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PLASTICIZERS
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
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..
External Internal
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
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..
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
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
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)
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 Uses
Colorless Varnishes & Paints
Transparent oily liquid Fragrance/Perfumes
Slight aromatic odor Alcohol denaturant
Soluble in most organic solvents Camphor substitute
Boiling point: 298oc
Density: 1.114-1.120 g/cc
Molecular weight: 222 g/mol
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 Uses
Colorless Celluloid
Clear oily liquid Varnishes/Lacquers
Slight sweet odor Mosquito repellent
Soluble in all organic solvents Additive in rubber
Boiling point: 282 oc Graphic film & sheets
Density: 1.180-1.190 g/cc
Molecular weight: 194g/mol
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 Uses
Organic chemical Food packaging
Dibutyl ester of sebacic acid Medical devices
Boiling point: 344.5 oc Pharmaceuticals application
Density: 0.94 g/cc As lubricant in shaving lotion
Molecular weight: 314 g/mol Flavouring additive in non-
alcoholic beverages, ice cream
etc.
13. DMS (DIMETHYL SEBACATE )
Structure:
Properties Uses
Colorless In light stabalizers
Trasnparent liquid Resins & Rubbers
Easily biodegradable Paint additive
Boiling point: 294 oc Softening agent
Density: 0.988-0.992 g/cc
Molecular weight: 230 g/mol
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
DINP DINCH
General
Purpose
Plasticizer
DIDP/
DPHP DOTP
Specialty
Plasticizer
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)
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.
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