Introduction To Polymers And Compounds In TPE’s Polymers • If we think of atoms, for example Carbon (C) and Hydrogen (H) as building blocks we can make many different structures by piecing different blocks (atoms) together. • Not all atoms go together but if we can build a stable structure we can make bigger building blocks called Monomers. Polymers • So if we take Carbon (C) and Hydrogen (H) we can make the simple monomer Ethylene. Polymers • If we join lots of these “monomer” building blocks together we then make a “polymer”, this word comes from Poly meaning many and mer which means unit as in Monomer (One Unit) , hence “many Monomers” (or many units). Polymers • If we think of a polymer as a chain we can think of each monomer as a link in that chain. The more links we have the longer the chain is, this is known as the molecular weight (Mw) of the polymer and can greatly affect properties such as strength, recovery and melt flow. Low Mw High Mw (e.g. Kraton 1651 has a higher Mw than Kraton 1654) Polymers • The polymer chains form entanglements between each other and this influences properties • The longer the chains the more entanglements, this increases properties such as strength and recovery but decreases properties like the melt flow rate. Polymers • Different Monomers can be produced and attached together to make different polymers, but also we can start to combine more than one Monomer to form more complicated polymers. These are known as Block Copolymers • SBS (Calprene 419) is a Block Copolymer made from Styrene Monomer and Butadiene Monomer Formulations • Our formulations at VTP are based upon combinations of polymers • Although we add other non-polymer ingredients it is the polymers that influence the main properties of the compound • Typically we would combine at least one “rubbery” material with at least one “plastic” material • The benefit of this is that we have a material that shows properties of rubber at room temperatures but can moulded or extruded like a plastic SBS [Styrene] – [Butadiene] – [Styrene] • “Rubbery” Material • Fina 409, Calprene 419, Calprene 411, Kraton D-1101 are all SBS. • Used in lower cost compounds but has lower performance. • Degrades quite easily above 200°C, especially if left at this temperature. • Sometimes difficult to disperse (i.e. nibs – Europrene) • Poor resistance to UV. • Medium capacity for retaining oil SBS [Styrene] – [Butadiene] – [Styrene] Different SBS grades are made by: • Using different ratio’s of [Styrene] to [Butadiene] • Making the chains longer or shorter (Mw) • Altering the structure of the chains • Extending with different amounts of oil SEBS [Styrene] – [Ethylene] – [Butylene] – [Styrene] • Rubbery Material • Kraton 1650, Kraton 1651, Kraton 1654, Calprene C6174S, Septon 4055 • More expensive material than SBS but has superior properties • Stable over 230°C and can remain at high temperatures for reasonable periods of time without any or much degredation • Can be difficult to disperse but easier than some SBS • Very Good resistance to UV • Extremely high capacity for retaining oil SEBS [Styrene] – [Ethylene] – [Butylene] – [Styrene] Different grades of SEBS are made by: • Using different ratios of the monomer blocks • Mw (Chain Length) is usually the biggest difference between grades EPDM [Ethylene] - [Propylene] - [Diene] Modified • EPDM is a synthetic rubber • Nordel IP3745, Royalene 694 and Royalene 539 are EPDM rubbers • EPDM is slightly more expensive than SBS but not as expensive as SEBS • EPDM is stable up to around 230°C but if left at temperatures above 200°C for any length of time can begin to degrade • Fairly easy to disperse in normal TPE style compounds. More complicated in TPV (XL) compounds • Very good resistance to UV EPDM [Ethylene] [Propylene] [Diene] Modified Different grades of EPDM are made by: • Using different Ethylene to Propylene ratio’s • Using different Diene’s for modification • Extending with different oil amounts Polypropylene (PP) [Propylene]n • Plastic material • Novolen 1100N, BP 100GA12, Moplen HP500N are all grades of PP • Plastics we use at VTP tend to be more economical than “rubbery” materials • PP is very stable and would not degrade until well above SBS and SEBS degradation temps, even after prolonged periods • Dispersion is not usually an issue with plastics • We have to make sure PP melts though, this happens at 160 165°C but we usually need to go higher than this to ensure that all of the material gets to this temperature • PP has no real issues with UV attack Polypropylene (PP) [Propylene]n Different PP grades are usually made by: • Using different structures • Different Mw • Provide different melt flow materials Polyethylene (PE) [Ethylene]n • Plastic material • Flexirene CM50, Flexirene MR50 and Eraclene MP94 are all types of PE • Again PE is more Economical than the “Rubbery” materials we use • As with PP, PE is very stable from degradation • Dispersion is not really an issue as long as we melt the PE. The melt temp of PE is around 135 to 145°C (this varies depending on type of PE) • PE has no real issues with UV Polyethylene (PE) [Ethylene]n Polyethylene's are a bit more complicated in the types available, typical variants are: • Based on densities (due to varying amounts of crystallisation) this can give quite different materials • Different Mw materials • Different melt flow materials Polystyrene (PS) [Styrene]n • Plastic Material • Empera 116 is a PS material • PS is more economical than “rubbery” materials but is more expensive than PP or PE • PS is quite stable but is more prone to problems than PP or PE • Dispersion again is not much of an issue but we have to soften material enough to compound in properly. PS doesn’t actually melt like PP or PE but softens enough around 145 - 155°C • PS can have some issues with UV Polystyrene (PS) [Styrene]n Different grades of PS are made by: • The amount of styrene in the polymer chain • The Mw of the grade • Different rubber types and amounts added to improve impact resistance (HIPS) Compounds 400 Series (SBS) • Example “Dryflex 400601” • Based on SBS (Kraton D-1101C) • Can be used for Injection Moulding and Extrusion • Would be used for general purpose low cost mouldings typically Compounds 400 Series (SBS) Dryflex 400601 Formulation: • SBS – Main Polymer Base – Main Influence on compound properties • PP – Plastic Phase – Influences compound properties and helps to process efficiently • Oil (Edelex) – This oil suits SBS the best. Used to soften the material and improve flow and process efficiency • Filler – Calcium Carbonate (e.g. Calmote UF) – Main use is to extend the compound and hence “cheapen” it as this material is significantly lower in cost than polymer Compounds 500 Series (SEBS) • Example “Dryflex 500600” • These grades are unfilled • Based on SEBS (Kraton G1651) • Can be used for Injection Moulding and Extrusion • Would be typically used for general purpose more demanding mouldings that require very easy colouring or a clean/transparent appearance • These would be used over the 400 Series if the application is for outdoors Compounds 500 Series (SEBS) Dryflex 500600 Formulation: • SEBS – Main Polymer Base – Main Influence on compound properties • PP – Plastic Phase – Influences compound properties and helps to process efficiently • Oil (Primol) – This oil suits SEBS the best and is medically approved (also suitable for food contact materials). Used to soften the material and improve flow and process efficiency • Stabilisers – Antioxidants and UV stabilisers (e.g. Irganox/Tinuvin or Polyad which is a pre-blend) – The use of these is to prevent or slow down the degradation from heat and oxygen when processing and UV rays during service. Compounds 600 and 660 Series (SEBS) • Example “Dryflex 600600 or 660600” • These grades are filled and semi-filled respectively • Based on SEBS (Kraton G1651) • Can be used for Injection Moulding and Extrusion • Would be typically used for general purpose more demanding mouldings • These would be used over the 400 Series if the application is for outdoors and the 500 series if a higher density is required or if the clean/transparent nature of the 500 series is not required and for cost purposes these grades are suitable Compounds 600 and 660 Series Dryflex 600600 or 660600 Formulation: • SEBS – Main Polymer Base – Main Influence on compound properties • PP – Plastic Phase – Influences compound properties and helps to process efficiently • Oil (Primol) – This oil suits SEBS the best and is medically approved (also suitable for food contact materials). Used to soften the material and improve flow and process efficiency • Stabilisers – Antioxidants and UV stabilisers (e.g. Irganox/Tinuvin or Polyad which is a pre-blend) – The use of these is to prevent or slow down the degradation from heat and oxygen when processing and UV rays during service. • Filler – Calcium Carbonate (e.g. Calmote UF) – Main use is to extend the compound and hence “cheapen” it as this material is significantly lower in cost than polymer Compounds 9000 Series (TPO) • Example “Dryflex 9012-001” • These grades are based on EPDM Rubber mixed with a PP plastic • These grades can be filled or unfilled • These can be used for injection moulding or extrusion • Usually used for economical injection moulding, especially in automotive. Car bumpers are the biggest usage for this material (not from VTP material) Compounds 9000 Series (TPO) • EPDM – One of the main polymer bases – Big influence on product properties • PP – Plastic phase and one of the main polymer bases – Big influence on product properties and processing • Calcium Stearate – Process Aid – Acts an internal lubricant to aid processing both when compounding and moulding/extruding • Stabilisers – Antioxidants and UV stabilisers (e.g. Irganox/Tinuvin or Polyad which is a pre-blend) – The use of these is to prevent or slow down the degradation from heat and oxygen when processing and UV rays during service. Compounds XL Series (TPV) • Example “Dryflex XL60100-001” • These grades are based on EPDM Rubber mixed with a PP plastic like a TPO, but the Rubber phase is vulcanised. • These grades can be filled or unfilled but usually conatin a small amount of filler • These can be used for injection moulding or extrusion depending on the actual grade • Usually used for higher end mouldings or extrusions that require better temperature resistance or better aggressive fluid resistance (Automotive under bonnet) Compounds XL Series (TPV) • EPDM – One of the main polymer bases – Big influence on product properties • PP – Plastic phase and one of the main polymer bases – Big influence on product properties and processing • Oil (Primol) – This oil suits EPDM the best and is medically approved (also suitable for food contact materials). Used to soften the material and improve flow and process efficiency • Cure Package – Provides the chemical reaction that vulcanises the EPDM rubber • Stabilisers – Antioxidants and UV stabilisers (e.g. Irganox/Tinuvin or Polyad which is a pre-blend) – The use of these is to prevent or slow down the degradation from heat and oxygen when processing and UV rays during service • Process Aid – Fatty Acid (e.g. Crodamide E) – Works as an internal lubricant when compounding and moulding/extruding. Also migrates to the surface to form a greasy layer that helps with de-moulding and helps material flow through the die when extruding Compounds 4000 Series (Glazing) • Example “Vitaprene 4058-101” • These grades are based on SBS mixed with a PE plastic (LLDPE) (Also other polymers incorporated) • These grades are usually reasonably well filled to reduce raw material costs • These grades are predominantly for extrusion • Usually used for glazing gaskets and seals Compounds 4000 Series (Glazing) • SBS – The main base polymer – used for cost purposes • EPDM – Also used in relatively high amount, improves properties such as UV resistance without using lots of expensive SEBS • PE – The main plastic component for processing and properties • SEBS – Used in small amount to improve some of the poorer properties of the other polymers • PP – Used in small amounts to influence specific properties and processing • Oil (Combination) – Used for softening, cost reduction and property/processing influence • Stabilisers – Essential with these grades due to nature of SBS for heat and UV and the fact that service of these materials is typically outdoors in the direct view of the sun • Fillers – Essential for lowering raw material costs due to competitive market and low margins • Black M/B – Contains Carbon Black which is used to provide the black colouration • Process aid – Fatty Acid – Essential to help flow through the die and help prevent build up of die dross or shark-skin effects Compounds Obviously there are many more polymers and additives we use, but what we have covered is the main bread and butter of VTP compounds and raw materials. We have only covered very basics of polymers as well but the concepts we have looked at should help to show why we use the different materials and how to some degree the formulations are developed