Presented at SPE International Polyolefins Conference February 28, 2012 Houston, TX Kasinath Nayak,...
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Transcript of Presented at SPE International Polyolefins Conference February 28, 2012 Houston, TX Kasinath Nayak,...
Presented at SPE International Polyolefins ConferencePresented at SPE International Polyolefins ConferenceFebruary 28, 2012 Houston, TX February 28, 2012 Houston, TX
Kasinath Nayak, Ph. D.Kasinath Nayak, Ph. D.
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
» Extrusion Studies
• Summary
Outline
2
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
Why Stabilize Polyolefins?
3
ROO·
RH
RO·
OH·
R·
RH
ROOH
O2
RH
ROH/H2O
impurity
O2, τ, Δ
Δ
Auto-catalytic oxidation reaction: 1 radical becomes 3 after 1 cycle
Auto-Oxidation Cycle and How to prevent
4
Radical Scavenger
Hydroperoxide
Decomposer
Chemical/Trade Name Chemical Structure Mol. Wt Benefits
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, CAS#1709-70-2:
ETHANOX 330775
Melt processing/LTHA, Low extractability
Tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate; CAS# 6683-19-8;
ETHANOX 3101178
Melt processing/LTHA
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate; CAS#27676-62-6;
ETHANOX 314
784
Melt processing/LTHA, Good gas-fading resistance
Octadecyl 3-(3’5’-di-t-butyl-4’hydroxyphenyl)propionate; CAS#2082-79-3;
ETHANOX 376531
Melt processing
HO CH2CH2CO(CH2)17CH3
O
HO CH2CH2CO(CH2)17CH3
O
O H
O H
H O
N
N
N
O
OO O H
O H
H O
N
N
N
O
OO
H O
O C
O4
H O
O C
O4
OH
OH
OH
Primary Antioxidants
5
Chemical name: 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)benzene
Mol. Wt.: 775.2; CAS #: 1709-70-2
Melting Point: 244°C
OH
OH
OH
High MW Crystalline Powder Electrically neutral
Superior Processing Stabilizer No imparted odor/taste
Provides long-term stability Good benefits in filled and
Biologically inert flame-retardant applications
Extremely low extractability
Reduced water-carryover
PROSPROS
6
ETHANOX 330
ETHANOX 330 antioxidant (1,3,5-trimethyl-2, 4,6-tris (3,5-di-tert-butyl-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
ETHANOX 330: Regulatory Compliances
OH
OH
OH
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
ETHANOX 330
8
OH
O
O4
Irganox 1010
Extraction Resistance: Hindered Phenolic Antioxidants
Ref.: Norman Allen et. al. Poly. Deg. & Stab. (1990) 145-157
No Loss of ETHANOX 330 occurred, showing negligible degree of extractability
0
0.02
0.04
0.06
0.08
0.1
0.12
0.2 0.9 1.57 2.06 2.94 3.89 4.8 5.77
Eth
anox
330
, wt%
Cross Section of Pipe, mm
Bore aged in air
Bore aged in water
Surface Bore
Extruded Pipe (OD=63mm) containing 0.1% Radio-labeled ETHANOX 330, aged @ 60°C for 3 months
9
Extraction Resistance of ETHANOX 330 in MDPE Pipe
MDPE Pipe formulations» I. 0.1% ETHANOX 330 +0.3%Cyassorb 531+0.1%Chimassorb 944+0.2%Irgalite Blue +0.2%TiO2
» 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
Environmental Depletion of Antioxidants in MDPE
0
20
40
60
80
100
120S
urf
ace
Mid
dle
Bo
re
Su
rfa
ce
Mid
dle
Bo
re
Su
rfa
ce
Mid
dle
Bo
re
Cross-Section of Pipe
% O
IT R
eta
ine
d
Ethanox 330 Irganox 1010
Exposed to AIR for 9 Months
Exposed to water at RT for 9 Months
Exposed to water & oven-aged @ 60 °C for 3
Months
% Oxidative Induction Time (OIT) Retention
11
25 mil Plaques in Boiling water
0
200
400
600
800
1000
1200
1400
1600
Ho
urs
to
Fa
ilu
re
Ethanox 330 Ethanox 310 Ethanox 330/DSTDP Ethanox 310/DSTDP
0 Day7 Days
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 Boiling Water on Antioxidant Activity in 3rd Gen Polypropylene
OIT @ 180°C
0
5
10
15
20
25
30
OIT
in M
inu
tes
Un-aged Aged 14 Days @105°C
Aged 7 Days inboiling water
Aged 14 Days inboiling water
Ethanox 330 Ethanox 310
© Copyright 2012 Albemarle Corporation - Strictly confidential - Proprietary information of Albemarle. 13
Effect of Oven-Aging and Boiling Water on OIT: LLDPE Polymer
Multi-Pass Ext. @ 260°C/30 rpm flat profile
0
2
4
6
8
10
1st Pass 3rd Pass 5th Pass
Extrusion Pass
MF
I ,g
/10
min
E-330
E-310
E-314
Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppmMelt Flow Index per ASTM D 1238-10
ETHANOX 330 (E-330) outperforms both ETHANOX 310 (E-310) and ETHANOX 314 (E-314) in maintaining melt flow stability.
14
Stability Test: Polypropylene Homopolymer
Multi-Pass Ext.@288°C/30 rpm flat Profile
0
5
10
15
20
25
30
35
1st Pass 3rd Pass 5th Pass
Extrusion Pass
MF
I, g
/10m
in
E-330
E-310
E-314
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)
Effect of Temperature on Melt Stability
0
5
10
15
20
25
1 2 3 4 5
Extruder Zone 4 (Die) Temperature in °C
MF
I, g
/10m
in
Ethanox 310
Ethanox 314
Ethanox 330
260°C 275°C 290°C 305°C 310°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
Stability Test (continued): Single Pass Extrusion Test
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 RPMMolding: Compression molded plaques (0.05 inc or 50 mil)
Ref: Proceeding of International Polyolefin Conference (2010), Houston, TX 17
Case Study-I: PE Pipe
0
50
100
150
200
250
Base Base +
Thioester
OIT
, min
E-330 Series E-314 Series E-310 Series
Enhanced
Additive Package
18
Relative OITs of Various AOx based formulations
0.7
0.75
0.8
0.85
0.9
0.95
1
1.05
As Is Water Chlorinated Water
Ch
an
ge in
OIT
B-1 (E-330) C-1 (E-314) D-1 (E-310)
Effect of Extractive Media @ 60 Deg C/7Days on OIT
19
Effect of Extractive Media on OIT
20
Hydrostatic Pressure Test (ISO 1167-73): PE 100 Pipe
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
Ethanox 330 is ~20% better than Irganox 1010 under hydrostatic pressure (static) test.
Lifetimes of PE-100 Pipe at 1100C
0 500 1000 1500 2000 2500 3000 3500
E-330/I-168Brass
I-1010/I-168Brass
E-330/I-168PVDF
I-1010/I-168PVDF
Hours to Failure
0.95 MPa
1.41 MPa
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-I: Outcome
Objective: Reduce the yellowness index colorImprove the line speed (reduce water carry over)
during film extrusion of raffia grade polypropylene Lower overall treat cost
22
Case Study-II: Improving Color/Line Speed in Raffia Grade Polypropylene
23
Water Carry Over Test
0
20
40
60
80
100
120
140
500ppm 1000ppm 500ppm 1000ppm
Antioxidant Loading
Lin
e S
pee
d,F
t/m
in
Ethanox 330
Ethanox 310
Ethanox 314
2470C 2750C
24
Effect of Antioxidants on Water Carry Over In a Homopolymer PP
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 DataYellowness indexMelt flow indexLine speed (Water Carry Over)
25
Case Study-II: Experimental Details
26
Multiple Extrusion and Water Carryover Data
Current Formulation
ALBlend A20
ALBlend B20
ALBlend C20
ALBlend D20
Line Speed
105 110 115 120 125 130
Avg. ft/min
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
Case Study-II: Outcome
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
speed28
Conclusions
For more information regarding Albemarle’s antioxidants, please visit www.ethanox.com.
29
ETHANOX 330: Add less, get more value