Presented at SPE International Polyolefins Conference February 28, 2012 Houston, TX Kasinath Nayak, Ph. D.

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