Phenol Free Stabilization of Polyolefins

Hayder Zahalka, Jonathan Hill, David Layton

Chemtura Global Technology

AddCon 2008
Barcelona, Spain

Content
Polymer Stabilization Color formation & gasfading Mechanism Examples of Phenol Free Formulations: PP PE Summary

Hydrocarbon Oxidation Without Antioxidant

ROO

RH

P O L Y M E R

O2

.
ROOH

2R + ROH + HOH

.
2RH RO

. .

+
HO

Most Polymers Require Stabilizers To Prevent Degradation

Hydrocarbon Oxidation With Primary Antioxidant

ROO O2 P O L Y M E R

ArOH

ArO

.
ROOH

2R + ROH + HOH

.
2RH RO

. .
Phenolic AOs Slow Degradation, and...

+
HO

Hydrocarbon Oxidation With Primary and Secondary Antioxidant

ROO P O L Y M E R O2

ArOH

Phenolic works here

ArO

.
P(OR)3 O

Shear

.
ROOH Phosphite works here

...Phosphites Break the Cycle

ROH

P(OR)3

Color Formation of Phenolic AO

OH +RO

O RO -ROH

-ROH

Quinone Methide Reductive Coupling O 2RO 2 ROH O Stilbenequinone OH HO

(yellow) 6

Gasfading BHT Yellowing

POO or

HO

CH3 H
NO2

.O

CH3

.
NO2

CH3

HONO

CH2

H2O, RT
O

CH3 NO2

Quinonemethide

Diphenylquinone Stilbenequinone
7

Examples of Phenol-Free Formulations

1. PP Fibers and Film 2. PE Film Many more.

POLYPROPYLENE FIBERS STABILIZATION

PP Fibers Requirements
Good Processing Stability: Melt flow protection and low color Development Low color development during storage and possible exposure to NOX gases

Good gasfading protection:

Long Term Thermal Stability: Increased life time of the PP fibers in end-use applications UV Stability: Control color fading and retain mechanical properties Maintain mechanical properties of the fibers

Good Spinnability:

POLYPROPYLENE FIBERS STABILIZATION

Additive Requirements for PP Fiber Applications

Good Extraction Resistance Low Volatility Effectiveness at different Processing Conditions High Speed / High Spinning Temperatures Low Peroxide Interactions Robust System for non CR and CR PP Excellent Hydrolytic Stability Good Cost/Performance Food Contact Approval

10

GENOX EP

R R N O CH3
R, R = C14-22
product form: solid FDA approval in PP/HDPE Formula Weight: 580-610 Working on FDA in PE Melting point: 85-105 C Excellent gas-fading resistance Vegetable Based Excellent Hydrolytic Stability Compared to competitors Tallow source

11

Amine Oxide Activity

Potential Mechanism
CH3 N R R N O CH3 R Hydroxylamine CH3 Amine Oxide R Nitroxyl Radicals N
OH RO or R
.

OH +

R alkene

RO OH

or R .

CH2 R

O-

O. +

R alkene

Nitrone and other nitrone intermediates

Both Primary and Secondary AO function

References:

More radical trapping leading to further stabilization of polymer

Pyrolysis of Amine Oxides in A. C. Cope, Ed., Organic Reactions, Vol. 11, pp. 361-368 (1960) New Aspects of Synthesis and Chemistry of Nitroxide Spin Labels, Chem. Reviews, Vol. 78, pp. 37-64 (1978) Chakraborty, et al. Journal of Applied Polymer Science, Vol. 30, pp. 3267-3281 (1985)

12

GENOX EP and Dried CaSt exposed for 2000 hours at ambient temperature and 70% relative humidity

TM

3 Weight 2 Gain % 1 0 0 1000 2000

CaSt

GENOX EP

TM

3000

Exposure Time (hours)

GENOXTM EP has no hydrolyzable functionality and gains far less weight than CaSt

Screen Pack Plugging (SPP) Comparison of TM GENOX EP formulation with P1 formulation

2500 2250 2000 1750 1500 Pressure, psi 1250 1000 750 500 250 0 0 60 120 180 240 300 360

GENOX TM EP/CaSt @ 500/500 ppm P1/CaSt @ 1000/500 ppm

Time, minutes

Excellent performance of GENOXTM EP formulation in preventing screen pack plugging.

Polypropylene
1. Peroxide initiated degradation Vis-Breaking (Controlled Rheology) 2. Without Peroxides

15

Structures of Primary and Secondary Antioxidants

C(CH3)3 O C CH2OCCH2CH2 OH C(CH3)3 4 4 (CH3)3C C(CH3)3 O 3 P

Anox20

AO2

Alkanox 240
O H (C H 3)3C

P1
C (C H
3)3

C(CH3)3 O (CH3)3C O P O O

(CH3)3C
O

CH N N CH (C H
3)3C 2

O N CH
2

P O O

C(CH3)3

O C (C H 3)3 O H

HO

C (C H

3)3

(C H 3)3C

Ultranox 626

P2

Anox IC-14

AO1

Structures of Secondary Antioxidant

t-Bu

t-Bu

t-Bu t-Bu O O P t-Bu

t-Bu O P O t-Bu Bu-t

PEP-Q

P3

Stabilization of PP Fibers: bright colored textile yarns

OH

Good resistance to gas fading

O N N O OH

N O

Allows optimum color stability Good hydrolytic stability Good extraction resistance Good cost/performance Wide FC approval

HO

AO1

O O P O

P1
18

Effect of Visbreaking on Stabilizer Performance PP Fiber grade-Multipass Extrusion @ 250C 60 50 40 MFI 30 20 10 0 1200 AO1/P1 700 AO1/P2 700 AO1/P3 400 Genox

Compound 1st pass 3rd pass 5th pass

Formulation

PP Fiber Grade-Visbreaking
8

Compound 1st pass 3rd pass 5th pass

6 YI

0 1200 AO1/P1 700 AO1/P2 Formulation 700 AO1/P3 400 Genox

Gas-Fading PP Fiber Grade 5 4 3 YI 2 1 0 0 8 16 24 32 40 48 56 NOx Exposure (hrs)

AO1/P1 1200 AO1/P2 700 AO1/P3 700 Genox 400

Polypropylene
1. Peroxide initiated degradation Vis-Breaking (Controlled Rheology) 2. Without Peroxides

22

PP Stabilization

C(CH3)3 O C CH2OCCH2CH2 OH
O

C(CH3)3 4
O

AO2

P1

23

PP Multipass Extrusion @ 260C

20
COMPOUND 1ST PASS 3RD PASS 5TH PASS

15

MFI

10

0 AO2/P1 1500ppm Genox 500ppm Formulation Genox 300ppm

PP Gas-Fading
3

AO1/P1 (1500) Genox-500 Genox-300

YI

0 0 5 8 19 21

-1 NOx Exposure (days)

Polyethylene
1. ZN-HDPE 2. ZN-LLDPE

26

Structures of Primary /Secondary Antioxidants

C(CH3)3 O C CH2OCCH2CH2 OH C(CH3)3 4 (CH3)3C C(CH3)3 O 3 P

AO2- Anox 20 OH (CH3)3C C(CH3)3

P1- Alkanox 240

C(CH3)3 O (CH3)3C O P O O

(CH3)3C P O O C(CH3)3

O CH2CH2COC18H37 AO3- Anox PP18 P2- Ultranox 626

ZN-HDPE Multipass Extrusion @ 210C

20 comp. 1st pass 3rd pass 5th pass 15

MFI (I-21)

10

0 AO2/P1 2100 Formulation Genox 400 ppm

ZN-HDPE Multipass Extrusion

0.5

2100 AO2/P1 400 ppm Genox YI -0.5

-1

-1.5 comp. 1st pass 3rd pass 5th pass Multipass Extrusion

Gas-Fading ZN-HDPE
10

6 2100 AO2/P1 400 Genox YI 4

-2 0 4 7 11 NOx Exposure (days) 14 19 21

Polyethylene
1. ZN-HDPE 2. ZN-LLDPE

31

LLDPE Gas-Fading
5

2 YI

AO3/P1 1700 AO3/P2 1000 Genox 300

-1

-2 0 4 12 14 20 23 NOx Exposure (days)

Genox EP In-Polymer Chemistry

Genox EP processed into PP, LLDPE Polymer exhaustively extracted (4x) with chloroform at 50oC/3h Extracts analysed by GC, NMR and LCMS (only hydroxylamine observed). Residual N content on extracted polymer by chemiluminescence LLDPE/1000ppm Genox EP/processed at 190oC
Alkenes = 400ppm Hydroxylamines = 280ppm Polymer-bound nitrogen ca. 6ppm (equivalent to 250ppm added Genox)

PP/600ppm Genox EP/processed at 230oC

Alkenes = 250ppm Hydroxylamines = 90ppm Polymer-bound nitrogen ca. 3ppm (equivalent to 130ppm added Genox)

Nitrogen becomes bound to the polymer backbone

33

Genox EP In-Polymer Chemistry

H3C O N CH2CH2R H2C N O

POO*

- POOH

CH2CH2R

Heat
H3C N CH2CH2R

H3C N

OH

H3C

O N

POOH -POH, H2O

H

CH2CH2R

- RCH=CH2

CH2CH2R

CH2R

R = C16-20 Genox

Hydroxylamine
H3C N O

The reaction scheme shows the degradation pathway of Genox EP under heating and polymer processing conditions Genox EP is converted into Alkyl methyl hydroxylamines with long chain alkenes formed as a by-product. Hydroxylamine can react directly with a radical via H atom transfer to give RNMeO* radical (primary antioxidant). Hydroxylamines can also react with hydroperoxides in a redox reaction forming different isomeric nitrones, alcohol and water (secondary antioxidant). The nitrones can then react with radicals to give polymerbound NO radicals

H2CR

Nitrones

P H2C N CH2CH2R O H2C O* N CH2CH2R

+ P*

34

Genox, Phenol Free Stabilizer system for PE/PP

R R N O CH3
R, R = C14-22
Product form: solid Formula Weight: 580-610 Melting point: 85-105 C

Delivers excellent MI/color in phenol free formulations No hydrolytic stability concerns No charring , low screen pack plugging Long alkyl chains ensure compatibility in PP Negligible color development under UV, NOx or gamma irradiation Vegetable Based Environmentally friendly (green)

Competitive cost/performance
35