America Chemical Society Meeting

San Diego CA 2001

Introduction to Polymer Stabilization
by Dr. R.E. King III Senior Staff Scientist II Ciba Specialty Chemicals Tarrytown NY 10591 April 1 - 5, 2001
RK / ACS 01 - 1-

Ciba

Outline of Presentation
l Auto-Oxidation & Stabilization l Review of Various Stabilizers Antioxidants
Primary: Phenols & Arylamines Secondary: Phosphites & Thiosynergist New Chemistries: Hydroxylamines & Benzofuranones

UV Stabilizers
Excited State Quenchers UV Absorbers Hindered Amines

l Recent Challenges in the Field l Conclusions & Recommendations l Acknowledgments

RK / ACS 01 - 2-

Autoxidation: Sites of Hydrogen Abstraction

Polyamides: Polyesters: Polyacetal: Unsaturated Systems: Polyolefins: Selected Polyethylenes
RK / ACS 01 - 3-

-CO-NH-CH2-CO-O-CH2-O-CH2-O-CH=CH-CH2-CH2-CH-CH2R H2C=CH-CH2-

F. Gugumus; Plastics Additives, Gachter & Muller, Ed., 3rd Ed., Ch. 1.

Representative Definition of Polyolefins

Polypropylene
R

Polyethylene

Of Course, Its Really Not This Simple .. Catalyst / Co-Catalyst Polymerization Process Finishing Step Method of Stabilization End-Use Application
RK / ACS 01 - 4-

General Polymerization Scenario

Possible Additive Addition Points =
* * *

V1
Reactor

V2

V3
* * *

V4

V5

Flash Deactivate Drying Storage

"Dry Blended Fluff"

Value Chain "Base Stabilized Pellets"

"Fully Formulated Pellets"

** Goal: Keep Molecular Architecture Intact **

RK / ACS 01 - 5-

Review: Stabilization of Polyolefins

Q. Why Do I Need to Use Stabilizers ?
l A. Stabilizers Used to Maintain the Polymer's

Original Strength, Flexibility and Toughness.

l Properties Need to be Maintained to Meet End

Use Applications that have Performance Targets

l Useful to Split Performance Targets (Economics)

Low End: Mid-Range: High End:

RK / ACS 01 - 6-

Non-Durable Goods Use it for a While Durable Goods

Scheme 1 - Autoxidation Cycle

Polymer
Energy; Shear; Melt Processing; Catalyst Residues R RO HO ROO ROOH Alkyl Radical Alkoxy Radical Hydroxy Radical Peroxy Radical Hydroperoxide

Polymer

Oxygen

Cycle II
RO + OH R + ROOH

Cycle I
ROO

Energy (UV Light, Heat) Catalyst Residues

Polymer
Path of Degradation

RK / ACS 01

- 7-

Products of Melt Processing

Alkyl Radicals l Peroxy Radicals Affect Melt Processing and l Alkoxy Radicals Long Term Thermal Stability l Hydroxy Radicals
l l l

Hydroperoxides

Affect Melt Processing, Long Term Thermal & UV Stability Affect Taste & Odor

Alcohols l Aldehydes l Ketones

l
RK / ACS 01

"Polymer"
- 8-

Its Just Not the Same

Types of Thermal Stabilizer Chemistries

l

Melt Processing Stability Phosphites Hindered Phenols Hydroxylamines Lactones Tocopherols (Vit. E)

Traditional

New Stuff

Long-Term Thermal Stability Hindered Phenols Thiosynergist (& Phenol) Hindered Amines

Traditional

New Stuff

RK / ACS 01

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Parallel Growth & Variety of Stabilizers

Volume Polymer
As new polymers filled more demanding applications, new additives needed to be developed

Solution Phase Slurry Phase zn-PP zn-PE Melt Phase HP-LDPE

Gas Phase zn-PP zn-PE AO: HMW & Specialty Phenolics & Phosphites

UV: HMW Absorbers Hindered Amines (HALS) AO: BHT; TNPP UV: Absorbers
1955 1965 1975 1985

1935
RK / ACS 01 - 10 -

1945

Mechanism of Activity: Phenolic Antioxidants

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Representative Commercial Phenolic AOs

O HO CH2 CH2 C O CH2 C O HO CH2 CH2 C O C18 H37 OH 4

OH
HO O HO CH2 P OC2 H5 O Ca2+ N O 2 N O N O

HO OH OH
OH H CH3 OH

OH

S
O HO (CH2)2 C N H 2 HO O
RK / ACS 01 - 12 -

C8H17 OH

C8H17
O

HO

CH 2

CH 2

(CH2)2-]2-S-

Phenolic Free Radical Chemistry

OH

+ RO O
RK / ACS 01 - 13 -

Species Attacked Predominantly

- ROH

Phenolic Free Radical Chemistry

O

+ RO

+ RO - ROH Disproportionation

OR O OH

Quinonemethide +

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Phenolic AO (BHT) Oxidation Chemistry

OH + RO - ROH O

+ RO - ROH

Quinonemethide
HO CH CH OH Coupling

+ 2 RO - 2 ROH

Stilbenquinone (Yellow)
RK / ACS 01 - 15 -

CH CH

Gas Fade / Gas Yellowing Chemistry

OH + NO2 H2O + R 2NH2 NO2 O - HONO CH H3C NO HONO +
Base (e.g. R2N-H)

Alkalinity (e.g. R2N-H)

NO
2

H3C

Quinonemethide
Coupling

- 2 ROH

Bis-Phenol
RK / ACS 01 - 16 -

Stilbenquinone

HO

HO

CH=CH

+ 2 RO

CH-CH

Changing the Reactivity of Quinone Methide Chemistry

O OH O

H Transfer Re-Aromatization
COOR COOR

ROO

COOR

x2
O COOR O COOR

COOR

COOR

= 34,800 @ 440 nm

= 116 @ 420 nm

RK / ACS 01

- 17 -

Klemchuk and Horng: Poly. Degrad. Stab. 1991, 34, 333.

Vitamin E (-tocopherol) Mechanisms {complicated version}

H 3C O

H 3C

O O

CH 3 CH 3 O R

H 3C H 3C

O O R

(j) QM
O H 3C H 3C CH 2 H 3C O O H 3C O R CH 3 +2 P (- >C=C<)

R CH 3

CH 3

CH 3

TRI (A,B,C) (g)

+ -Toc +POO

OH

CH 3 CH 3 H 3C R H 3C O R +2 POO CH3 CH 3

-Toc
OH H 3C CH 3 POO H 3C O R CH 3 H 3C H 3C

-Toc
O CH 3

O R CH 3

dimerize (i)

-Toc

(h)

+ -Toc (I) (-Toc. )

SPD (E)

CH 3

(a)

O R R R CH 3

(b) Toc benzyl

OH H 3C H 3C O CH 2

OH

(k)
O H 3C CH 3 H 3C O CH2

(e)
OH

(d)

dimerize (c)

H 3C H 3C O R

CH 2

CH 2

QM

Formyl--Toc (G)
OH H 3C O H H 3C H 3C

OH CH2

(p)

CH 3 O CH 3 H 3C R via Toc-benzyl

CH 3

O H 3C O R CH 3 R CH3
OH

CH 3

DHD (F) (l ,c) O2

OH H 3C CH 2OO

(m)
CH2OOH

(n)

H3 C H3 C

Formyl-chroman-3-en (H)
OH H 3C O

O R OH CH3

Intermolecular H-abstraction (+ PH)

H 3C
CH2 OOH

H3C

H 3C O R CH 3

(o)

Intramolecular H-abstraction

O R CH 3

H3C O R CH3

Al-Malaika, Ashley and Issenhuth

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Mechanism of Activity: Phosphites

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Decomposition of Hydroperoxides
R-O + OH Heat Light R-OOH Ti(III) Cu(II) R-OO + H+ + Cu(I) R-O + OH + Ti(IV) R-O + OH

RK / ACS 01

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Oxidation of Phosphites to Phosphates

(RO)3 P + R'OOH
Phosphite P(III)

(RO)3 P=O + R'OH

Phosphate P(V)

(RO)3 P=O + R'OOH

No Reaction

Relative rates of reaction for various R groups: alkyl > aryl > sterically hindered aryl
P.P Klemchuk, Antioxidants in Ullmanns Encyclopedia of Industrial Chemistry, VCH Publishers, Deerfeild Beach, FL, 91 (1985)

RK / ACS 01

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Representative Commercial Phosphites

C9H19 O P
O P

O ]3-P

O H37C18 O P O

O P O O C18H37

2
H CH3

O O P O

OC2H5

2
O P F O

O O P O

O P O O

O P O O 3
O O
RK / ACS 01 - 22 -

CH2 CH2

O P O

P O O

Hydrolysis of Phosphites
O (RO)3 P O (RO)2 P H
+ +

H2O

(RO)2

P H O

ROH

Dialkyl Phosphite

H2O

(RO)

P H OH

ROH

Alkyl Phosphorus Acid

O (RO) P H OH
+

O H2O HO P H OH
Phosphorus Acid
+

ROH

Relative rates of reaction for various R groups: alkyl > aryl > sterically hindered aryl
RK / ACS 01 - 23 -

Mechanism of Activity: Diarylamines

RK / ACS 01

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Chemistry of Secondary Arylamines Synergy with Hindered Phenols

NH R R

+ ROO
R
NH

+ ROOH
R

N R R
R

+
OH

+
O

Pospisil in Developments in Polymer Stabilization, G. Scott, Ed., Vol. 1, Ch.1. Varlamov et al.: Kinetics and Catalysis 1994, 35, 838.
RK / ACS 01 - 25 -

Mechanism of Activity: Thioethers/Thioesters

RK / ACS 01

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Chemistry of Thiosynergists Reaction with Hydroperoxides

O R O S O O R ROOH R O O S O O O R

+ ROH

heat
O O S OH O O S OH

ROH + R O

ROOH

x2
O R O S O S O O R

+ H2O

Armstrong et al.: Eur. Poly. J. 1979, 15, 241.

RK / ACS 01 - 27 -

Mechanism of Activity: Hydroxylamines

RK / ACS 01

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Stabilization Chemistry of Hydroxylamines

R N OH R R

H N O. R

R + N O R

Hydroxylamine
R

Nitroxyl Radical
R

Nitrone

N OH + ROOH R R

+ N O

+ ROH + HOH

Hydroxylamine
R + N O R R. R *R

Nitrone

N R H

O.

*R

*R + N O

Nitrone
RK / ACS 01 - 29 -

*Nitroxyl Radical

*Nitrone

Mechanism of Activity: Benzofuranones (Lactones)

RK / ACS 01

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Stabilization Chemistry of Benzofuranones

R = Carbon or Oxygen Centered Radical O O H O R R-H O R O O R
O O O O

Highly Stabilized Radical

tBu-OO O O H CN
Ph Ph O Ph Ph Ph O Ph

tBu-OO O O CN O O CN

Ph Ph O O O Ph

Benzofuranone (Lactone) chemistry is a powerful radical trap for R, RO, and ROO
RK / ACS 01 - 31 -

O O

Effective Temperatures for Stabilizers

Long Term Thermal Stability (No Melt Processing Stability)

Hindered Amine

Long Term Thermal Stability

Melt Processing Stability

Hindered Phenol

Long Term Thermal Stability

(No Melt Processing Stability)

Thiosynergist (& Phenol)

Phosphite Hydroxylamine Lactone alpha-tocopherol (E)

(No Long Term Thermal Stability)

Melt Processing Stability

50

100

150

200

250

300

RK / ACS 01

- 32 -

Temperature (C)

Scheme 2 - Inhibited Autoxidation Cycle

Polymer
Energy; Shear; Melt Processing; Catalyst Residues

Carbon Centered Radical Traps Improve Efficiency of Traditional Stabilizers

Cycle II
RO + OH R + ROOH

Cycle I

Oxygen

ROO

Phenolic AOs react with free radicals to yield inactive products (ROH and H20)
RK / ACS 01 - 33 -

Phosphites react with hydroperoxides to yield inactive products (ROH)

Phenolic AOs react with oxygen centered radicals

Path of Degradation

Path of Stabilization

Melt Processing / Long Term Stability

Chain Enlargement
Decreasing

Chain Breaking
Increasing

Molecular Weight
Increasing

No apparent change

Melt Flow Rate

Decreasing

Heat History: Multiple Extrusion; Oven Aging;

RK / ACS 01 - 34 -

Impact of Various Stabilizers Classes in Polypropylene: PO161-95/CR13195 Single Pass Extrusion Melt Flow Rate Data (Nominal = 4.5 dg/min) 15

13

11 dg/min 9 7 5 0 I-3114
RK / ACS 01 - 35 -

500 I-1330

1000 Stabilizer Loading (ppm) I-168 FS-42 HP-136

1500 CH-944

2000 DSTDP

Example #1
Enhanced Free Radical Trapping Efficiency
0.1% AO-1 / P-1, 1st pass 0.1% AO-1 / P-1, 3rd pass 0.1% AO-1 / P-1, 5th pass
Melt Flow (230C/2.16 kg)

0.06% AO-1/P-1 + 0.01 L-1, 1st pass 0.06% AO-1/P-1 + 0.01 L-1, 3rd pass 0.06% AO-1/P-1 + 0.01 L-1, 5th pass

60 45 30 15 0

Melt flow rate control of binary blends of AO / P is insufficient at high temps; Addition of 15% Lactone makes a big difference !

250C / 482F

280C / 536F

310C / 590F

Spheripol Polypropylene Homopolymer; 0.075% Calcium Stearate; Extrusion: 20 mm single screw, L/D = 25; Multiple pass extrusion at different temperatures
RK / ACS 01 - 36 -

Example #2
Inhibiting Gas Fading / Gas Yellowing Chemistry
Gas Fading is a discoloration phenomenon that is sometimes observed during storage of fabricated articles.

Selected Variables l Phenolic Antioxidants (Level and Type) l Phenolic Antioxidant / Phosphite Ratio l Surface Area (Pellet, Part or Fiber) l HALS (Alkalinity and Structure) l Resin (Catalyst Residues) l Spin Finish / Lubricants l Acid Scavengers
RK / ACS 01 - 37 -

Phenol vs. Phenol Free Stabilization

Phenol Based Stabilization (Phenol / Phosphite) l Advantages
Excellent Melt Flow Control Good Initial Color Long Term Thermal Stability (< 150oC) Relatively Easy to Analyze l Potential Disadvantages Tendency to Discolor:
After Prolonged Melt Processing Exposure to Oxides of Nitrogen Exposure to Gamma Irradiation Sensitive to Catalyst Residues

l Industry Standard (Entrenched ~ last 20 Years)

RK / ACS 01 - 38 -

Triangles of Polymer Discoloration

l Polymers stabilized with phenolic AOs can be

susceptible to discoloration if the system is abused

>Heat >Shear

Surface Area

Thermally Induced Discoloration Phenol Oxygen NxOy

Gas Fade Induced Discoloration Phenol

RK / ACS 01

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Gas Fade / Gas Yellowing Chemistry

OH + NO2 H2O + R 2NH2 NO2 O - HONO CH H3C NO
2

O HONO +
Base (e.g. R2N-H)

Alkalinity (e.g. R2N-H)

NO
2

H3C

Quinonemethide
Coupling

- 2 ROH

Bis-Phenol
RK / ACS 01 - 40 -

Stilbenquinone

HO

HO

CH=CH

+ 2 RO

CH-CH

Effective Temperatures for Stabilizers

Long Term Thermal Stability (No Melt Processing Stability)

Hindered Amine
Long Term Thermal Stability Melt Processing Stability

Hindered Phenol

* Traditional approach is to use an AO/P blend; Yet the tendency to discolor was not acceptable for color sensitive applications

Long Term Thermal Stability

(No Melt Processing Stability)

Thiosynergist (& Phenol) Phosphite Hydroxylamine Lactone alpha-tocopherol (E)

* Need new stabilizer system (w/o phenolic AO)

(No Long Term Thermal Stability)

Melt Processing Stability

50

100

150

200

250

300

RK / ACS 01

- 41 -

Temperature (C)

Phenol vs. Phenol Free Stabilization

Phenol Free Systems (HALS / Hyperactive / Phosphite) l Advantages
Good Melt Flow Control Excellent Initial Color and Color Maintenance Excellent Gas Fade Resistance Excellent Discoloration Resistance / Gamma Radiation Long Term Thermal Stability ( < 120oC) l Potential Disadvantages Its Different (vs. Phenol / Phosphite) Different Method of Analysis (vs. Phenol / Phosphite) l Becoming Industry Standard (~ last 3- 5 Years)
RK / ACS 01 - 42 -

Example #2: Color Stability

Gas Fade Resistance / Color Maintenance
N N (CH2)6 N N N N H N H n

O O N O O
n
N H

Hindered Amines Provide UV / Long Term Thermal Stability

O O H CH3

OH H 37C 18 N C18H37

CH3

Phosphite

Hydroxylamine

Lactone

Provide Melt Processing Stability

RK / ACS 01 - 43 -

Graph 3A - YI Color Maintenance; Gas Fade Exposure @ 60C; Knit Socks 1200 ppm HA-2/ L-1/ P-1 (non-AO "New / Improved") 1200 ppm HA-2/ NOH/ P-1 (no-AO "New / Improved")

Compared to phenol based systems, the phenol free systems offer excellent gas fade resistance.

1200 ppm HA-1/ NOH/ P-1 (no-AO "New / Improved") 1200 ppm HA-1/ NOH (no-AO "State of the Art") 1800 ppm HA-1/ P-1 (no-AO "1st Generation")

2000 ppm AO-2/ P-1 (AO Standard "B") 4 3 2 1 0 Wks 1500 ppm AO-1/ P-1 Wks (AO Standard "A") Wks Wks 0 Wks
- 44 -

10 YI Color

15

20

25

RK / ACS 01

Types of UV Stabilizer Chemistries

l UV Absorbers Hydroxyphenylbenzophenones Hydroxyphenylbenzotriazoles Hydroxyphenyltriazines l Excited State Quenchers Nickel based complexes l Free Radical Traps Hindered Amines

RK / ACS 01

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Mechanism of Activity: UV Absorbers

RK / ACS 01

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Representative UV Absorbers
H H

N N

light
N

N N

CH3 O H O O H

CH3 O

light
OC8 H17

OC8 H17

Calvert and Pitts: Photochemistry, Wiley, New York, 1967, p.534. Heller and Blattmann: Pur. Appl. Chem. 1973, 36, 141. Kramer: Angew. Makromol. Chem. 1990, 183, 67.
RK / ACS 01 - 47 -

UV Spectra
1.5 TINUVIN 234 TINUVIN 328 TINUVIN 326 TINUVIN 327 TINUVIN P

1 Abs 0.5 0 250

275

300

325

350

375

400

425

(nm)
20 mg/L in EtOAc

RK / ACS 01

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Mechanism of Activity: Excited State Quenchers

RK / ACS 01

- 49 -

UV Energy Quenchers
+ UV Light

O R-C-R

O* R-C-R

Quencher*

Quencher

- Energy dissipated as lower frequency light

(Some Chemistries Withdrawn due to Issues with Nickel in the Environment)

RK / ACS 01 - 50 -

Mechanism of Activity: Hindered Amines

(as free radical scavengers)

RK / ACS 01

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Representative Hindered Amine Stabilizers

N N (CH2)6 N N N

O O N O O
n n

R HN

R N N R= N C4H9 N N N N C4H9 H NH R

N H

N H

N H

R N

N N

(CH2)6

N N

H R
N

N N ]2O

N O

N N N

N N H N H

R
O n

R=

N C4H9

CH3

O O O O

H N N N N N N N H N H
RK / ACS 01 - 52 -

H N N N N N N n N N N N N H N

N H N H

O H17C 8O N

O N

O C (C H2)8 C O

OC8 H17

Hindered Amines
UV Stabilization via Free Radical Scavenging
R R [Oxid] R R

R* = - H - CH3 - OR

N R* [H+] R

N O

N O

R=O + ROH

ROO

N+ R* H

NOTE: An acidified hindered amine cannot easily enter into the free radical scavenging cycle

N-H and N-R Hindered Amine Stabilizers (HAS) fit most needs regarding light stability, but can be alkaline (basic) N-OR type HAS enter the UV stabilization cycle quickly, and are not alkaline, in comparison to N-H & N-R type HAS - 53 -

RK / ACS 01

Example #3
Interactions with Other Co-Additives ( + , = , - )
Dominant pKa's of Various Hindered Amines (Piperidinyl Group) HALS-8 (N-OR) HALS-4 (N-OR)

HALS-1 (N-R)

HALS-2B (N-CH3) HALS-2 (N-CH3)

HALS-5 (N-H) HALS-3B (N-H) HALS-3 (N-H) 0 2 4 6 8 10

pKa (as measured by titration of Conjugate Acid)

RK / ACS 01 - 54 -

Example #3
Interactions with Other Co-Additives ( + , = , - )
Light Stability of Flame Retardant Fiber
Hours to 50% Tenacity 500 400 300 200 100 0 0.05% HALS
No Flame Retardant
HAS-1 HAS-5

0.05% HALS

0.50% HALS

5% Brominated Flame Retardant

Stabilized PP homopolymer; 15 dpf; Carbon Arc Exposure

RK / ACS 01

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Conclusions
Importance of New Stabilizer Chemistries l Stabilizers should be used as tools to obtain the best products with the most value
l Fine tuning accomplished with the physical as

well as the aesthetic and ancillary properties

RK / ACS 01

Better melt flow rate retention (MW; MWD) Lower initial YI color and color maintenance Inhibition of gas fade discoloration Enhanced additive compatibility Reduced taste and odor (organoleptics) Resistance to ion or irradiation induced oxidation Suppression of gels and other imperfections

- 56 -

Impact of Performance vs. Concentration

Stable Polymer Powerful Additives Easy Processing Lower Temperatures Brief Residence Times Less Shear Diminishing Returns

Performance

The Zone
Unstable Polymer Weaker Additives Difficult Processing Higher Temperatures Long Residence Times High Shear

Insufficient Amount

RK / ACS 01

- 57 -

Additive Loading

Parallel Growth & Variety of Stabilizers

Volume Polymer
All Process Types m-PP m-PE Gas Phase zn-PP zn-PE AO: Hyperactives UV: N-OR HALS

Solution Phase Slurry Phase zn-PP zn-PE Melt Phase HP-LDPE

AO: HMW & Specialty Phenolics & Phosphites

UV: HMW Absorbers Hindered Amines (HALS) AO: BHT; TNPP UV: Absorbers

1935
RK / ACS 01 - 58 -

1955

1975

1995

Hans Zweifel - in Memorial (1939-2001)

l Dr. Hans Zweifel was a friend as well as

a scientific leader. He helped me to maintain a balance between business support vs. the science of additives

l Hans was also:

Lecturer for Polymer Additives at the Swiss Federal Institute of Technology (ETH) Zrich. Head of New Product Management at Ciba Specialty Chemicals Author of numerous publications & textbooks as well as editor of the new Plastic Additives Handbook Excellent guide in our off hours adventures in Switzerland
RK / ACS 01 - 59 -