The development of new PVC resins for low emission applications. Chris Howick Ineos Vinyls

Transcription

1 The development of new PVC resins for low emission applications Chris Howick Ineos Vinyls

2 Outline Background to PVC» Suspension PVC Emulsion PVC PVC for interior applications Indoor Air Quality and Interior automotive air quality 17/05/2007 2

3 PVC Polymerisation Technologies Mass/Bulk Polymerisation» Limited volumes Suspension Polymerisation» Monomer/water suspension» Monomer soluble initiation» Powder blend formation Emulsion Polymerisation» Monomer/water dispersion (small droplets), stabilised by surfactants» Generally water soluble initiation» Used for plastisol and organosol formation 17/05/2007 3

4 Suspension PVC Polymers 17/05/2007 4

5 Emulsion PVC Polymers 17/05/2007 5

6 S-PVC: Powder Blend 17/05/2007 6

7 E-PVC: Plastisol Formation 17/05/2007 7

8 PVC End Product Classification Rigid or Unplasticised PVC» PVC-U» Does not contain a plasticiser Flexible or Plasticised PVC» PVC-P» Contains plasticiser PVC is unique in its ability to accept and retain large quantities of plasticiser and have its properties significantly altered by such addition 17/05/2007 8

9 GLOBAL PVC MARKET Flexibles 35% Coatings Bottles 2% Others 7% Flooring 3% 3% Wire Cables 8% Pipes/Fittings 38% 65% Film Sheet 18% Rigids Profile/Tubes 20% 17/05/2007 9

10 Plastisol Additives Simple Plastisol contains PVC resin and plasticiser but this requires additional additives to produce a end product that meets the requirements of the processor and end product» Thermal stabilisers» High Performance Plasticisers» Pigments» Fillers» Viscosity Modifiers» Blending resins and copolymers» UV Stabilisers» Chemical Blowing Agents» Solvents 17/05/

11 E-PVC Plastisol Applications Flooring» Can be a four layer construction» Contract Areas aimed at EU Directive 89/106/EEC (Construction products) Wallcoverings» Single PVC layer on paper much thinner than flooring ( gsm)» Contract areas also aimed at 89/106/EEC Compliance Synthetic Leather for automotive applications» Typically two or three PVC layers on a fabric support (or unsupported)» Fogging of windscreen Raw material screening DIN VOC emission analysis 17/05/

12 Plastisol Formulation INGREDIENT TYPICAL LEVEL (%) POTENTIAL EFFECT ON CHEMICAL EMISSION PVC Resin None (see fogging) Fillers None Pigments 1 10 None Plasticiser Low (as SVOC) Stabiliser 1 2 High (depends on type) Chemical Blowing Agent 0 2 Low (gases lost in processing) Viscosity Modifiers High (depends on type) Solvents 0 2 High 17/05/

13 Figure 1: Performance of various E- PVC resins in DIN Fog (mg) Resin EP7485 (Ineos) EP7080 (Ineos) EP7073 (Ineos) US Gen Pur resin 17/05/

14 Volatile Loss Headspace GC VOC Emission Work at Ineos Vinyls With advent of EN adopting more work using FLEC and Thermal Desorption GC-MS for»screening of Plastisol Additives for their VOC release potential»comparing PVC based products with its principle alternatives 17/05/

15 Plastisol Formulation Development: New E-PVC Resins Target is to reduce viscosity modifiers and solvents These are needed to maintain low pumping and low coating viscosity»low viscosity at low shear»low viscosity at high shear Resin chemistry has a fundamental contribution to the viscosity of the plastisol Late 1990s and early 2000s has seen the development of new families of E-PVC resins aimed at producing lower viscosity plastisols so as to minimise or eliminate the use of volatile plastisol ingredients 17/05/

16 500 Viscosity (Poise) Standard msp Modified msp 0 A B C Formulation A = 100 PVC, 50 DEHP B = 100 PVC, 40 DEHP C = 100 PVC, 50 DEHP, 50 PHR CaCO3 17/05/

17 Akcrostab Stabilisers Oven Volatility at 150 C % Weight loss Conventional stabiliser General Purpose Stabiliser Low Volatility Stabiliser Akcrostab Stabiliser Time (mins) 17/05/

18 Akcrostab Stabilisers 17/05/

19 Akcrostab FLEC Analysis Stabiliser type Emission factor (μg/m 2 hr) as equiv. of toluene General Purpose Stabiliser 215 Conventional Stabiliser 66 Akcrostab Stabiliser 27 Solid Stabiliser 5 Akcrostab Stabiliser has lowest FLEC emissions of liquid stabilisers 17/05/

20 Latest results: flooring formulation Intensity (%age) Intensity (%age) :00 6:00 8:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 24:00 Retention Time :00 4:00 6:00 8:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 24:00 Retention Time 17/05/

21 Conclusions FLEC has been a valuable tool for screening of emission potential of plastisol additives New ranges of resins capable of giving plastisols with low viscosity at low and high shear have been developed Resins with very low potential for automotive windscreen fogging (as well as low VOC emission) have also been developed PVC based products compare very well with competitive materials with respect to VOC emission Further inter-material comparisons and resin developments are continuing 17/05/