An expanding global supplier for the Plastics Industry

PVC Stabilization and Sustainability

Foro Técnico ProVinilo 2016

September 8, 2016

Mexico City, Mexico

Dr. Peter Frenkel

Drew Clock

Galata Chemicals

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Outline

• Sustainability of PVC

• PVC degradation and stabilization

• Functions and types of PVC stabilizers

• Impact of regulatory restrictions on compositions of PVC heat stabilizers

• Selected heat stabilizers for rigid and flexible PVC

• Heat stabilizers for Luxury Vinyl Tile (LVT) flooring materials

• Bio-based chemicals and plastics

• Labeling of bio-based materials

• Bio-based PVC through plasticizers

• Life Cycle Assessment

• Conclusions

Galata Chemicals - Product Chemistries

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Primary Plasticizers Drapex Alpha® Primary Plasticizers

Secondary Plasticizers Drapex® Epoxidized Soybean Oil

Drapex® Epoxidized Tall Oil

Mixed Metal Stabilizers Mark® Mixed Metals Heat Stabilizers

Tin Stabilizers Mark® Organotin Heat Stabilizers

Heavy Metal-Free Stabilizers Mark OBS® Stabilizers

Polymer Modifiers Blendex® Polymer Impact Modifiers

Blendex® Process Aids

Organotin Specialties Fomrez® Organotin Specialties

Mark® Organotin Specialties

Liquid Phosphite Esters Markphos® Liquid Phosphites

Solid Antioxidants Marknox® Phenolic Antioxidant

Markphos® Phosphite Antioxidants

Thioesters Marknox® Thioesters

Anti-Static Agents Markstat® Anti-static Agents

Galata Chemicals is a leading producer

of specialty chemicals and additives

used primarily in the Plastics industry.

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Global Reach

Manufacturing Technical Center Corporate / Sales Office Warehouse / Terminal

SOUTHBURY, CT Global Headquarter

LAMPERTHEIM, GERMANY Anti-Static Agents Epoxidized Oils Liquid Phosphite Esters Mixed Metal Stabilizers Primary Plasticizers Tin Stabilizers

HONG KONG Asia Office

MUMBAI, INDIA India Sales Office

TARAPUR, INDIA Thioesters

DAHEJ, INDIA Solid Antioxidants Liquid Phosphite Esters

Galata has an established global footprint with sales in over 50 countries

BRADFORD, ONTARIO Acrylic Impact Modifiers Acrylic Process Aids Tin Stabilizers

TAFT, LOUISIANA Anti-Static Agents Epoxidized Oils Mixed Metal Stabilizers Organotin Specialties Primary Plasticizers Tin Stabilizers

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Sustainability of PVC

Thermoplastic Materials Total Carbon

content, %

Polyethylene

Polypropylene

Polystyrene

Rigid Poly(vinyl chloride)

86

86

92

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PVC is of low total carbon content compared with other conventional thermoplastics

• Low carbon footprint

• Low energy consumption

• Low emission generation

• Low waste generation

• Durability

• Recyclability

• Versatility

• Green Building credits

PVC Degradation and Stabilization

• Degradation under the influence of heat and UV light is an intrinsic property of PVC

• PVC degradation may occur via three mechanisms: radical, ionic and molecular

• PVC degradation results in loss of mechanical properties and discoloration

• Formed polyenes containing greater than five conjugated double bonds are colored

• Thermal stabilization of PVC can be achieved via

− Reaction with allylic chlorides (it is faster than the chain propagation reaction)

− Scavenging HCl that catalyzes initiation and propagation of dehydrochlorination

− Shortening polyene sequences

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Complexity of PVC Degradation (“Zipper chain” Mechanism)

Literature:

•A.R. Amer,

J.S. Shapiro,

J.Macromol.

Sci. 14, 185

(1980)

•R.Bacaloglu,

M.H.Fisch,

Polym.Deg.Sta

b. 47, 33 (1995)

•W.H.Starnes et

al, Macromol.

29, 7631 (1996)

Function of PVC Stabilizers

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Prevent/reduce degradation of PVC due to exposure to heat, light and in-process

stress/shear that result in the reaction of dehydrochlorination

Types of PVC Stabilizers

• Solid and Paste Mixed Metal stabilizers

• Liquid Mixed Metal stabilizers

• Alkyl Tin-containing stabilizers

• Heavy metal-free stabilizers

• Lead Stabilizers

Drivers for the Development of PVC Stabilizers

• Regulatory and Environmental Restrictions on chemicals

• Regulations for the construction industry and indoor air quality

• General trend on sustainability

• Raw material cost and feedstocks

• More demanding performance requirements

• Inter-material competition

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Current and especially new stabilizers address performance and regulatory

requirements in a sustainable manner

Examples of Restrictions on Components of PVC Stabilizers

• Implementation of RoHS

(Restriction on Hazardous Substances in electrical and electronic products)

− Restrictions on Lead

− Restrictions on Cadmium

• Voluntary commitment of European Stabilizer Producers Association to phase out

lead by 2015

• Implementation of REACh

(Registration, Evaluation, Authorization and Restriction of Chemicals)

− Phase-out of butyltin compounds in Europe

− Phase out p-t-butyl benzoic acid

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Selected Heat Stabilizers for Rigid PVC

Methytins Butyltins Octyltins Ca/Zn Heavy Metal-Free

Mark 1900 Mark 292 Mark 17MOK Mark 3260 Mark OBS 701

Mark 1984E Mark 2270F Mark 17 MOK A Mark CZ2000 Mark OBS 703

Mark 1910 Mark 2294 Mark 17 MOK D Mark 3022

Mark 1992 Mark 3174 Mark T682 TS-1569

Mark 1942 Mark T650 TS-1570

Mark 1988 TS-1573

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• Galata Chemicals (Witco Corporation) voluntarily exited the cadmium stabilizer business in 1994

• Galata heat stabilizer Product Offering (trade names: Mark® and Mark® OBS®) for rigid PVC

− Complete line of REACh-compliant octyltin- and methyltin stabilizers for Europe

− Complete line of all organotin stabilizers for other parts of the world

− Solid and certain liquid Calcium/Zinc stabilizers

− Heavy metal-free stabilizers

• Organotin stabilizers are liquids; offer high efficiency, transparency and toughness

Heat Stabilizers for PVC and CPVC Pipes

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Stabilizers

Attributes

Applications

GP Pipe Conduit NSF

Pipe

Profile,

Sheet

Injection

Molding

CPVC

Mark 1942 More lubricating, improved cost-

in-use Y Y

Mark 1939 Industry Standard Y Y Y

Mark 1988 Advanced fusion and lubrication Y Y Y

Mark 2903 High efficiency Y Y

Mark 1925 High efficiency and more

lubricating Y Y

Mark 2909 High efficiency, long-term

stability Y

Mark 1993 High efficiency, extended long-

term stability Y Y Y

Mark 2911 Advanced heat stability in large

diameter pipe Y Y Y

Mark 1982 High efficiency Y

Mark 292 Industry Standard Y

Mark 17MOK A More lubricating Y

Mark OBS 703 Heavy metal-free Y

Solid Organotin Stabilizers

(“Dry Liquid Concentrates” - DLC)

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• A range of organotin stabilizers in a solid form is in development

• Target performance attributes

– lower odor

– Lower VOC

– lower tin content

– comparable-to-superior heat stability

– handled via the standard metering equipment for solids

• Samples are available

Selected Performance Attributes of Organotin DLC

Components Loadings, phr

SE 950 PVC Resin 100.00

Rheolube RL-165 1.20

Calcium Stearate 1.50

Stearic acid 0.20

Process Aid 1.00

Impact Modifer 5.00

UFT (Calcium Carbonate,) 5.00

Stabilizer (ortanotins) 1.50

15

0

5

10

15

20

25

30

35

40

45

50

0 5 10 15 20

Ye

llow

ne

ss I

nd

ex

Time, min

Dynamic Heat Stability

Mark 292

"DLC Mark 292"

Parameters Mark 2909 “DLC Mark 2909”

Decomposition

Time, min:sec 20:32 33:48

Volatility,

% wt. loss 2.6 2.1

Odor Intensity

(1-5 Scale ) 5 3

Examples of Indoor Air Quality Initiatives for Building Materials

• North America

− US Green Building Council: LEED (Leadership in Energy and Environmental Design)

− “ReGreen” (Residential Remodeling)

− Greenguard Environmental Institute

− Green Guide for Health Care

− Green Building Initiative: Green Globes System

− California Proposition 65

• Europe

− AgBB (Committee for Health-related Evaluation of Building Products)

Effective since 2000; most recent update in 2012

Examples of Applications: flooring, wall-covering

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Implications of Indoor Air Quality Initiatives

on Designing PVC Stabilizers

• Examples of Restricted Components

− Phenol

− Nonylphenol

− 2-Ethylhexanolic acid

− Low-boiling hydrocarbons

− Total VOC

• A range of phenol-free, nonylphenol-free,

and dodecylphenol-free liquid Ba/Zn

stabilizers designed for the most sensitive

applications is in development

– Samples will be available in Q4, 2016

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Selected Heat Stabilizers for Flexible PVC

LMM SMM Paste

Liquid Heavy

Metal- Free Ca/Zn Ba/Zn Ca/Zn Ba/Zn Ca/Zn

Mark CZ180 Mark 4885 Mark 6105 Mark 6765 Mark CZ 11 Mark OBS 2305

Mark 3023 Mark 4754LV Mark 6092 Mark 6782 Mark 152 Mark OBS 2405

Mark 3071 Mark 9586 Mark 6246 Mark 6783 Mark OBS 1200

Mark 3079 Mark 9552 Mark 3022 Mark 3243

Mark 9555 Mark 3227 Mark 3244

Mark 3260 Mark 3245

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Calendered Laxuary Vinyl Flooring (LVT)

(“Static Press” Lamination of Individual Layers)

PU Coating- UV cured

PVC Transparent Wear layer : Mark 3244 or Mark 3245

PVC Printing Layer: Mark 3260

PVC Middle Layer: Mark 3022

Glass Fiber

PVC Back Layer: Mark 3022 or Mark 3243

Compound and Test Protocol

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Component phr

PVC Resin 1 100.00

Stabilizer 1.70

DOTP 34.5

ESO 3.0

Acrylic Process Aid 3.0

Stearic Acid 0.15

Calcium Carbonate 66.67

Evaluations Equipment Test Conditions

Static Heat Stability Blue M Oven 177o C, 190

o C, 15’/10’ Intervals

Mill Stability Collin Mill 177o C (30 rpm)

Static Heat Stability

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Mark 3022 is a superior stabilizer (the

static test) to the Market Control

Continuous Rolling Test (Mill Stability)

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Mark 3022 is a superior stabilizer (the

dynamic test) to the Market Control.

It extended the Time-to-Sticking”

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Stabilizer Processing

Technology

Applications Characteristics Type Physical

Form

Recommended

Dosage (phr)

Mark 3244

Mark 3245

Calendering

Transparent wear

layer

Phenol free, 2-EHA free,

Nonylphenol free, low odor. Very

good initial color and color hold,

good self-lubrication

Ca/Zn

Solid

(powder)

1.4 - 1.7

Mark 3052

Calendering/

Extrusion

Transparent wear

layer

Phenol free, 2-EHA free,

Nonylphenol free, low odor. Very

good initial color and color hold,

good self-lubrication

Ca/Zn

Solid

(powder)

1.2 - 1.7

Mark 3260

Calendering

Transparent wear

layer and

Pigmented Printing

layer

Phenol free, 2-EHA free,

Nonylphenol free, low odor, good

early color, good self-lubrication,

suitable especially for rigid PVC

Ca/Zn

Solid

(powder)

1.5 – 2.0

Mark 3243

Mark 3022

Calendering

Highly filled layer

.

Phenol free, 2-EHA free,

Nonylphenol free, low odor, good

early color, good self-lubrication

Ca/Zn

Solid

(powder)

1.0 - 1.5

Drapex 39

Spread

coating and

Calendering

All layers Epoxy co-stabilizer deodorized

“low odor” ESBO Liquid 2.0 – 4.0

Galata’s Low VOC, AgBB-compliant Heat Stabilizers for LVT Flooring

Methods for Preparation of Bio-based Plastics

1. Bio-polymers

2. Traditional plastics from bio-based monomers

3. Traditional plastics with bio-based fillers and reinforcements

4. Blends of bio- and petroleum-based polymers and co-polymers

5. Blends of bio- and petroleum-based monomers

(Plastics and Sustainability by M. Tolinski; John Wiley & Sons and Scrivener Publishing;

2012, p. 251-252)

Traditional methods differ by the nature of monomers and fillers

6. Traditional plastics plasticized by bio-based plasticizers – unique approach

− Example: PVC plasticized with bio-based plasticizers

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Main Applications

Product Grades of Drapex Alpha 200 Series

Drapex Alpha 200

Drapex Alpha 200C

Drapex Alpha 210

Drapex Alpha 215

GP Pigmented & Filled ●

Flooring ● ●

Wall Covering ●

Shoes ● ●

Other Specialties ● ●

Automotive ● ●

Roofing Membrane ●

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Natural Oil-based Primary Plasticizer Technology (NOPP)

Blending Performance with Sustainability™

Performance Reference to DINP

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Performance Scale

• Drapex Alpha 200 series performance attributes

– Improved Efficiency (reduced consumption)

– Improved Low-temperature brittleness point

– Considerably lower Volatility

– Four-fold increased the Decomposition Time (Congo Red method)

– Improved Extraction Resistance in sunflower oil and hexane; reduced water pick-up

– Enhanced Processability (lower torque, rapid fusion, no plate-out, smooth melt flow)

• Drapex Alpha 200 eliminates a need for using ESBO as a secondary Plasticiser

Plasticiser Efficiency

(Shore A

Hardness)

Process-

ability

Volatility Extraction

Resistance

Low Temp.

Flexibility

UV-light

Stability

Decomp.

Time

In-process

Color

Development

DINP/ESBO

(control) 0 0 0 0 0 0 0 0

Drapex Alpha + + + + + 0 + 0

Worse Same Better

- 0 +

USDA’s BioPreferred Product Label

• Department of Agriculture launched a labeling initiative to identify commercial bio-based

products from renewable feedstock (Federal Register on January 20, 2011)

• Manufacturers and distributors will be able to affix a USDA Certified Biobased product label on

qualifying products and intermediates

• Minimum bio-based content required to have a product certified: 25% (in accordance with

ASTM D-6866/carbon dating technique)

• The label looks similar to the one used by USDA for organic foods

• By its design, the seal is to give bio-based products the same boost that the Energy Star

program gave to energy-efficient appliances

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Blending Performance with Sustainability™

Attainable Bio-based Content

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• Drapex Alpha 200 is an excellent source of renewable carbon in flexible PVC formulations

• Drapex Alpha 200 enables in many cases a complete replacement of conventional

Plasticizers at high loadings, resulting in flexible PVC of high bio-based content

• Drapex® Alpha 200 (loaded at >30 phr) enables attaining >25% bio-based content in

flexible PVC and makes it suitable for USDA Bio Preferred Labeling

Plasticiser Loading, phr Calculated Bio-based Content, %

Drapex Alpha 200

Drapex Alpha 200

Drapex Alpha 200

30

40

60

>25

>30

>40

• Bio-based flexible PVC can be obtained with the use of bio-based Plasticisers

Bio-based Plasticiser + PVC = Bio-based Flexible PVC

Microbiological Resistance

(ASTM G21-96: Resistance of Synthetic Polymeric materials to Fungi)

Plasticizer at 40 phr Rating Observation

DINP (control) at 40 phr

1.7

Drapex Alpha 200 at 36 phr

(at same Shore A hardness)

1.0

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Observed

Growth, %

Rating

Scale

Description

0 0 No microbial growth

<10 1 Very restricted microbial growth

10-30 2 Intermittent infestation

30-60 3 Substantial microbial growth

>60 4 Massive microbial growth

• Rating 1.0: meets acceptance criteria

• Ratings are an average of 3 measurements

on each of 5 different tested microorganisms

• Compared with DINP, compounds

plasticized with Drapex Alpha 200 imparts

an increased microbial resistance

Life Cycle Assessment: Cradle-to-Gate

The study followed guidelines of and is compliant with the international

standards for Life Cycle Assessment ISO 14040:2006 and 14044:2006

Comparison: 1 kg Drapex Alpha 200 vs. 1 kg Avg. Phthalate*

*Note: Average Phthalate is represented by an average result for DEHP, DINP and DIDP

Environmental Impacts Drapex Alpha 200 Avg. Phthalate

Global Warming Potential, kg CO2 eq. -0.40 1.96

Cumulative energy demand, MJ 32.98 51.69

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1 kg of Drapex Alpha 200 used to replace 1 kg of Average Phthalate results in

• Reduced Global Warming Potential by 2.36 kg CO2 eq.

• Reduced energy consumption for manufacturing by 36%

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Advantages of Bio-based Chemicals (Compared with the petroleum-based products)

•Renewable Feedstock

-Replenishment is faster and better controlled

•Positive Environmental Impact (Established Based on Life Cycle Assessment)

-Reduced water and energy consumption to produce

-Reduced Global Warming Potential, lowering output of green house gases (CO2)

• Lower volatile emissions

• Reduced amounts of undesirable components

Bio-based chemicals, such as stabilizers and plasticizers, contain reduced amounts of

undesirable components, lower emissions and carbon footprint and address public

concerns in the most sustainable manner

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• Modern design of heat stabilizers addresses processing

and performance requirements of PVC in a sustainable

manner

• Galata Chemicals is a reliable partner and a global

leader in developing and providing sustainable stabilizer

and plasticizer technical solutions for all major markets

and applications

Conclusions

Blending Performance with Sustainability

Disclaimer

The information contained herein is believed to be reliable, however is based upon laboratory

work with small scale equipment and does not necessarily indicate end-product performance.

Because of variations in methods, conditions and equipment used commercially in processing

these materials, Galata Chemicals makes no representations, warranties or guarantees,

express or implied, as to the suitability of the products for particular applications, including

those disclosed, or the results to be obtained. Full-scale testing and end-product performance

are the responsibility of the user. Galata Chemicals shall not be liable for and the customer

assumes all risk and liability for use and handling of any materials beyond Galata’s direct

control. Nothing contained herein is to be considered as permission, recommendation nor as

inducement to practice any patented invention without permission of the patent owner.

Contact Information

North America Galata Chemicals, LLC

464 Heritage Rd., Suite A1, Southbury, CT 06488

Phone: +1 203 236 9000 Email: info@galatachemicals.com

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