 Phthalates accounted for 75% of global demand of
plasticizers in 2014.
 A Phthalate ester derived from phthalic acid by an
esterification reaction.
 Mechanism: phthalic acid to phthalate ester

H
 PHTHALATE PLASTICIZERS

Properties:
Colorless
Oily liquid (like vegetable oil)
Ester odour
High boiling point
Inert and very stable over long periods
 1. DEHP/DOP
( DI(2-ETHYLHEXYL) PHTHALATE)

Structure:

 Properties  Uses
 Insoluble in H2o  Used in medical devices
 Soluble in mineral oil, hexane,  Toys
most organic solvents  Pacifiers
 Easily dissolved in bodily fluids,  Vinyl Upholstery
such as saliva and plasma.  Food containers
 Boiling point: 386.9oc  Table cloths
 Density: 0.9732 g/L  Shower curtains
 Molecular weight: 390.5618  Raincoats ( and the list goes
g/mol on……..)
 1. DEHP/DOP
( DI(2-ETHYHEXYL) PHTHALATE)

Market: Regional Segment Major Players:

analysis a. Eastman, USA
a. North America b. Exxonmobil Chemical,
b. Europe USA
c. China c. LG Chem, Korea
d. Japan d. BASF, Germany
e. Southeast Asia e. UPC Technology
f. India f. Nan Ya Plastics, Taiwan
g. Aekuyung
Petrochemical, Korea
h. KLJ Group, India
i. Guangdong Chunda
Chemical, China
 2. DIBP (DI ISOBUT YL PHTHALATE)

Structure:

 Properties  Uses
 Colorless  Protective coatings
 Ester odor oily liquid  Paints
 Boiling point: 327 oc  Food packaging
 Density: 1.030-1.040 g/cc  Footwear
 Molecular weight: 278 g/mol  Hose pipes
 3. DBP (DI BUT YL PHTHALATE)

Structure:

 Properties  Uses
 Colorless  Artificial leather
 Ester odor oily liquid  Rubber products
 Boiling point: 340 oc  Polymeric building materials
 Density: 1.041-1.045g/cc  Paints
 Molecular weight: 278 g/mol  Varnishes & lacquers
 Hose pipes
 Footwear
 4. BBP (BENZYL BUT YL PHTHALATE)

Structure:

 Properties  Uses
 Boiling point: 370 oc  Artificial leather
 Density: 1.1 g/cc  Vinyl foams
 Molecular weight: 312 g/mol  Food conveyor belts
 Traffic cones
 Flooring
 5. DINP (DIISONONYL PHTHALATE)

Structure:

 Properties  Uses
 Insoluble in H2O  Replaced DEHP in toys when
 Soluble in most organic initially determined to be
solvents carcinogenic.
 Boiling point: 250oc  Vinyl flooring
 Density: 0.98 g/cc  Wire and cable
 Molecular weight: 418.6 g/mol  Wood veneer/finish
 Sealants
 Carpet backing
 6. DIDP (DIISODECYL PHTHALATE)

Structure:

 Properties  Uses
 Insoluble in H2O  Plastisol application
 Soluble in most organic solvents  Wire and cable
 Boiling point: 255oc  Lacquers
 Density: 0.96 g/cc  Sealants
 Molecular weight: 446.67 g/mol  Polymers
 Anti-corrosion paints
 Anti-fouling paints
 7. DPHP (DI (2-PROPYLHEPT YL) PHTHALATE)

Structure:

 Properties  Uses
 Colorless  High temperature application
 Odorless  Wire & cable
 Soluble in most organic solvents  Automotive interior trim
 Insoluble in water  Roofing membranes
 Boiling point: 251-254 oc  tarpaulins
 Density: 0.957-0.965 g/cc
 Molecular weight: 446 g/mol
 8. DEP (DI ETHYL PHTHALATE)

Structure:

 Properties
 Colorless
 Transparent oily liquid
 Slight aromatic odor
 Soluble in most organic solvents
 Boiling point: 298oc
 Density: 1.114-1.120 g/cc
 Molecular weight: 222 g/mol
 Uses
 Varnishes & Paints
 Fragrance/Perfumes
 Alcohol denaturant
 Camphor substitute
 9. DDDP (DI-DO-DECYL PHTHALATE)

Structure:

 Properties  Uses
 Colorless  Wire and cables
 Odorless  PVC products
 Soluble in most organic solvents  Availing elasticity with least
 Boiling point: 256-257 oc migration
 Density: 0.939-0.945 g/cc
 Molecular weight: 502.77 g/mol
 10. DMP (DI METHYL PHTHALATE)
Structure:
 Properties
 Colorless
 Clear oily liquid
 Slight sweet odor
 Soluble in all organic solvents
 Boiling point: 282 oc
 Density: 1.180-1.190 g/cc
 Molecular weight: 194g/mol
 Uses
 Celluloid
 Varnishes/Lacquers
 Mosquito repellent
 Additive in rubber
 Graphic film & sheets
 11. DOTP (DI OCT YL TEREPHTHALATE)

Structure:

 Properties  Uses
 Clear viscous liquid  High temperature application
 Soluble in most organic solvents  Vinyl gloves
 Boiling point: 400 oc  Wall covering
 Density: 0.980-0.986 g/cc  Vinyl flooring
 Molecular weight: 390 g/mol  Synthetic rubber
 Carpet
 12. DBS (DI BUT YL SEBACATE )
Structure:
 Properties
 Organic chemical
 Dibutyl ester of sebacic acid
 Boiling point: 344.5 oc
 Density: 0.94 g/cc
 Molecular weight: 314 g/mol
 Uses
 Food packaging
 Medical devices
 Pharmaceuticals application
 As lubricant in shaving lotion
 Flavouring additive in non-
alcoholic beverages, ice cream
etc.
 13. DMS (DIMETHYL SEBACATE )

Structure:

 Properties
 Colorless
 Trasnparent liquid
 Easily biodegradable
 Boiling point: 294 oc
 Density: 0.988-0.992 g/cc
 Molecular weight: 230 g/mol
 Uses
 In light stabalizers
 Resins & Rubbers
 Paint additive
 Softening agent
 14. ATBC (ACET YL TRIBUT YL CITRATE)

Structure:

 Properties  Uses
 Colorless  Latex adhesives
 Odorless oily liquid  Food packing
 Insoluble in water  Medical products
 Soluble in organic solvents &  Toys
alcohols  Safety glass
 Boiling point: 173 oc
 Density: 1.050 g/cc
 Molecular weight: 402.5 g/mol
 CLASSIFIED PLASTICIZERS

BBP DBP

DOP
(DEHP) DiBP

The main focus of attention is on the plasticizers BBP, DBP, DOP

(DEHP) and DiBP which have been classified as SVHC (Substances of
Very High Concern) by the ECHA (European Chemicals Agency).
 GENERAL PURPOSE PLASTICIZER

DINP DINCH
General
Purpose
Plasticizer

DIDP/
DPHP DOTP

The phase out of classified phthalates has triggered its substitution by

the general purpose plasticizers DINP, DIDP, DPHP, DINCH and
Terephthalates such as DOTP
 SPECIALT Y PLASTICIZER

Specialty
Plasticizer

Di-benzoates Citrates Terephthalates

In applications where fast fusing properties are required, the use of

general purpose plasticizers creates challenges as their performance
in these applications is not ideal imposing their use in combination
with higher concentrations of specialty plasticizers to achieve the
viscosity and gelling properties required in these outlets.
 GENERAL PURPOSE & SPECIALT Y
PLASTICIZER
 General Purpose Plasticizers
Used for high volume products suitable for a wide range of
applications and processing techniques

 Specialty Plasticizers
Provide for distinctive properties such as reduced volatility or
plasticity in low temperature conditions serving in selected
applications
Typically correspond to smaller volume products used in combination
with general purpose plasticizers but have premium prices compared
to these general plasticizers.
Fast fusion properties provided to plasticized polymer allowing for
lower processing temperatures and shorter cycle times
Easily compatible with PVC and other polymers
Biodegradability
 TOXICIT Y (LD50 & LC50)

S NO. LD50 LC50

1 Lethal dose Lethal concentration

The dose means the organism In this, fish or daphnia are placed in water
2
ingests the toxic substance. with a concentration of the toxic substance.

The LD50 is a single dose of a

LC50 is the concentration of the chemical in
chemical that, when fed to a group
3 the air or water that will kill 50% of the test
of test animals or applied dermally,
animals with a single exposure
will kill 50% of the animals.

Unit: mg/l
Unit: mg/kg
It is the estimated air concentration of a
4 It stands for mg of substance per kg
substance administered via inhalation route.
of body weight administered per day.
Sometimes, ppm is used.

the smaller the LD50 value, the the larger the LC50 value, the lower the
5
more toxic the chemical is toxicity.
 TOXICIT Y DATA (LD50 & LC50)

LD 50 LC50
S NO. Phthalates/Citrates Oral-Rat Oral-Mice Commonly Used Fish (mg/l)- Commonly Used
(mg/Kg) (mg/Kg) Term 96 hrs Term

1 BBP (Benzyl Butyl Phthalate) 2330 4170 Slightly Toxic 1.7 Extremely Toxic

2 DOTP (Di Octyl Terephthalate) 5000 3200 Slightly Toxic 984 Moderately Toxic
Practically Non-
3 DINCH 5000 5000 100 Moderately Toxic
toxic
DPHP (Di 2-Propylheptyl Practically Non-
4 5000 5000 10000 Practically Non-toxic
Phthalate) toxic
Practically Non-
5 DEP (Di Ethyl Phthalate) 6178-8600 9168-31000 12 Highly Toxic
toxic
Practically Non-
6 DBP (Di Butyl Phthalate) 8000 3500 0.85 Extremely Toxic
toxic
Practically Non-
7 DIBP (Di IsoButyl Phthalate) 15000 10000 0.9 Extremely Toxic
toxic
Relatively
8 DOP/DEHP (Di Octyl Phthalate) 30600 33500 0.67 Extremely Toxic
Harmless
Relatively
9 ATBC (Acetyl tri-n-butyl Citrate) 31400 NA 38-60 Highly Toxic
Harmless
Relatively
10 DINP (Di isoNonyl Phthalate) 50000 50000 500 Moderately Toxic
Harmless
Relatively
11 DIDP (Di IsoDecyl Phthalate) 64000 97000 10000 Practically Non-toxic
Harmless
 CARCINOGENICIT Y

S NO. Phthalates/Citrates IARC NTP ACGIH

1 DOP/DEHP (Di Octyl Phthalate) 3 R A3
2 BBP (Benzyl Butyl Phthalate) 3 NL NL
3 DBP (Di Butyl Phthalate) NL N NL
4 DIBP (Di IsoButyl Phthalate) NL NL NL
5 DEP (Di Ethyl Phthalate) NL NL NL
6 DINP (Di isoNonyl Phthalate) NL NL NL
7 DOTP (Di Octyl Terephthalate) NL NL NL
8 DIDP (Di IsoDecyl Phthalate) NL NL NL
9 DINCH NL NL NL
10 DPHP NL NL NL

11 ATBC (Acetyl tri-n-butyl Citrate) NL NL NL

 CARCINOGENICIT Y

 NTP- National Toxicology Program, U.S. Department of Health

and Human Services
Group K: known to be human carcinogens
Group R: reasonably anticipated to be human carcinogens.
 IARC- International Agency for Research on Cancer
Group 1: carcinogenic to humans
Group 2A: probably carcinogenic to humans
Group 2B:possibly carcinogenic to humans.
Group 3 - Not classifiable as to its carcinogenicity to humans
Group 4 - Probably not carcinogenic to humans
 ACGIH- American Conference of Governmental Industrial
Hygienists
Group A1: confirmed human carcinogen
 Group A2: suspected human carcinogen
Group A3: confirmed animal carcinogen with unknown relevance to
humans.
 https://www.upmarketresearch.com/reports/Global -Dioctyl-
Phthalate-DOP-Plasticizer-Industry -Market- Analysis-Forecast-
2018-2023
 https://www.chemarc.com/content/article/plasticizer ---a-
market-scenario/59a539454826ad1aa37985f9
 http://kljindia.com/plasticizers.html