by Luis Cruz, Ben Labovitz, and Eric Farone

Liquid Stabilizers for Flexible Vinyl Barium-Cadmium-Zinc some still in use Barium-Zinc most common today worldwide Barium-Calcium-Zinc and Calcium Zinc up and coming Non-metallic stabilizers Tins

Summary of Today s Topic What do stabilizers for flexible vinyl do? What do they do we wish they wouldn t do? What are stabilizers made of? What about calcium zinc liquids?

Preconceived Notions Barium-Zinc liquid stabilizers offer the best heat stability performance. Calcium Zinc liquid stabilizers are not up to par in heat stability. Calcium Zinc liquids plate-out. Calcium Zinc liquids are more volatile. Low volatile stabilizer systems sacrifice heat stability performance.

What Does A Stabilizer Need To Do? Scavenge HCl Replace labile chlorines Scavenge free radicals Remove/quench metal chlorides Prevent oxidation Prevent or delay the formation of conjugated double bonds Remain compatible with the polymer matrix

Things Stabilizers Do We Wish They Wouldn t Contribute to volatile emissions Impart odor Reduce printability Plate-out Add haze to clear vinyl Limited shelf stability

Non Phenolic- What does this mean? Less than 0.5% TOTAL SIMPLE PHENOL(CAS #108-95-2) Nonylphenol free Alkyl phenol free Organo phosphite can not hydrolyze to produce phenol

Anatomy of a typical Liquid Ba/Zn Stabilizer Ba Salt Zn Salt Organo Phosphite Co-stabilizers 1-10% Carrier/Solvent 5-50% (May contain up to 40% solvent) 5-20% (May contain solvent) 20-80% (Can hydrolyze to form simple phenol) 0-50% (Volatility varies)

Anatomy of a Liquid Ba/Zn Stabilizer continued Zn: Protects Early Color; reacts directly with polymer chain. Replaces labile chlorines generating strong lewis acids which catalyze further degradation. Ba: Provides long-term heat stability; Regenerates Zinc carboxylates and forms weak lewis acids. Organophosphite: Chelate metals, antioxidant, decomposes hydroperoxides. Co-Stabilizers: Metal boosters, AO, lubricants, compatibilizers. Solvent/Carrier: Eases handling and mixing, maintains shelf stability, volatility varies.

PVC and VOCs Stabilizers can contribute to the volatility of a PVC compound. All mixed metal liquids contain solvents or compounds that can generate volatile materials. Common VOCs from PVC- Phenol Low boiling hydrocarbon solvents Low molecular weight alcohols Glycols/glycol ethers

Properties of Typical Calcium Zinc Liquid Systems Calcium metal globally abundant and sustainable Primarily used for niche markets, such as FDA food contact applications Typical calcium zinc liquids impart inferior heat stability due to low metal content Standard calcium intermediates often contain high solvent levels for shelf stability High neutral/low over based metals salt content increases plate out tendency Higher potency solid calcium zinc stabilizers impart haze and handling difficulties Existing calcium zinc stabilizers have a limited range of stabilization applications

Properties of ultra high efficiency Calcium Zinc Liquid system How? Halstab has patented an over based calcium intermediate technology that makes possible: High metal content calcium intermediates which provide superior efficiency. Highly over based calcium intermediate reduces plate out tendency Very efficient intermediate allows formulation of high potency liquid calcium zinc stabilizers for clear and filled applications Sustainability calcium metal is a abundant worldwide. Heavy metal free Food grade possible Very low volatility Low odor Clear liquid Makes shelf stable products Expected compliance with REACH protocol

Test Compound Clear White PVC Resin 67 K value 100 100 DIDP 45 45 Epoxidized Soybean Oil 2 2 Calcium Carbonate --- 35 Titanium dioxide --- 1 Oxidized Polyethylene 0.25 0.25 Stabilizer 3 3

Two-Roll Mill Test Conditions 330ºF Roll Temperature 5 minute mixing cycle 20 mils film thickness 20:18 RPM Roll Ratio

Static Thermal Stability Test Conditions Blue M electric oven with rotating shelf 375 F 5, 10, or 15 minute intervals Chips cut from milled sheets

Early Screening Tests

Static Thermal Stability- 10 and 15 minute intervals

Static Thermal Stability- 5 minute intervals

Dynamic Mill Stability Test Conditions 365 ºF Roll Temperature 15 mils film thickness 30:18 RPM Roll Ratio Sample every 5 minutes

Dynamic Mill Stability

Torque Rheometer Test Conditions Head Type #6 60 gram charge- CLEAR 65 gram charge- WHITE 90 and 60 RPM 190 C and 180 C bowl temperature

Torque Rheometry 190 C, 90 RPM

Torque Curves Ba/Zn Control NEW Ca/Zn Liquid

Torque Rheometry 180 C, 60 RPM

Two Roll Mill Plate Out Test

Surface Tension Hold AccuDyne Test Marker Pens from Diversified Enterprises Film samples held at 100 F in 100% humidity. Film samples pressed together between glass plates under pressure. Polymeric Film

Surface Tension Hold

Volatility-1 hour in 110 C oven

Thermo Gravimetric Analysis-

Phenolic Content New Ca/Zn Liquid Ba/Zn Control Liquid Potential Simple Phenol Content Free Phenol Total Nonylphenol content <0.5% <0.5% 0% ~25% 1-3% 2%

Conclusions New ultra high efficiency Ca/Zn liquid stabilizers can be used to replace Ba/Zn liquids. Patented, food grade calcium intermediate technology (PlastiStab 2266) allows for the formulation of ultra high performance Ca/Zn liquid stabilizers. New Ca/Zn liquid stabilizers and Calcium intermediates are REACH friendly.