ETHANOX® 330 : A Proven
Antioxidant Solution for Polyolefins
Presented at SPE International Polyolefins Conference
February 28, 2012 Houston, TX
Kasinath Nayak, Ph. D.
Outline
Why Stabilize Polyolefins?
» Need for a viable stabilizer
ETHANOX 330
» Chemical Identity
» Compatibility with Polymer matrix
• Supporting Extraction Data
» Test Data
• Extrusion Study
» Case Studies/Applications
• PE Pipe
• PP Raffia Film
» Conclusions
2
Why Stabilize Polyolefins?
Degradation resulting in
» Loss of physical properties and performance
» Discoloration: yellowing, pinking, and black specks
Objectives of stabilization
»
»
»
»
Extraction resistance
Processing stability
Color prevention
Long term heat aging
(LTHA) stability
Extractability of additives can have a
profound negative effect on
polyolefin stability, physical
properties and resistance to color
change
3
Auto-Oxidation Cycle and How to prevent
O2
RH
O2, τ, Δ
impurity
RH
ROO·
ROOH
R·
RO·
Δ
Hydroperoxide
Decomposer
ROH/H2O
OH·
RH
Auto-catalytic oxidation reaction: 1
radical becomes 3 after 1 cycle
Radical
Scavenger
Antioxidants interrupt the
oxidative cycles by
removing the peroxy
radicals and preventing
the formation of
hydroperoxides.
4
Primary Antioxidants
Chemical/Trade Name
Chemical Structure Mol. Wt
OH
1,3,5-trimethyl-2,4,6-tris(3,5-di-tbutyl-4-hydroxybenzyl)benzene,
CAS#1709-70-2:
ETHANOX 330
Tetrakismethylene(3,5-di-t-butyl4-hydroxyhydrocinnamate; CAS#
6683-19-8;
ETHANOX 310
Melt processing/LTHA,
Low extractability
775
OH
HO
Melt processing/LTHA
HO
O
O
1,3,5-tris(3,5-di-t-butyl-4hydroxybenzyl)isocyanurate;
CAS#27676-62-6;
Octadecyl 3-(3’5’-di-t-butyl4’hydroxyphenyl)propionate;
CAS#2082-79-3;
ETHANOX 376
C
1178
4
O H
O
N
O
ETHANOX 314
Benefits
N
N
O
O H
784
Melt processing/LTHA,
Good gas-fading
resistance
H O
Melt processing
O
HO
CH2CH2CO(CH2)17CH3
531
5
ETHANOX 330
OH
Chemical name: 1,3,5-trimethyl-2,4,6-tris (3,5di-tert-butyl-4-hydroxybenzyl)benzene
Mol. Wt.: 775.2; CAS #: 1709-70-2
OH
Melting Point: 244°C
HO
PROS

High MW Crystalline Powder

Electrically neutral

Superior Processing Stabilizer

No imparted odor/taste

Provides long-term stability

Good benefits in filled and

Biologically inert

Extremely low extractability

Reduced water-carryover
flame-retardant applications
6
ETHANOX 330: Regulatory Compliances
ETHANOX 330 antioxidant (1,3,5-trimethyl-2, 4,6-tris (3,5-di-tertbutyl-4-hydroxybenzyl) benzene (CAS reg. No. 1709-70-2):
Permitted for use in Adjuvants per FDA 21 CFR 178.2010 for indirect
food contact applications:
For Use only:
 At levels not to exceed 0.5% by weight of polymers except nylon
resins identified in sect.177.1500 of this chapter.
 At levels not to exceed 1% by weight of nylon resins identified in
Sec. 177.1500 of this chapter.
Global Compliances
 EU, Japan, and other Asia-Pacific Countries
7
Extraction Resistance:
Hindered Phenolic Antioxidants
OH
HO
OH
O
O
HO
ETHANOX 330
4
Irganox 1010
Hydrolysis of the ester groups of Irganox 1010 in de-ionized
water and resulting migration from PP films were
demonstrated via HPLC
ETHANOX 330 lacks these ester linkages thus exhibiting
superior resistance to hydrolysis
Ref: M. Bertoldo and F. Ciardelli, Polymer 45(2004) 8751-8759
8
Extraction Resistance of ETHANOX 330
in MDPE Pipe
Extruded Pipe (OD=63mm) containing 0.1% Radio-labeled ETHANOX 330,
aged @ 60°C for 3 months
Ethanox 330, wt%
0.12
0.1
0.08
Bore aged in air
0.06
Bore aged in water
0.04
0.02
0
0.2
Surface
0.9
1.57
2.06
2.94
3.89
4.8
5.77
Bore
Cross Section of Pipe, mm
No Loss of ETHANOX 330 occurred, showing negligible
degree of extractability
9
Ref.: Norman Allen et. al. Poly. Deg. & Stab. (1990) 145-157
Environmental Depletion of
Antioxidants in MDPE
MDPE Pipe formulations
» I. 0.1% ETHANOX 330 +0.3%Cyassorb 531+0.1%Chimassorb 944+0.2%Irgalite Blue +0.2%TiO 2
» II. 0.1% Irganox 1010 +0.3%Cyassorb 531+0.1%Chimassorb 944+0.2%Irgalite Blue +0.2%TiO2
Pipe Dimension
 Outer Diameter = 66mm
 Thickness of cross-section = 6mm
Environmental Conditions
 Exposed to air for 9 months
 Exposed water at ambient temperature for 9 months
 Exposed to water and oven-aged @ 60°C for 3 Months
Oxidative Induction Time (OIT)
 Accelerated aging test done 200°C per ASTM D3895-07
10
% Oxidative Induction Time (OIT) Retention
Ethanox 330
Irganox 1010
120
Exposed to water
at RT for 9 Months
Exposed to water &
oven-aged @ 60 °C for
3 Months
80
60
40
20
Bore
Middle
Surface
Bore
Middle
Surface
Bore
Middle
0
Surface
% OIT Retained
100
Exposed to AIR
for 9 Months
Cross-Section of Pipe
11
Effect of Boiling Water on Antioxidant
Activity in 3rd Gen Polypropylene
25 mil Plaques in Boiling water
1600
0 Day
7 Days
1400
Hours to Failure
1200
1000
800
600
400
200
0
Ethanox 330
Ethanox 310
Ethanox 330/DSTDP
Ethanox 310/DSTDP
Formulations: 1st Set:PP Homopolymer (3dg/min) containing Aox(600)/DHT4A(250ppm)
2nd Set: PP Homopolymer(3dg/min) containing Aox(600)/DSTDP(600ppm)/DHT-4A(250ppm)
Ethanox 330 is shown to have more resistance to boiling water
12
Effect of Oven-Aging and Boiling Water
on OIT: LLDPE Polymer
OIT @ 180°C
Ethanox 330
30
Ethanox 310
OIT in Minutes
25
20
15
10
5
0
Un-aged
Aged 14 Days @ Aged 7 Days in Aged 14 Days in
105°C
boiling water
boiling water
© Copyright 2012 Albemarle Corporation - Strictly confidential - Proprietary information of Albemarle.
13
Stability Test: Polypropylene Homopolymer
Multi-Pass Ext. @ 260°C/30 rpm flat profile
MFI ,g/10 min
10
8
6
4
E-330
E-310
E-314
2
0
1st Pass
3rd Pass
5th Pass
Extrusion Pass
Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppm
Melt Flow Index per ASTM D 1238-10
ETHANOX 330 (E-330) outperforms both ETHANOX 310 (E-310) and ETHANOX 314 (E314) in maintaining melt flow stability.
14
Stability Test (continued)
MFI, g/10min
Multi-Pass Ext.@288°C/30 rpm flat Profile
35
30
25
20
15
E-330
10
E-310
5
E-314
0
1st Pass
3rd Pass
5th Pass
Extrusion Pass
Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppm
Multiple extrusion passes at higher temperature resulted in similar trend in melt flow rates, but
much greater differences were seen between Ethanox 330 and other two antioxidants.
15
Stability Test (continued): Single Pass
Extrusion Test
Effect of Temperature on Melt Stability
MFI, g/10min
25
Ethanox 310
20
Ethanox 314
15
Ethanox 330
10
5
260°C
275°C
290°C
305°C
310°C
0
1
2
3
4
5
Extruder Zone 4 (Die) Temperature in °C
Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppm
Ethanox 330 and Ethanox 314 are fairly equal in maintaining melt flow stability up to 290°C, but
Ethanox 330 exhibited better melt-flow stability at temperatures above 290°C.
16
Case Study-I: PE Pipe
Base Resin: ExxonMobil’s HDPE ( D ~ 0.954g/cc,
and MI ~ 0.5dg/min)
 Base Additive Package:
Phenolic/Phosphite/Hydrotalcite
@1500ppm/750ppm/500ppm
 Enhanced Additive Package:
Phenolic/Phosphite/Hydrotalcite/AM-1/DS-1/HN-1/N-1 @
1500/750/500/1000/1500/500/500 ppm
Compounding:
Initial Extrusion: by Haake TW100 Twin Screw Extruder
(180/200/200/200°C) @ 30 RPM
 Molding: Compression molded plaques (0.05 inc or 50 mil)
Ref: Proceeding of International Polyolefin Conference (2010), Houston, TX
17
Relative OITs of Various AOx based
formulations
250
OIT, min
200
150
100
50
0
Base
E-330 Series
Base +
Thioester
Enhanced
Additive Package
E-314 Series
E-310 Series
18
Effect of Extractive Media on OIT
Effect of Extractive Media @ 60 Deg C/7Days on OIT
1.05
Change in OIT
1
0.95
0.9
0.85
0.8
0.75
0.7
As Is
B-1 (E-330)
Water
C-1 (E-314)
Chlorinated Water
D-1 (E-310)
19
Hydrostatic Pressure Test (ISO 116773): PE 100 Pipe
0
Lifetimes of PE-100 Pipe at 110 C
I-1010/I-168
PVDF
E-330/I-168
PVDF
0.95 MPa
1.41 MPa
I-1010/I-168
Brass
E-330/I-168
Brass
0
500
1000
1500
2000
2500
3000
3500
Hours to Failure
PE100 (Density = 0.96/MFI=0.37 @5kg/190°C); and extruded Pipe of 20 mm OD & 2mm wall thickness
containing Phenolic/Phosphite/Cal St.(1000/1000/1000ppm)/Carbon black(2.5%) with Brass or PVDF
fittings
20
Ethanox 330 is ~20% better than Irganox 1010 under hydrostatic pressure (static) test.
Case Study-I: Outcome
ETHANOX 330 outperforms both ETHANOX 310 and ETHANOX 314 in
maintaining least loss in Oxygen Induction Time (OIT) after extraction in
de-ionized water and chlorinated water.
Hydrostatic Pressure Tests (Static) showed
 ETHANOX 330 is approx. 10 – 20% better than Irganox-1010.
Special ALBlend Packages with thioesters and amines are shown to
exhibit exceptional OITs, thus showing promises for HDPE pipe
applications to extend the life expectancy beyond 100 years.
Hence, ETHANOX 330 is an antioxidant of choice for polyolefin water pipe
applications because of its resistance to hydrolysis and water extraction.
21
Case Study-II: Improving Color/Line
Speed in Raffia Grade Polypropylene
Objective:
Reduce the yellowness index color
Improve the line speed (reduce water carry over)
during film extrusion of raffia grade polypropylene
Lower overall treat cost
22
Water Carry Over Test
23
Effect of Antioxidants on Water Carry
Over In a Homopolymer PP
140
Line Speed,Ft/min
2470C
2750C
120
100
80
Ethanox 330
Ethanox 310
Ethanox 314
60
40
20
0
500ppm
1000ppm
500ppm
1000ppm
Antioxidant Loading
24
Case Study-II: Experimental Details
Four ALBlend samples vs. a Specific Customer
formulation were tested
 ALBlend A20: E330/E368/Cal. St. @ 1600 ppm
 ALBlend B20: E330/E368/Cal. St. @ 1700 ppm
 ALBlend C20: E330/E368/Cal. St. @ 1650 ppm
 ALBlend D20: E330/E368/DHT-4A/Cal. St. @ 1500 ppm
 Current formulation
Test Data
 Yellowness index
 Melt flow index
 Line speed (Water Carry Over)
25
Multiple Extrusion and Water Carryover Data
Line Speed
ALBlend D20
Better line
speed, better
color and
comparable
melt flow
stability
ALBlend C20
ALBlend B20
ALBlend A20
Current Formulation
105
110
115
120
125
130
Avg. ft/min
26
Case Study-II: Outcome
ALBlend containing ETHANOX 330 was chosen
for optimum performance:
 Reduced yellowness index color from 4.19 to 2.04 after the 5th
pass.
 Improved line speed from 113 ft/min to 122 ft/min.
27
Conclusions
Extraction Resistance
 ETHANOX 330 exhibits superior hydrolytic stability resulting in
excellent extraction resistance when in contact with extracting media
Processing Stability:
 ETHANOX 330 shows better performance in maintaining melt flow
stability
Oxidative Induction Time (OIT) Retention:
 ETHANOX 330 exhibits better OIT retention
Resistance to Hydrostatic Pressure:
 ETHANOX 330 outperforms in hydrostatic pressure test
Lower Water Carryover:
 Formulations based on ETHANOX 330 result in low color and higher line
speed
28
ETHANOX 330:
Add less, get more value
For more information regarding Albemarle’s
antioxidants, please visit www.ethanox.com.
29