Acrylonitrile Butadiene Styrene

Resin (ABS)
 Introduction
• ABS comprises
– The dispersed phase of SAN copolymer grafted on
polybutadiene rubber
– The continuous phase of SAN copolymer
• Composed of three kinds of monomers
– Acrylonitrile (21 to 27%)
– Butadiene (12 to 25%)
– Styrene (54 to 63%)
• Developed to improve the brittleness which is the
disadvantage of polystyrenes, through addition of a
rubber component while maintaining hardness and
fluidity, which are the advantages of polystyrenes
 Production and Producers of ABS
• Two Methods • GE Plastic and Dow
– Emulsion Chemical in the US
Polymerization • Lanxess and BASF in
– Mass/Bulk Germany
Polymerization
• Chimei in Taiwan
• LG Chem. in Korea, etc.,
Emulsion Polymerization
Emulsion Polymerization
 Emulsion Polymerization
• Preparation of polybutadiene latex
– Initiators : Pot. persulphate or oil-soluble
initiators using a redox system
– Particle size can be controlled by the
• Ratio between monomer and water as used
• Reaction temperature
• Latex agglomeration (Chemical: Acid or Physical :
Freezing process)
 Emulsion Polymerization

Preparation of ABS latex

• ABS resins are produced in the form of a bimodal type
comprised of two kinds of particle sizes
– For better surface and impact resistance properties.
• The particle size is generally in the range of 0.1 to 0.4 μm.
Method (1)
• The graft polymerization is also accomplished in the
concurrent presence of two kinds of polybutadiene latex
having different particle sizes
Method (2)
• After the graft polymerization, the respective
polybutadiene latexes may be mixed in a certain ratio
 Emulsion Polymerization
Preparation of ABS latex (Conti…)
• Water soluble or Oil-soluble initiator using
the redox system
• Ratio between PBD latex and styrene and
acrylonitrile monomers (1:1)
• The ratio between styrene and acrylonitrile
(7:3)
• The reaction time is usually 4 to 6 h
 Emulsion Polymerization
Coagulation and recovery
• Antioxidant solution
– Phenolic or phosphate based
– Prevent the oxidation during the coagulation and drying steps
• Coagulant: Dilute acids or CaCl2 Solution
• Particle size distribution:
– Amount of coagulator
– Coagulating temperature
– Stirring speed
– Residence time
• Slurry is centrifuged to remove water and then washed to
remove the impurities
• The water content after drying is kept below 2%
 Mass polymerization
Polymerization:
• Rubber + Styrene
• Chemicals and co-monomer (acrylonitrile)
• Solvent (ethyl benzene <5%)
Phase Inversion:
• Continuous phase: SAN copolymer
• Dispersed phase : PBD
Devolatilization:
• The monomer, co-monomer and low-boiling
compounds are removed from the polymer
Pellatization:
Mass polymerization
Properties of ABS resins
Properties of ABS resins
 Properties of ABS
• The properties of ABS resins can be
controlled
– Changing the composition, MW, MWD of SAN
– The particle size and size distribution of PBD
– The grafted ratio
 Properties of ABS resins
• Impact resistance • Good dimensional stability
• Processability • Good resistance to acids
• Gloss property and alkalis
• Good mechanical properties • High abrasion resistance
• High heat distortion • Superior processing
temperature versatility
• Outstanding surface • Wide range of properties
finishing • Glass transition
• Metal plating Temperature
• Good toughness and rigidity – Rubber phase : -73 0C
• Low creep – Matrix (SAN) phase : 109 0C
 Limitations of ABS resin
• Effect humidity
• Poor resistance to UV rays
• Environmental Stress Cracking (ESC) occurs
when ABS comes in contact with certain
organic solvents and surfactants
• Flame resistance
 Grades of ABS
Depending on the raw materials and additives
• General-purpose ABS
• Flame-retardant ABS
• Extrusion ABS
• Heat-resistant ABS
• Transparent ABS
• Weatherable ABS,
• ABS alloys (ABS/PVC, ABS/PC, ABS/PA,
ABS/PMMA) etc.,
 Flame-retardant ABS
• The flame-retardant ABS resin is prepared by addition of
– Flame retardant
• Halogen based : Tetrbromo bisphenol A along with antimony
trioxide (Sb2O3)
• Halogen free : Phosphorous – Nitrogen synergism
– Impact modifier
• Chlorinated polyethylene (3 to 5%)
– Lubricant
• Amide and metal salt-based
– Stabilizer
• Antioxidant and UV stabilizers
Eco Labels in European Countries
 Flame-retardant ABS
Applications
• Office automation equipment including
copiers and printers
• Electric and electronic equipments
• Computer monitor housings
 Extrusion ABS
• Sheet
– Sheet may be used itself
– Thermoformed : which is applied to refrigerator
inner door cabinets, bathtubs, door covers, etc.,
• Profile extrusion
– Sashes
– Pipes
Extrusion Grade ABS
 Extrusion ABS
• Thermoformability
– Hot tensile behavior
– Larger area of the stress-strain curve exhibits an
excellent thermoformability property
– Rubber content, acrylonitrile content, and
molecular weight
 Transparent ABS
• Quaternary copolymer composed of
– Butadiene
– Styrene
– Acrylonitrile
– Methyl methacrylate
• Core-shell structure
– Core component : PBD or SBR
– Shell component : Random copolymer of styrene,
ACN and MMA
 Heat-Resistant ABS
• Heat resistance of 110 to 115°C has been
commercialized for the special application
• Blending various kinds of Styrenic matrix
– α-methyl styrene-co-acrylonitrile
– α-methyl styrene-co-methyl methacrylate
styrene-co-maleic anhydride
 Weatherable ABS
• Poor weatherability due to the double bond of the
butadiene rubber
– Change in the appearance and color of the resin
– Exhibits a rapid deterioration of mechanical properties
• Protection against weather
– Ultraviolet stabilizer
– Painting
– Metal plating
– Replacing BD with Acrylic rubber (ASA resin) or EPDM
rubber (AES resin)
 Weatherable ABS
Applications
• Fields related to electricity: Switch case, housing
(washing machine, refrigerator, ventilator,
pump, room cooler, etc.), fluorescent lamp,
mercury lamp cover, antenna cover, door horn,
• Fields related to automobiles: headlight body,
radiator grill, limp body, parts of farming
machines
• Others: Industrial articles, bolts, signal boards,
parts of fire extinguishers
 Applications of ABS
• Appliance parts
• Electronic/electrical
• Transportation (automotive)
• Blend with other polymers for many different
applications
 Applications of ABS
• World consumption of ABS resins is led by
appliances and electronic/electrical applications,
accounting for more than two-thirds of total world
ABS resin consumption in 2016
• The next-largest end use for ABS resins is in the
transportation sector (automobiles)
• Electronics uses will grow at more than 4% per year
• Appliances and transportation uses will increase at
3–4% per year through the forecast period
World consumption of ABS resin -2016
Applications of ABS
 References
• http://www.tudosobreplasticos.com/en/mat
eriais/abs.asp
• https://www.versalis.eni.com/irj/go/km/doc
s/versalis/Contenuti%20Versalis/IT/Documen
ti/La%20nostra%20offerta/Licensing/Stirenici
/ESE_Tecniche_ABS_0411.pdf
• http://www.toyo-eng.com/jp/en/products/p
etrochmical/ps/
• http://www.steinwall.com/wp-content/uplo
ads/2016/05/Acrylonitrile-Butadiene-Styrene
-ABS.pdf