An expanding global supplier for the Plastics Industry

Transcription

1 An expanding global supplier for the Plastics Industry

2 PVC Stabilization and Sustainability Foro Técnico ProVinilo 2016 September 8, 2016 Mexico City, Mexico Dr. Peter Frenkel Drew Clock Galata Chemicals

3 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 3

4 Galata Chemicals - Product Chemistries Galata Chemicals is a leading producer of specialty chemicals and additives used primarily in the Plastics industry. Primary Plasticizers Secondary Plasticizers Mixed Metal Stabilizers Drapex Alpha Primary Plasticizers Drapex Epoxidized Soybean Oil Drapex Epoxidized Tall Oil Mark Mixed Metals Heat Stabilizers Tin Stabilizers Mark Organotin Heat Stabilizers Heavy Metal-Free Stabilizers Mark OBS Stabilizers Polymer Modifiers Organotin Specialties Liquid Phosphite Esters Solid Antioxidants Thioesters Anti-Static Agents Blendex Polymer Impact Modifiers Blendex Process Aids Fomrez Organotin Specialties Mark Organotin Specialties Markphos Liquid Phosphites Marknox Phenolic Antioxidant Markphos Phosphite Antioxidants Marknox Thioesters Markstat Anti-static Agents 4

5 Global Reach BRADFORD, ONTARIO Acrylic Impact Modifiers Acrylic Process Aids Tin Stabilizers LAMPERTHEIM, GERMANY Anti-Static Agents Epoxidized Oils Liquid Phosphite Esters Mixed Metal Stabilizers Primary Plasticizers Tin Stabilizers SOUTHBURY, CT Global Headquarter TAFT, LOUISIANA Anti-Static Agents Epoxidized Oils Mixed Metal Stabilizers Organotin Specialties Primary Plasticizers Tin Stabilizers DAHEJ, INDIA Solid Antioxidants Liquid Phosphite Esters HONG KONG Asia Office TARAPUR, INDIA Thioesters MUMBAI, INDIA India Sales Office Manufacturing Technical Center Corporate / Sales Office Warehouse / Terminal 5 Galata has an established global footprint with sales in over 50 countries

6 Sustainability of PVC Low carbon footprint Low energy consumption Low emission generation Low waste generation Durability Recyclability Versatility Green Building credits Thermoplastic Materials Polyethylene Polypropylene Polystyrene Rigid Poly(vinyl chloride) Total Carbon content, % PVC is of low total carbon content compared with other conventional thermoplastics 6

7 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 7

8 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) 8

9 Function of PVC Stabilizers 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 9

10 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 Current and especially new stabilizers address performance and regulatory requirements in a sustainable manner 10

11 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 11

12 Selected Heat Stabilizers for Rigid PVC 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 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

13 Heat Stabilizers for PVC and CPVC Pipes Stabilizers Mark 1942 Attributes More lubricating, improved costin-use GP Pipe Conduit Y Y Applications NSF Pipe Profile, Sheet Injection Molding CPVC 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 longterm 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 13

14 Solid Organotin Stabilizers ( Dry Liquid Concentrates - DLC) 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 14

15 Yellowness Index Selected Performance Attributes of Organotin DLC Components Loadings, phr SE 950 PVC Resin Rheolube RL Calcium Stearate 1.50 Stearic acid 0.20 Process Aid 1.00 Impact Modifer 5.00 UFT (Calcium Carbonate,) 5.00 Parameters Mark 2909 DLC Mark 2909 Decomposition Time, min:sec Volatility, % wt. loss Odor Intensity (1-5 Scale ) 20:32 33: Stabilizer (ortanotins) Dynamic Heat Stability Mark 292 "DLC Mark 292" Time, min 15

16 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 16

17 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,

18 Selected Heat Stabilizers for Flexible PVC LMM SMM Paste Ca/Zn Ba/Zn Ca/Zn Ba/Zn Ca/Zn Liquid Heavy Metal- Free 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

19 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

20 Compound and Test Protocol Component phr PVC Resin Stabilizer 1.70 DOTP 34.5 ESO 3.0 Acrylic Process Aid 3.0 Stearic Acid 0.15 Calcium Carbonate Evaluations Equipment Test Conditions Static Heat Stability Blue M Oven 177 o C, 190 o C, 15 /10 Intervals Mill Stability Collin Mill 177 o C (30 rpm) 20

21 Static Heat Stability Mark 3022 is a superior stabilizer (the static test) to the Market Control 21

22 Continuous Rolling Test (Mill Stability) Mark 3022 is a superior stabilizer (the dynamic test) to the Market Control. It extended the Time-to-Sticking 22

23 Galata s Low VOC, AgBB-compliant Heat Stabilizers for LVT Flooring 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) 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) 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) 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) Drapex 39 Spread coating and Calendering All layers Epoxy co-stabilizer deodorized low odor ESBO Liquid

24 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 ) 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 24

25 Natural Oil-based Primary Plasticizer Technology (NOPP) Product Grades of Drapex Alpha 200 Series Main Applications GP Pigmented & Filled Drapex Alpha 200 Drapex Alpha 200C Drapex Alpha 210 Drapex Alpha 215 Flooring Wall Covering Shoes Other Specialties Automotive Roofing Membrane 25

26 Performance Reference to DINP Plasticiser DINP/ESBO (control) Efficiency (Shore A Hardness) Processability Volatility Extraction Resistance Low Temp. Flexibility UV-light Stability Decomp. Time Drapex Alpha In-process Color Development Performance Scale Worse Same Better 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 Blending Performance with Sustainability 26

27 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 27

28 Attainable Bio-based Content Bio-based flexible PVC can be obtained with the use of bio-based Plasticisers Bio-based Plasticiser + PVC = Bio-based Flexible PVC Plasticiser Loading, phr Calculated Bio-based Content, % Drapex Alpha 200 Drapex Alpha 200 Drapex Alpha >25 >30 >40 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 Blending Performance with Sustainability 28

29 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 Observed Growth, % Rating Scale Description 0 0 No microbial growth <10 1 Very restricted microbial growth Intermittent infestation 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 29

30 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 CO 2 eq Cumulative energy demand, MJ kg of Drapex Alpha 200 used to replace 1 kg of Average Phthalate results in Reduced Global Warming Potential by 2.36 kg CO 2 eq. Reduced energy consumption for manufacturing by 36% 30

31 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 (CO 2 ) 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 31

32 Conclusions 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 Blending Performance with Sustainability 32

33 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 Phone: info@galatachemicals.com 33