New Developments in Alkyl phenol Free, Phenol Free, Low VOC Liquid

Stabilizers for Flexible PVC

VINYLTEC 2015

Luis CruzNorth American Business Manager

AM Stabilizers10-2015

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Summary of Topics• Overview of current regulations impacting PVC heat

stabilizers and driving development.

• Discussion of sources of Phenol in liquid mixed metal stabilizers.

• Alkyl Phenol Free and Phenol Free Ba/Zn and Ca/Zn liquid stabilizers for flexible PVC

• Heat stability and performance data of new Ba/Zn and Ca/Zn liquids

• Conclusions

• California Prop. 65- “Safe Drinking Water and Toxic Enforcement Act of 1986. State legislation intended to protect citizens and drinking water “from chemicals known to cause cancer, birth defects, or other reproductive harm, and to inform citizens about exposures to such chemicals.”

• REACH- A European Union regulation aimed at protecting human health and the environment from Chemical risks.

• German AgBB Specification and DIBt Regulation- Restrictions on VOC emissions from construction products. Very tight restriction on Phenol emissions.

• California Specification 01350- Restrictions on VOCs from products used indoors.

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Regulations Impacting PVC

California’s Proposition 65• List of Chemicals known to the state of California

to cause cancer or reproductive harm. http://oehha.ca.gov/prop65

• Most up to date list is August 25, 2015 which can be found at: http://oehha.ca.gov/prop65/prop65_list/files/P65single082515.pdf

• Some common or formerly common PVC additives appear on the list- BPA, BHA, BBP, Cadmium, Lead, DEHP, DIDP, DINP, DBP and many more….

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California Prop 65 Substances Common to PVC

• Certain Phthalate Plasticizers- DINP, DEHP, DBP, DnHP, DINP, DIDP, BBP

• Benzene- impurity in some solvents.

• Bisphenol A- Added back to the Prop. 65 list as of May 2015.

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• SVHC= Substance of Very High Concern

• Essentially a black list of chemicals (substances).

• A Candidate list of substances for Authorization.

• Once a substance is listed as an SVHC replacement is indicated. Even if Authorization is granted sunset date applies!

• Updated regularly, currently 163 substances as of June 15, 2015 : http://echa.europa.eu/candidate-list-table

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REACH and SVHCs

REACH

• 4-nonyl phenol (and all isomers) added to the Candidate list as of December 19, 2012

• 4-dodecyl phenol has been assigned the classification of Reproductive Toxic material Category 1B, meaning very likely it will become an SVHC.

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• German AgBB Specification and DIBt Regulation

• Sets very tight restrictions on VOCs especially phenol.

• In order to reliably pass this specification it is necessary to have total phenol content of the PVC article in the low PPM range.

• Phenol is a common VOC from flexible PVC

• What is the source of phenol?

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Synthesis of Phosphite Esters !

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PCl3 + 3 PhOH → P(OPh)3

Where PhOH = Phenol

P(OPh)3 + 3 ROH → P(OR)3 + 3 PhOH

Where ROH = Primary Alcohol, i.e. isodecyl-OH

Step 1:

Step 2:

*Phenol is removed from the finished product.

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Common Types of Organo Phosphites used in PVC Heat Stabilizers !

•  Diphenyl isodecyl phosphite- 2 moles phenol, 1 mole isodecyl alcohol !

•  Phenyl diisodecyl phosphite- 2 moles isodecyl alcohol, 1 mole phenol !

•  Triisodecyl phosphite- 3 moles of isodecyl alcohol !

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Phenol Content Definitions !

•  Free Phenol- Quantity of un-bound phenol present in the product. Typically represents residual phenol not removed from product. !

•  Total Phenol- Quantity of potential phenol IF all of the phosphite were completely hydrolyzed. !

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Free and Total Phenol in Organo phopshites!

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Phosphite Type FREE PHENOL

TOTAL PHENOL

Diphenyl isodecyl phosphite- 2 moles phenol, 1 mole isodecyl alcohol !

<1%

~50%

Phenyl diisodecyl phosphite- 2 moles isodecyl alcohol, 1 mole phenol !

<1% ~20%

Triisodecyl phosphite- 3 moles of isodecyl alcohol !

<1% <1%

Ultra Low Phenol Grade Triisodecyl phosphite- 3 moles of isodecyl alcohol !

Non- Detect Non-Detect

*Non-detect = less than 10 PPM

* *

Low Phenol Liquid Mixed Metal Stabilizers

• Selection of phosphite grade is critical.

• Non-detect (<10 PPM) phenol levels are possible.

• “Low Phenol” is 0.5% MAX TOTAL Phenol

• “Ultra Low Phenol” is non-detect or 10 PPM MAX TOTAL Phenol.

• Cross contamination must be considered!13

Sources of Alkyl Phenols in Liquid Mixed Metal Stabilizers for PVC

• May be added directly as an anti-oxidant.

• As a metal-phenate. Typically Ba or Ca.

• eg.- barium bis(nonylphenolate)

• As an impurity or hydrolysis product of TNPP (tris nonyl phenyl phosphite).

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Designing a Stabilizer System for PVC Today

• Option 1- Use an all powder system. This eliminates many of the common bad actor substances such as phenol, alkyl phenols, VOCs, phthalates, solvents.

• However, powder stabilizers have disadvantages- Clarity in PVC is not as good. Early color is not as good. Migration resistance is not as good. Material handling.

• Option 2- Use a liquid stabilizer that does not contain the bad acting substances.

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Heat stability and Clarity of new Ba/Zn and Ca/Zn liquids

• Ba/Zn Liquid Stabilizer with Low Phenol Content (0.4% MAX TOTAL Phenol) containing an alkyphenol.

• VS

• Ba/Zn and/or Ca/Zn Liquid Stabilizer that is Alkyl phenol Free and Ultra Low Phenol Content (Non-Detect TOTAL Phenol content.

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EXPERIMENTAL CONDITIONS

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Dynamic Mill Test Conditions

365 F(front and back rolls)

10 minute interval chips

25 mils

30:18 Roll Ratio(Front:Back)

100 gram charge

Static Thermal Stability Test Conditions

365 F(front and back

rolls)5 minute mix

25 mils

20:18 Roll Ratio(Front:Back)

120 gram charge

Oven Stability Test Conditions

375 F

7.5 minute interval chips

Press Plaque Test Conditions

350 F

30K PSI

5 minute heat & cool

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VinylTec

Test Formulation: Resin k=70 – 100phr DOTP – 45phr ESO – 2phr

Two-Roll Mill & Static Thermal Stability 365ºF mill 5 minute mix 25 mils 20/18 120g 375ºF oven

Alkylphenol-free Ba/Zn Total Phenol = Non-Detect @ 4phr R1

Alkylphenol-free Ba/Zn Total Phenol = Non-Detect @ 4phr R2

Ba/Zn with Nonylphenol Total Phenol = 0.4% @ 4phr

0 7.5 15 22.5 30 37.5 45 52.5 60

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VinylTec

Test Formulation: Resin k=70 – 100phr DOTP – 45phr ESO – 2phr

Dynamic Mill Stability 365ºF mill 10 minute intervals 30/18 100g 25 mils

Alkylphenol-free Ba/Zn Total Phenol = Non-Detect @ 4phr R1

Alkylphenol-free Ba/Zn Total Phenol = Non-Detect @ 4phr R2

Ba/Zn with Nonylphenol Total Phenol = 0.4% @ 4phr

10 20 30 40 50 60 70

Stuck to Roll

Stuck to Roll

Stuck to Roll

2015

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VinylTec

Test Formulation: Resin k=70 – 100phr DOTP – 45phr ESO – 2phr

Press Plaque 350ºF press 30,000 PSI 5 minute Heat & Cool

Alkylphenol-free Ba/Zn Total Phenol = Non-Detect @ 4phr R1 B-value = 7.49

Ba/Zn with Nonylphenol Total Phenol = 0.4% @ 4phr B-value = 7.35

Alkylphenol-free Ca/Zn Liquid Total Phenol = Non-Detect @ 4phr B-value = 9.97

Ca/Zn Powder Total Phenol = Non-Detect @ 4phr B-value = 13.68

Press Plaque Diagram

Alkylphenol-free Ba/Zn Total Phenol = Non-Detect @ 4phr R2 B-value = 7.43

New Ca/Zn Alkyl Phenol and Phenol Free Liquid vs. Low Phenol Ba/Zn Liquid

Ba/Zn Liquid w/Nonylphenol

Total Phenol= 0.4%Ca/Zn Liquid

Alkyl phenol Free Total Phenol= ND

Dynamic Mill Lubricity 365 F, 30:18 Roll Ratio, 0.3 mm

5 minute intervals

Conclusions• Regulations continue to impact flexible PVC formulations

• Lower VOC content and lower Phenol content are important now.

• EU regulations are more stringent, especially for Phenol emissions.

• Nonyl phenol is an SVHC now and dodecyl phenol will likely be and SVHC in the future.

• Ba/Zn and Ca/Zn liquid stabilizers can be formulated to meet today’s and tomorrows regulations.

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Thank You!

Ben Labovitz Research and Development Manager

blabovitz@amstabilizers.com 219-844-3980 ext. 241

219-512-4381 (cell)

Nick Kruse Lab Manager

nkruse@amstabilizers.com 219-844-3980 ext. 242

219-313-3127 (cell)

Maureen Valle Lab Technician

mvalle@amstabilizers.com

Luis Cruz North American Business Manager- Vinyl Additives Lcruz@amstabilizers.com

219-844-3980 ext. 251 (330)-635-0159 (cell)