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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
[email protected] 219-844-3980 ext. 241
219-512-4381 (cell)
Nick Kruse Lab Manager
[email protected] 219-844-3980 ext. 242
219-313-3127 (cell)
Maureen Valle Lab Technician
Luis Cruz North American Business Manager- Vinyl Additives [email protected]
219-844-3980 ext. 251 (330)-635-0159 (cell)